CA1326577C - Organopolysiloxane microemulsion, process for its production and application thereof - Google Patents
Organopolysiloxane microemulsion, process for its production and application thereofInfo
- Publication number
- CA1326577C CA1326577C CA000565500A CA565500A CA1326577C CA 1326577 C CA1326577 C CA 1326577C CA 000565500 A CA000565500 A CA 000565500A CA 565500 A CA565500 A CA 565500A CA 1326577 C CA1326577 C CA 1326577C
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- CA
- Canada
- Prior art keywords
- mol
- gamma
- microemulsion
- formula
- organopolysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
Abstract
ABSTRACT
A microemulsion with an average particle size not exceeding 0.15 micrometers of organopolysiloxane composed of trifunctional siloxane units with the formula RSiO3/2 and difunctional siloxane units with the formula R12SiO is characterized by transparency, by excellent mechanical, dilution, and blending stabilities and by an excellent stability against pH variations. The microemulsion is prepared by process comprising the slow addition, to an aqueous emulsion-polymerization catalyst solution, of a crude emulsion prepared from an organotrialkoxysilane having the formula RSi(OR1)3, a cyclic organopolysiloxane having the formula (R12SiO)n, a surfactant, and water. A microemulsion which consists of 30 to 95 mol% trifunctional siloxane units and 70 to 5 mol% difunctional siloxane units is useful as a fiber-treatment agent that can impart slip resistance to fibrous material without stiffening the hand, while at the same time not causing oil spots.
A microemulsion with an average particle size not exceeding 0.15 micrometers of organopolysiloxane composed of trifunctional siloxane units with the formula RSiO3/2 and difunctional siloxane units with the formula R12SiO is characterized by transparency, by excellent mechanical, dilution, and blending stabilities and by an excellent stability against pH variations. The microemulsion is prepared by process comprising the slow addition, to an aqueous emulsion-polymerization catalyst solution, of a crude emulsion prepared from an organotrialkoxysilane having the formula RSi(OR1)3, a cyclic organopolysiloxane having the formula (R12SiO)n, a surfactant, and water. A microemulsion which consists of 30 to 95 mol% trifunctional siloxane units and 70 to 5 mol% difunctional siloxane units is useful as a fiber-treatment agent that can impart slip resistance to fibrous material without stiffening the hand, while at the same time not causing oil spots.
Description
~ I 326577 ;~
ORGANOPOLYSILOXANE MICROEMULSION, PROCESS FQR ITS
PRODUCTION AND APPLICATION THEREOF
The present invention relates to an organopolysiloxane microemulsion, a process for its production, and a fiber-treatment composition based on said organopolysiloxane microemulsion. More specifically, the present invention ! relates to a microemulsion of organopolysiloxane having difunctional and trifunctional organosilo~ane units, to a process for the production of such a microemulsion, and to a fibertreatment composition which is based on said micro-1 emulsion.
3~ With regard to emulsions of organopolysiloxane having ;l difunctional and trifunctional organosiloxane units (below, referred to as di/tri organopolysiloxane~, Japanese Patent Application Laid Open Number 54-131661 ~131,661/79) describes such emulsions obtained by the emulsion polymerization of cyclic organosiloxane and functional group-containing Qrganotrialkoxysilane -Furthermore, fabrics made rom natural fiber such as cotton, flax, silk, wool, angora and mohair; regenerated fiber such as rayon and bemberg; semisynthetic fiber such as acetate; or synthetic fiber such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, spandex, and, among the long-ibar weaves in particular, taffeta, twill, Georgette, gauze, etc., with their especially coarse textures, readily undergo slip due to yarn separation. As a consequence, thermosetting resins such as epoxy, melamine, glyoxal, etc.; thermoplastic resins such as acrylic, etc.; latexes such as natural rubber, styrene/butadiene, etc.; and colloidal silica, among others, have been used as sli~ ibitors.
.
..
.
:
.
.
~.:
.
However, the emulsions of di/tri organopolysiloxane known in the art consist of organopolysiloxane emulsions having average particle sizes of at least 0.3 microns, and accordingly, the stability (mechanical stability) with respect to the processes necessarily encountered in fiber treatment (agitation, circulation, expression of the treat-ment bath, etc.), the stability (dilution stability) against dilution (for example, 20-fold to 100-folcl dilution with water), and the stability (blending stability) with regard to use with additives are all unsatisfactory. As a consequence, such an emulsion undergoes de-emulsification, and the organo-polysiloxane floats to the top of the treatment bath. It will then appear as oil drops ~oil spots) on the fibrous material, thus generating the serious problem of "staining."
Furtharmore, because the stability (mechanical stability) with respect to the processes necessarily encountered in release agent applications (agitation, circulation, etc.), the stability (dilution stability) against dilution (for example, 20-fold to 100-fold dilution with water~, and the stability (blending stability) with regard to use with additives are all unsatisfactory, such emulsions undergo de-emulsification and the organopoly-siloxane separates. This adheres to the surface of the molding, creating the serious problem of oil spots.
When fiber is treated with a thermosetting resin (e.g., epoxy, melamine, glyoxal~ etc.), thermoplastic resin ~e.g., acrylic, etc.), or a latex (e.g., styrene/butadiene, natural rubber, etc.) ln order to e~uip fibrous material with slip resistance, slip resistance is in fact obtained, but the hand becomes particularly stiff. Furthermore, the use of colloidal silica sufers from the problem of sedimentation of the colloidal silica unless this particular process is , " ~ ..
; ~ '`' ~
, .
-'' carried out at low temperatures for short periods of time with strict management of the pH of the treatment bath.
. ~
The present invention, having as its object a solution to the aforementioned problems, provides a di/tri organopoly-siloxane microemulsion which has excellent mechanical, dilution, blending, and pH stabilities; a fiber-treatment composition which imparts slip resistance without causing the fibrous material to have a stiff hand, which does not cause oil spots, and which has an excellent mechanical, dilution, blending, and pH stabilities; and a process for the production of such a microemulsion.
This object, and others which will occur to one upon considering the following disclosure and appended claims, is realized by the process of the pres~nt invention for preparing an organopolysiloxane microemulsion havinq a particle size not exceeding 0.15 micrometers which consists of emulsion polymerization, by the gradual addition to an aqueous emulsion-polymerization catalyst solution, of a crude emulsion prepared from lO to 95 mol% organotrialkoxysilane having the formula RSi(OR1)3, from 90 to 5 mol% as R12SiO
units of cyclic organopolysiloxane having the formula (R12SiO)n, a surfactant and water.
Because the present invention-s organopolysiloxane microemulsion has an average particle size not exceeding 0.15 micrometers it is characterized by transparency, by excellent mechanical, dilution, and blending stabilities and by an excellent stability against pH variations. These properties allow it to be used to prepare a fiber-treatment composition having excellent mechanical, dilution, and blending stabilities, and stability against pH changes that can impart slip resistance to fibrous material without stiffening the hand, while at the same time not causing oil spots.
.
:' ~ `
, .
4 `
.
The aforesaid objects are accomplished by a micro-emulsion composition comprising an organopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 10 to 95 mol% trifunctional siloxane units with the formula RSiO3/2 wherein R is a monovallent organic group and 90 to 5 mol% difunctional siloxane units with the formula R12SiO wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group.
To explain the preceding, the present invention's organopolysiloxane microemulsion is a microemulsion of an organopolysiloxane composed of 10 to 95 mol% trifunctional siloxane units with the formula RSiO3/2 and 90 to 5 mol%
diunctional siloxane units with the formula R 2SiO, and it has an average particle size not exceeding 0.15 micrometers.
R in the abov~ formula is a monovalent organic group, and is exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl; substituted alXyl groups such as 2-phenylethyl and 2-phenylpropyl; 3,3,3-trifluoropropyl;
alkenyl groups such as vinyl and propenyl; aryl and substituted aryl groups such as phenyl and tolyl; and organofunctional groups such as gamma-aminopropyl, gamma-(N-ethylamino)propyl, gamma-(N-butylamino)propyl, 4-~N-cyclohexylamino)butyl, 4-(N-phenylamino)butyl, N-aminoethylaminopropyl, beta-~N,N-dimethylamino)ethyl, gamma-glycidoxypropyl, 3,4-epoxycyclohexylpropyl, gamma-mercaptopropyl, and gamma-methacryloxypropyl. The R
groups in the organopolysiloxane may be identical or different.
R1 in the above formula is a monovalent hydrocarbon or halogenated hydrocarbon group, and is exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl; substituted alkyl groups such as 2-phenylethyl and 2-phenylpropyl; 3,3,3-trifluoropropyl; alkenyl groups such as vinyl and propenyl;
:
: , :
. ~ , , .
:' ;`
.j , and aryl and substituted aryl groups such as phenyl and tolyl. Th@ groups R in ~he organopoly~iloxane may be identical or different.
With regard to the constituent proportions of the siloxane units, 10 to 95 mol% trifunctional siloxane unit~
and gO to 5 mol% difunctional siloxane units are re~uired.
Preferred values are 20 to 90 mol% trifunctional siloxane units and 80 to 10 mol% difunctlonal ~iloxane units. In the case of less than 10 mol% trl~unctional siloxane units, the organopolysiloxane will not ~f~ord a durabls rubber or resin coating after removal of the water fraction. On the other hand, tha microemulsion will not be stable when 95 mol%
trifunctio~al ~iloxane units is exceeded.
The average particle size in the emulsion must not exceed 0.15 micrometers, and preferably doe3 not exceed 0.12 micrometers. When thi~ average particle size exceed~ 0.15 micrometers, the organopoly~iloxane will separat~ clue to the reduced mechanical, dilutio~, and blending ~tabili ia~, and oil spots will then appear on tho treated matarial.
Furthermore, unlos~ the ob~ect of tho invention i~
adversely affected, the organopolysiloxane in the instant microemulsion may contain small quantities, not to exceed lO
mol%, of units expres~ed ~y SiO2 and/or units expressed by R3SiOl/2.
The organopolysiloxane microemulgion of the present invention can be prepared by the proces3 o thi~ invention or the production of a microemulsio~ composition comprising an organopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 10 to 95 m~l%
tri~unctional ~iloxane units with the o~mula RSiO3/2 wherein R is a monovalent organic group a~d 90 to 5 mol% difunctional ~iloxane units with the formula R12$iO wherein R1 i~ a . .
"
. . . :
:....
.
.~ monovalent hydrocarbon or halogenated hydrocarbon group, ~aidprocess comprising gradually adding to an aqueous emulsion-polymerization catalyst solution a crude emulsion composed of -I ~A) 10 to 95 mol% organotrialkoxysilane having the formula s, RSi(OR1)3 wherein R is a monovalent organic group and R1 is a ~,~ monovalent hydrocarbon or halogenated hydrocar~on group, (B) - 90 to 5 mol% as R 2SiO units of cyclic organopolysiloxane having the formula (R12SiO)n wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group and n is an , integer having a value of 3 to 10, (C) surfactant, and (D) water and maintaining the resulting mixture at O to 90C
I until the desired emulsion polymerization has been achieved.
The organotrialkoxysilane RSi(ORl)3 comprising component (A) is one starting material for the microemulsion of the pre~ent in~Jention9 and is the essential component for ~,~; providing a network organopoly~iloxane. R in the above ~i formula is a monovalent organic group, and is exemplified as above. Rl is a monovalent hydrocarbon or halogenated hydrocarbon group, again exemplified as above. This component may consist of one species or two or more species.
Concrete examples of this component are methyltrimethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, beta-aminoethyltrimethoxysilane, beta-aminoethyltriethoxysilane, beta~aminoethyl~triisopropoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltri n-propoxysilane, gamma-aminopropyltri-n~butoxysilane, `~
4-aminocyclohexyltriethoxysilane, 4-aminophenyltriethoxysilane~
N-aminoethyl-gamma-aminopropyltrimethoxysilane, ~'' .~ .
.
: ,.~, ,: : .
c 1 326~77 N-aminoethyl-gamma-aminopropyltricyclohexylsilane, beta-glycidoxyethyltrimethoxysi lane, beta~glycidoxyethyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and gamma-methacryloxypropyltriethoxysilane.
The cyclic organopolysiloxane (R12SiO)n comprising component (B) is, like component (A), a starting material for the present invention's microemulsion. Rl in the formula is a monovalent hydrocarbon or halogenated hydrocarbon group, and is exemplified as above. n is an integer having a value of 3 to 10. This component may consist of the single species or of two or more species. The groups R1 in the single molecule may be the same or may differ.
The use ratio between components (A) and (B) is to be a value which provides 90 to 5 mol% as R12SiO units of component (B) against 10 to 95 mol% component (A~. It is preferably a value providing 80 to 10 mol% as R12SiO of component (B) against 20 to 90 mol% component (A).
The siloxane unit molar ratio in the organopolysiloxane after emulsion polymerization can be freely adjusted by means of the molar ratio between component (A) and component (B~ in the crude emulsion.
Furthermore, as long as the object of the present invention is not adversely affected, small quantities, affording no more than 10 mol% as siloxane units, of he~aalkyldisiloxane, tetraalkoxysilane, etc., may be added.
The surfactant comprising component (C) is the essential component for converting components (A) and (B) into the , ' .
~`
crude emulsion. Surfactants operative in the present invention are the anionic, cationic, and nonionic surfactants.
~ xamples of the anionic surfactants are alkylbenzene-sulfonic acids such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenPsulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, and myristylbenzenesulfonic acid; the sulfate esters of polyoxyethylene monoalkyl ethers such as H2o~c2H4o)2so3H~ CH3(~H2~CH20(C2H~0)8S H
ORGANOPOLYSILOXANE MICROEMULSION, PROCESS FQR ITS
PRODUCTION AND APPLICATION THEREOF
The present invention relates to an organopolysiloxane microemulsion, a process for its production, and a fiber-treatment composition based on said organopolysiloxane microemulsion. More specifically, the present invention ! relates to a microemulsion of organopolysiloxane having difunctional and trifunctional organosilo~ane units, to a process for the production of such a microemulsion, and to a fibertreatment composition which is based on said micro-1 emulsion.
3~ With regard to emulsions of organopolysiloxane having ;l difunctional and trifunctional organosiloxane units (below, referred to as di/tri organopolysiloxane~, Japanese Patent Application Laid Open Number 54-131661 ~131,661/79) describes such emulsions obtained by the emulsion polymerization of cyclic organosiloxane and functional group-containing Qrganotrialkoxysilane -Furthermore, fabrics made rom natural fiber such as cotton, flax, silk, wool, angora and mohair; regenerated fiber such as rayon and bemberg; semisynthetic fiber such as acetate; or synthetic fiber such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, spandex, and, among the long-ibar weaves in particular, taffeta, twill, Georgette, gauze, etc., with their especially coarse textures, readily undergo slip due to yarn separation. As a consequence, thermosetting resins such as epoxy, melamine, glyoxal, etc.; thermoplastic resins such as acrylic, etc.; latexes such as natural rubber, styrene/butadiene, etc.; and colloidal silica, among others, have been used as sli~ ibitors.
.
..
.
:
.
.
~.:
.
However, the emulsions of di/tri organopolysiloxane known in the art consist of organopolysiloxane emulsions having average particle sizes of at least 0.3 microns, and accordingly, the stability (mechanical stability) with respect to the processes necessarily encountered in fiber treatment (agitation, circulation, expression of the treat-ment bath, etc.), the stability (dilution stability) against dilution (for example, 20-fold to 100-folcl dilution with water), and the stability (blending stability) with regard to use with additives are all unsatisfactory. As a consequence, such an emulsion undergoes de-emulsification, and the organo-polysiloxane floats to the top of the treatment bath. It will then appear as oil drops ~oil spots) on the fibrous material, thus generating the serious problem of "staining."
Furtharmore, because the stability (mechanical stability) with respect to the processes necessarily encountered in release agent applications (agitation, circulation, etc.), the stability (dilution stability) against dilution (for example, 20-fold to 100-fold dilution with water~, and the stability (blending stability) with regard to use with additives are all unsatisfactory, such emulsions undergo de-emulsification and the organopoly-siloxane separates. This adheres to the surface of the molding, creating the serious problem of oil spots.
When fiber is treated with a thermosetting resin (e.g., epoxy, melamine, glyoxal~ etc.), thermoplastic resin ~e.g., acrylic, etc.), or a latex (e.g., styrene/butadiene, natural rubber, etc.) ln order to e~uip fibrous material with slip resistance, slip resistance is in fact obtained, but the hand becomes particularly stiff. Furthermore, the use of colloidal silica sufers from the problem of sedimentation of the colloidal silica unless this particular process is , " ~ ..
; ~ '`' ~
, .
-'' carried out at low temperatures for short periods of time with strict management of the pH of the treatment bath.
. ~
The present invention, having as its object a solution to the aforementioned problems, provides a di/tri organopoly-siloxane microemulsion which has excellent mechanical, dilution, blending, and pH stabilities; a fiber-treatment composition which imparts slip resistance without causing the fibrous material to have a stiff hand, which does not cause oil spots, and which has an excellent mechanical, dilution, blending, and pH stabilities; and a process for the production of such a microemulsion.
This object, and others which will occur to one upon considering the following disclosure and appended claims, is realized by the process of the pres~nt invention for preparing an organopolysiloxane microemulsion havinq a particle size not exceeding 0.15 micrometers which consists of emulsion polymerization, by the gradual addition to an aqueous emulsion-polymerization catalyst solution, of a crude emulsion prepared from lO to 95 mol% organotrialkoxysilane having the formula RSi(OR1)3, from 90 to 5 mol% as R12SiO
units of cyclic organopolysiloxane having the formula (R12SiO)n, a surfactant and water.
Because the present invention-s organopolysiloxane microemulsion has an average particle size not exceeding 0.15 micrometers it is characterized by transparency, by excellent mechanical, dilution, and blending stabilities and by an excellent stability against pH variations. These properties allow it to be used to prepare a fiber-treatment composition having excellent mechanical, dilution, and blending stabilities, and stability against pH changes that can impart slip resistance to fibrous material without stiffening the hand, while at the same time not causing oil spots.
.
:' ~ `
, .
4 `
.
The aforesaid objects are accomplished by a micro-emulsion composition comprising an organopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 10 to 95 mol% trifunctional siloxane units with the formula RSiO3/2 wherein R is a monovallent organic group and 90 to 5 mol% difunctional siloxane units with the formula R12SiO wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group.
To explain the preceding, the present invention's organopolysiloxane microemulsion is a microemulsion of an organopolysiloxane composed of 10 to 95 mol% trifunctional siloxane units with the formula RSiO3/2 and 90 to 5 mol%
diunctional siloxane units with the formula R 2SiO, and it has an average particle size not exceeding 0.15 micrometers.
R in the abov~ formula is a monovalent organic group, and is exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl; substituted alXyl groups such as 2-phenylethyl and 2-phenylpropyl; 3,3,3-trifluoropropyl;
alkenyl groups such as vinyl and propenyl; aryl and substituted aryl groups such as phenyl and tolyl; and organofunctional groups such as gamma-aminopropyl, gamma-(N-ethylamino)propyl, gamma-(N-butylamino)propyl, 4-~N-cyclohexylamino)butyl, 4-(N-phenylamino)butyl, N-aminoethylaminopropyl, beta-~N,N-dimethylamino)ethyl, gamma-glycidoxypropyl, 3,4-epoxycyclohexylpropyl, gamma-mercaptopropyl, and gamma-methacryloxypropyl. The R
groups in the organopolysiloxane may be identical or different.
R1 in the above formula is a monovalent hydrocarbon or halogenated hydrocarbon group, and is exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl; substituted alkyl groups such as 2-phenylethyl and 2-phenylpropyl; 3,3,3-trifluoropropyl; alkenyl groups such as vinyl and propenyl;
:
: , :
. ~ , , .
:' ;`
.j , and aryl and substituted aryl groups such as phenyl and tolyl. Th@ groups R in ~he organopoly~iloxane may be identical or different.
With regard to the constituent proportions of the siloxane units, 10 to 95 mol% trifunctional siloxane unit~
and gO to 5 mol% difunctional siloxane units are re~uired.
Preferred values are 20 to 90 mol% trifunctional siloxane units and 80 to 10 mol% difunctlonal ~iloxane units. In the case of less than 10 mol% trl~unctional siloxane units, the organopolysiloxane will not ~f~ord a durabls rubber or resin coating after removal of the water fraction. On the other hand, tha microemulsion will not be stable when 95 mol%
trifunctio~al ~iloxane units is exceeded.
The average particle size in the emulsion must not exceed 0.15 micrometers, and preferably doe3 not exceed 0.12 micrometers. When thi~ average particle size exceed~ 0.15 micrometers, the organopoly~iloxane will separat~ clue to the reduced mechanical, dilutio~, and blending ~tabili ia~, and oil spots will then appear on tho treated matarial.
Furthermore, unlos~ the ob~ect of tho invention i~
adversely affected, the organopolysiloxane in the instant microemulsion may contain small quantities, not to exceed lO
mol%, of units expres~ed ~y SiO2 and/or units expressed by R3SiOl/2.
The organopolysiloxane microemulgion of the present invention can be prepared by the proces3 o thi~ invention or the production of a microemulsio~ composition comprising an organopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 10 to 95 m~l%
tri~unctional ~iloxane units with the o~mula RSiO3/2 wherein R is a monovalent organic group a~d 90 to 5 mol% difunctional ~iloxane units with the formula R12$iO wherein R1 i~ a . .
"
. . . :
:....
.
.~ monovalent hydrocarbon or halogenated hydrocarbon group, ~aidprocess comprising gradually adding to an aqueous emulsion-polymerization catalyst solution a crude emulsion composed of -I ~A) 10 to 95 mol% organotrialkoxysilane having the formula s, RSi(OR1)3 wherein R is a monovalent organic group and R1 is a ~,~ monovalent hydrocarbon or halogenated hydrocar~on group, (B) - 90 to 5 mol% as R 2SiO units of cyclic organopolysiloxane having the formula (R12SiO)n wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group and n is an , integer having a value of 3 to 10, (C) surfactant, and (D) water and maintaining the resulting mixture at O to 90C
I until the desired emulsion polymerization has been achieved.
The organotrialkoxysilane RSi(ORl)3 comprising component (A) is one starting material for the microemulsion of the pre~ent in~Jention9 and is the essential component for ~,~; providing a network organopoly~iloxane. R in the above ~i formula is a monovalent organic group, and is exemplified as above. Rl is a monovalent hydrocarbon or halogenated hydrocarbon group, again exemplified as above. This component may consist of one species or two or more species.
Concrete examples of this component are methyltrimethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, beta-aminoethyltrimethoxysilane, beta-aminoethyltriethoxysilane, beta~aminoethyl~triisopropoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltri n-propoxysilane, gamma-aminopropyltri-n~butoxysilane, `~
4-aminocyclohexyltriethoxysilane, 4-aminophenyltriethoxysilane~
N-aminoethyl-gamma-aminopropyltrimethoxysilane, ~'' .~ .
.
: ,.~, ,: : .
c 1 326~77 N-aminoethyl-gamma-aminopropyltricyclohexylsilane, beta-glycidoxyethyltrimethoxysi lane, beta~glycidoxyethyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and gamma-methacryloxypropyltriethoxysilane.
The cyclic organopolysiloxane (R12SiO)n comprising component (B) is, like component (A), a starting material for the present invention's microemulsion. Rl in the formula is a monovalent hydrocarbon or halogenated hydrocarbon group, and is exemplified as above. n is an integer having a value of 3 to 10. This component may consist of the single species or of two or more species. The groups R1 in the single molecule may be the same or may differ.
The use ratio between components (A) and (B) is to be a value which provides 90 to 5 mol% as R12SiO units of component (B) against 10 to 95 mol% component (A~. It is preferably a value providing 80 to 10 mol% as R12SiO of component (B) against 20 to 90 mol% component (A).
The siloxane unit molar ratio in the organopolysiloxane after emulsion polymerization can be freely adjusted by means of the molar ratio between component (A) and component (B~ in the crude emulsion.
Furthermore, as long as the object of the present invention is not adversely affected, small quantities, affording no more than 10 mol% as siloxane units, of he~aalkyldisiloxane, tetraalkoxysilane, etc., may be added.
The surfactant comprising component (C) is the essential component for converting components (A) and (B) into the , ' .
~`
crude emulsion. Surfactants operative in the present invention are the anionic, cationic, and nonionic surfactants.
~ xamples of the anionic surfactants are alkylbenzene-sulfonic acids such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenPsulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, and myristylbenzenesulfonic acid; the sulfate esters of polyoxyethylene monoalkyl ethers such as H2o~c2H4o)2so3H~ CH3(~H2~CH20(C2H~0)8S H
3(cH2)l9cH2o(c2H4o)4s03H7 and CH3(CH2)8CH2C6H40(C2H40)2S03H; and alkylnaphthylsulfonic acids.
Examples of the cationic surfactants are quaternary ammonium hydroxides and their salts such as octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide, dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide,and cocotrimethylammonium hydroxide.
Examples of nonionic surfactants are the polyoxyalkylene alkyl ethers, the polyoxyalkylene alkylphenol ethers, the polyoxyalkylene alkyl esters, the polyoxyalkylene sorbitan alkyl esters, polyethylene glycols, polypropylene glycols, and diethylene glycol.
The surfactant may be used as the single species or a~
the combination of two or more species, with the exception of the combination of anionic surfactant with cationic surfactant. In concrete terms, it is permissible to use a single species of anionic surfactan$, or the combination of : '`, ' : .,.,~ ::
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:', g ; two or more species of anionic surfactants, or a single( species of nonionic surfactant, or the combination of two or `, more species of nonionic surfactants, or a single species of cationic surfactant, or the combination of two or more i species of cationic surfactants, or the combination of two or 3 more species respectively selected from anionic and nonionic surfactants, or the combination of two or more species `~ respectively selected from cationic and nonionic surfactants.
! The surfactant comprising component (C) is used in the , crude emulsion in that quantity which provides for the 1 formation of an emulsion, and this will vary with the type of surfactant. As a consequence, this quantity of use is not specifically restricted, but is preferably about 2 - 50 wt%
~ based on 100 weight parts of components (A) and (B).
! The water comprising the component (D) in the crude emulsion is preferably used in a quantity which gives an organopoly~iloxane concentration of about 10 60 wt%.
i The crude emulsion is prepared by mixing the organo-, trialkoxysilane comprising component (A), the cyclic organo-;! polysiloxane comprising component (B), the surfactant comprising component (C), and the water comprising component ~J (D) to homogeneity, and by passing khis mixture through an emulsifying device such as an homogenizer, colloid mill, or line mixer, etc.
The organopolysiloxane microemulsion of the present invention can be obtained by means of an emulsion polymerization in which the crude emulsion prepared as above is gradually added to a separately prepared aqueous emuIsionpolymerization catalyst solution.
, These emulsion-pol~merization catalysts encompass anionic and cationic catalysts. The anionic catalysts are exemplified by mineral acids such as hydrochloric acid and sulfuric acid, and by the alkylbenzenesulfonic acids, sulfate :
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e ter~ of polyoxyethylene monoalkyl ethers, and alkylnaphthylsulfonic acids given as examples of the surfactant comprising component (C). The cationic catalysts are exemplified by alkali metal hydroxides such a~ potassium hydroxide and sodium hydroxide, and by the guaternary ammonium hydroxides and salts thereof given as examples for the surfactant comprising component (C3. However, due to the low catalytic activity of the quaternary ammonium salts, they ~hould be used in combination with an alkali m~tal hydroxide for activation.
Furthermore, with regard to the ionicitie~ of the surfactant and catalyst, when an anionic surfactant is u~ed as the component (C) in the crude emulsion, an anionic emulsion-polymerization cataly~t should be used in production of the microemulsion.
When a cationic surfactant is used a the component ~C) in the crude emulsion, a cationic emulsion-polymerization catalyst should be used for production of the microemulsion.
~ hen a nonionic surfactant i8 used as the component (C) in the crude emulsion, an anionic or cationic emulsion-polymerization catalyst should be used for production of the microemulsion.
The quantity of use of said emulsion-polymerization catalyst will vary with the type of cataly~t and o i~ not specifically restricted. However, when using a mineral acid or alkali metal hydroxide catalyst, this quantity is preferably 0.2 to 5.0 weight part and more preferably 0.5 to 3.0 weight parts for each 100 weight parts of the combined quantity of organotrialkoxysilane comprising component (A) and cyclic organopolysiloxane comprising component ~B). For the u e of alkylbenzenesul~onic acid, sulfate esters of polyoxyethylene monoalkyl ethers~ alkylnaphthylsulfonic acid9 or quaternary ammonium hydroxides or salts thereof, this "
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., guantity is preferably 0.5 to 50 weight parts and more preerably 1.0 to 30 weight parts for each 100 weight parts of the combined quantity of organotrialkoxysilane comprising component (A~ and cyclic organopolysiloxane comprising component (B). Nonionic surfactant as exemplified for component (C) may be added at this point in order to improve the stability during emulsion polymerization.
The temperature o the aqueous catalyst solution is preferably 40 to 95C when the crude emulsion is gradually added thereto, such as by dripping. The rate of addition will vary with the type and concentration of the catalyst and the temperature of the aqueous catalyst solution. Addition can be rapid at high catalyst concentrations or elevated aqueous catalyst solution temperatures. However, in order to produce microemulsions having smaller particle sizes, in general it is preferred that the crude emulsion be dripped in so as to obtain both dispersion and transparency.
After the termination of addition, the present invention's organopolysiloxane microemulsion having an average particle size not exceeding 0.15 micrometers is produced by an emulsion polymerization at O to 90C until the specified viscosity is achieved. After this emulsion polymerization, it is preferred that the catalyst be neutralized, with alkali in the case of an anionic polymerization catalyst and with acid in the case of a cationic polymerization catalyst. Furthermore, while the organopolyæiloxane concentration during emulsion polymerization is not specifically restricted, it is preferably 5 to 50 wt%. The present invention's organopolysiloxane microemulsion obtained as above can be used as a mold-releas~ agent, relea~e agent, paink additive, defoamer, lustrant, plastic coating agent, fiber-treatment agent, etc.
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~ 326577 The fiber-treatment agent of the present invention is based on a microemulsion comprising an orqanopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 30 to 95 mol% trifunctional siloxane units with the formula RSiO3/2 w:herein R is a monovalent organic group and 70 to 5 mol% difunctional siloxane units with the formula R12SiO wherein Rl is a monovalent hydrocarbon or halogenated hydrocarbon group.
Forty-five to 90 mol% trifunctional siloxane units and 55 to 10 mol% difunctional siloxane unit~ are preferred. The slip resistance becomes unsatisfactory at below 30 mol~ of said trifunctional siloxane units.
In addition, as long as the object o the invention is not compromised, the fiber-treatment agent of the present invention may as desired contain additional water; resin finishing agents such as glyoxal resin, melamine resin, urea resin, polyester resin, and acrylic resin; rubber latexes such as styrene/butadiene latex and natural rubber latex;
organohydrogenpolysilo~ane emulsion and organoalkoxysilane emulsion; surfactants; preservatives; colorants; the salts between organocarboxylic acids and metals such as iron, lead, antimony, cadmium, titanium, calcium, bismuth, zirconium, etc.; organic amino compounds as condensation catalysts, such as triethanolamine, triethylenediamine, dimethylphenylamine, etc.; among others.
Fibrous mat~rial is treated with the fiber-treatment agent of the present inve~tion using such methods as spraying, roll application, brush coating, i~nersion, etc.
The add-on will vary with the fibrous material and so is not specifically restricted, but is generally in the range of 0.01 to 10.0 wt% as organopolysiloxane fraction based on the fibrous material. The fibrous material is then treated by, :
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., '' 13 :j il for example, standing at room temperature, axposure to a hot l air current, heating, etc.
`, With regard to substance, the fibrous material is 6 exemplified by natural fibers such as wool, silk, flax, cotton, angora, mohair, and asbestos; by regenerated fibers such as rayon and bemberg; by semisynthetic fibers such as acetate; by synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, and spandex; and by inorganic fibers such as glass fiber, carbon fiber, and silicon carbide fiber. In its form it is exemplified by the staple, filament, tow, top, and yarn, and in its structure it is exemplified by knits, weaves, and nonwovens.
The present invention will be explained in the following wit~ reference to illustrative examplas, in which parts =
weight parts and % = wt% unless otherwise specified, and the viscosity is the value at 25C. Me denotes the methyl group.
Example 1 Water, 158.5 parts, 1.5 parts hexadecyltrimethylammonium 6 chloride, 150.0 parts methyltrimethoxysilane, and 15.0 parts cyclic dimethylsiloxane tetramer were placed in a 500 mL
beaker and mixed to homogeneity using a propeller stirrer.
6 This mixture was then passed once through an homogeni~er at a pressure of 300 kg/cm2 to afford a crude emulsion. Water, 152.7 parts, 10 parts hexadecyltrimethylammonium chloride, and 0.8 parts sodium hydroxide were separately placed in a 500 mL four-neck flask eq~lipped with a stirrer, reflu~
condenser, addition funnel, and thermometer. After dissolution, the liquid was maintained at 85C with slow stirring. The previously prepared crude emulsion was then gradually dripped into the aqueous catalyst solution over 90 minutes. After addition, emulsion polymeri7ation was carried out by stirring for an additional 30 minutes at 85C. Ater ~, , ' 1, ' :
~i 1 326577 ;
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polymerization and cooling, 1.2 parts acetic acid was added to adjust the pH to 7, thus to afford a microemul~ion o organopolysiloxane composed of 84.4 mol% CH3SiO3/~ units and 15.6 mol% (CH3)2SiO u~its (Microemulsion A). The average particle size in this microemulsion was measured using a ~uasi-elastic light scattering instrument (Malrer, USA), and a value of 0.05 micrometers wa~ obtained. The external appearance was slightly white and tran~parent, and the transmittance at 580 nanometers was 67%. A 10 mL portion of this microemulsion was collected, and a nonvolatile fraction of 22.0% was measured at 105C. In addition, 25 mL of this microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes. There wa~ no separation of the microemul3ion. The microemulsion was also maintained at 25C
fQr 6 months and wa~ found to be ~table. with no change occurring. Finally, the microemulsion s 50-fold dilution with water was maintained at 25~C for 10 hours. This emulsion was stable, undergoing no change.
Exam~le 2 Water~ 150.0 parts, 6.7 parts polyoxyethylene (45 mol) nonylphenol ether, 50.0 parts vinylkrimethoxysilane, and 15.0 parts cyclic dimethylsiloxane tetramer were placed in a 500 mL beaker and then mixed to homogeneity using a propeller stirrer. This mixture was passed through an homogenizer once at a prescure of 300 kg/cm~ in order to prepare a crude emulsion. Water, 175.3 parts, and 10.0 parts dodecylbenzenesulfonic acid were placed in a 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, followed by dissolution and maintenance at a liguid temperature of 85C with slow stirring. The previously prepared crude emulsion was gradually dripped into thi~ aqueous catalyst solution over 120 minute~, followed by maintenance after addition at 85C
., ,' ~,i :i ;: ::: .. : :.;~ :
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~ , for an additional 60 minutes in order to carry out emulsion polymerization. After emulsion polymerization and cooling9 5 parts triethanolamine was added to adjust the pH to 7, thus affording a microemulsion of organopoly~i:Lo~ane composed of 62.5 mol% CH~=CHSiO3/2 units and 37.5 mol% (CH3)2SiO units-(Microemulsion B). The average particl~ size in this microemulsion was measured at 0.07 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 53%. A 10 mL
portion of this microemulsion was collected, and a non-volatile fraction of 23.0% was measured at 105C. When 25 mL
of the microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes, no microemulsion separation was observed. When the microemulsion was maintained at 25C for 6 months, the microemulsion was stable, undergoing no change.
When the microemulsion's 50-fold dilution with water was maintained at 25C for 10 hours, the emulsion was stable, undergoing no change.
ExamPle 3 Water, 158.5 parts, 10.5 parts polyoxyethylene (40 mol) nonylphenol ether, 1.5 parts hexadecyltrimethylammonium chloride, 150.0 parts gamma-glycidoxypropyltrimethoxysilane, and 15.0 parts cyclic phenylmethylsiloxane tetramer were placed in a 500 mL beaker, and were mixed to homogeneity using a propeller stirrer. This mixture was passed through an homogenizer once at a pressure of 350 kg/cm2 to prepare a crude emulsion. Water, 152.7 parts, 10 parts hexadecyl-trimethylammonium chloride, and 0.8 parts sodium hydroxide were placed in a 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, followed by dissolution and maintenance at a li~uid temperature of 85C with slow stirring. The previously prepared crude ~mulsion was gradually dripped into this . ~ . . ..
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:i 16 :, aqueous catalyst solution over 90 minutes, followed by maintenance at 85C for an additional 30 minutesi after addition in order to carry out emulsion polymerization. After polymerization and cooling, 1.2 parts acetic acid was added to afford a microemulsion (Microemulsion C) of an organopoly-siloxane composed of 14.8 mol% C6H5(CH3)SiO units and 85.2 mol% unit~ having the following formula.
2 \ /C~H2CH2CH2CH2Si3/2 O
The average particle size in this microemulsion was measured at 0.07 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 68%. A 10 mL portion of this microemulsion i~ was collected, and a nonvolatile fraction of 20.5% was ' measured at 105~C. When 25 mL of this microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes no microemulsion separation was observed. When the microemulsion was maintained at 25C for 6 months, it was stable, without any change. When the microemulsion s 50-fold dilution with water was maintained at 25C for 10 hours, the emulsion was stable, undergoing no change.
, Example 4 , Water, 78.5 parts, 4.0 parts polyoxyethylene ~40 mol) ; nonylphenol ether, 30.0 parts methyltrimethoxysilane, and 37.5 parks cyclic dimethylsiloxane tetramer were placed in a 500 mL beaker, and were then mixed to homogeneity using a propeller stirrer. This mixturç was passed through an ~, homogenizer once at a pressure of 350 Xg/cm2 to prepare a crude emulsion. Water, 138.9 parts, 9.0 parts hexadecyltrimethylammonium chloride, and 0.7 parts sodium hydroxide were placed in a 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, followed by dissolution and maintenance at a ' ~ ' ' ' ~ 326577 liquid temperature of 85C with slow stirring. The previously prepared crude emulsicn was gradually dripped into this aqueous catalyst solution over 100 minutes. After addition, emulsion polymerization was conducted by maintenance at 85C for an additional 45 minutes. After polymerization and cooling, 1.0 part acetic acid was added to adjust the pH to 7, thus affording a microemulsion of organopolysiloxane composed of 30.4 mol% CH3SiO3/2 units and 69.6 mol% (C~3)2SiO units. The average particle size in this microemulsion was measured at 0.05 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 65%. A 10 mL
portion of this microemulsion was collected, and a nonvolatile fraction of 22.5% was measured at 105C. A 25 mL
portion ~f this microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes: no microemulsion separation was observed. When the micro~mulsion was maintained at 25C f~r 6 months, it was stable, without any change. When the microemulsion s 50-fold dilution with water was maintained a 25C for 10 hours, the emulsion was stable, undergoing no change.
Example 5 Water, 132 parts, 27 parts polyoxyethylene (40 mol) octylphenol ether, 133 parts methyltrimethoxysilane, and 21 parts cyclic dimethylsiloxane tetramer were placed in a 500 mL beaker, and were then mixed to homogeneity using a propeller stirrer. This mixture was then passed once through an homogenizer at a pressure of 350 kg~cm2 in order to prepare a crude emulsion. Sodium hydroxide, 0.3 parts, was dissolved in 664 parts water in a 19 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, and this was then maintained at a liquid temperature of 85C with slow stirring. The previously !
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i~ 1 326577 prepared crude emulsion was gradually dripped uinto this aqueous catalyst solution over 100 minutes. After auddition, emulsion polymerization was conducted by maintenance at 85C
for an additional 45 minutes. After polymerization and cooling, the p~ was adjusted to 7 by adding 1.0 part acetic acid, thus to afford a microemulsion of organopolysiloxane composed of 75 mol% CH3SiO3/2 units and 25 mol% (CH3)2SiO
units. The average particle size in this microemulsion was measured at 0.08 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 63%. A 10 mL portion of this microemulsion was collected, and a nonvolatile fraction of 15.3% was measured at 105C. A 25 mL portion of this microemulsion wa~ placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes: no microemulsion separation was observed. When the microemulsion was maintained at 25C for 6 months, it Was stable, without any change. When the microemulsion's 50-fold dilution with water was maintained at ', 25~C for 10 hours, the emulsion was stable, undergoing no change.
, Comparison Example 1 I Cyclic dimethylsiloxane tetramer, 40 parts, was added to I an aqueous solution of emulsifying agent composed of 2.0 I parts dodecylbenzenesulfonic acid and 55.5 parts water. After stirring to homogeneity, this was passed through an homogenizer twice at a pressure of 400 kg/cm ~ then maintained at 90C for 2 hours, cooled to 25C, and then maintained at this temperature for 4 hours in order to carry out emulsion polymerization. An emulsion-polymerized emulsion was obtained by neutralization by the addition of 2 parts 50% aqueous triethanolamine. The average particle size in this emulsion was measured at 0.4 micrometers. It was milky white in its external appearance, and the transmittance 1 326~77 .
at 580 nanometers was 0~. When this emulsion was maintai~ed at 25C for 6 months, the appearance of oil drops at tha surface wa~ ob~erved to a minor degree. When thi~ emulsion's 50-fold dilution with water was maintained at 25C for 10 hours, a small oil ~ilm appeared on the sur~ace.
Example 6 Microemulsion A as prepared in Examp:Le 1, 20.0 parts, was combined with 660.0 part~ water to prepare a treatment bath having an organopolysiloxane fraction concentration of 0.5~. A prepared 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immersed in this bath for 30 second~, removed, expressed to 100% on a mangle roll, and then dried for 10 minute~ at 105C. The ~lip resi3tance and flexural rigidity were mea~ured as specified below, and these re~u}t~ are reported in Table 1.
SliP resistance Test specimensj 2 cm x 7 cm, were taken from the woven fabric in both the warp and filling directions. U ing a raæor blade, 2 cm of fabric was cut off from one end of the longer dimension, leaving 2 yarns at the center. A 0.5 cm wide strip which included these residual yarn~ was excised for a length o 2 cm from the other end. The test æpecimen was then installed in an"Instron"tensile tester using a ~rip distance of ~ cm, and was pulled at 1 cm/minute. The maximum load registered in pulling the 2 yarns out by 3 cm wa~
designated as the slip r~sistance (g).
Elexural r1qidity Thls was measured according to JIS L-1096, "General Woven Fabric Test Me~hods'l, Method C (Clark method). The flexural rigidity i8 expressed in millimeter~.
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: 20 Table 1 Slip Resistance (q~ Flexural Ri~idity (mm) Sample WarpFillinqWarp Fillina Example 6 976 576 41 37 :' Untreated 832 520 42 37 .~ Fabric `, Comparison 251 146 43 39 :. Example 2 Comparison 619 411 41 37 Example 3 . Comparison 933 616 55 46 Example 4 :. .
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Comparison ExamPle 2 `~ An emulsion was prepared by ~tirring 15 parts amino-modified dimethylpolysiloxane ~viscosity = 1,100 centistoke~) having the following formula.
(Me2Sil)400(MeSiO)8SiMe3 (C~2)3NHCH2CH2NH2 ; One part emulsifying agent with the formula C12H250(C2H40)6H, 3 parts emulsifying agent with the formula C12H250(~2H~0)8H, and 81.75 parts water to homogeneity and by then adding 0.25 parts acetic acid. This was diluted 250-fold with water to prepare a treatment bath having a silicone fraction concentration of 0.5%. A 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immersed in ; this bath for 30 seconds, removed, expre~sed to 100% on a '~ mangle roll, and then dried for 10 minutes at 105C. The slip resi tance and flexural rigidity were measured as specified in Example 6, and these results are reported in Table 1.
Com~arison Exam~le 3 3 Trimethylsilyl-terminated dimethylpolysiloxane having a viscosity of 350 centistokes, 40 parts, 4.0 parts polyoxyethylene nonylphenol ether (8.5 mols EO~, and 56 parts water were stirred to homogeneity. An emulsion was prepared by passing this mixture through a colloid mill. This w~s diluted 50-fold with wa-ter in order to prepare a treatment bath having a silicone fraction concentration of 0.5%. A 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immersed in this bath for 30 seconds, removed, expressed to 100% on a mangle roll, and then dried for lO minutes at 105~C. The slip resistance and flexural rigidity were measured as specified in Example 6, and these results are reported in Table 1.
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"Sumitex Resin M-3"*~melami~e resin from Sumitomo Kagaku Kogyo Kabushiki Kai~ha~, used with 10% Accelerator ACX as catalyst, wa~ diluted with water to prepare a treatment bath having a resln ~raction concentration o 0.5%. A 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immer~ed in thi~ bath ~or 30 ~econd , removed, expre~sed to 100% on a mangle roll, a~d the~ dried for 10 minutes at 105C. The ælip resistance and ~lexural rigidity were measured a~ specified in Example 6, and the~e re~ults are reported in Table 1.
Example_7 Water, ~60.0 parts, was combined with 20.0 parts Microemulsion B prepared as in Example ~ in order to prepare a treatment bath having an organopoly~iloxane fractlon concentration of 0.5%. A 40 cm x 40 cm taff2ta 3ample (~etoron finished yarn woven fabric, dyed only, no re~in i~ finish) wa~ immersed in this bath for 30 econds, removed, expre~sed with a mangle roll to 100%, and th~n dried at 105C
for 10 minute~. The sllp re3istan~e and flexural rigidity were mea~ured by the te~t methods of Example 6, and these results are reported in Table 2.
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Table_2 Slip Resistance (a) Flexural Ri~iditY (mm) Sample Warp FillinqWarP Fillinq Example 7 970 576 41 37 Untreated 832 520 42 37 Fabric Comparison 251 146 43 39 Example 5 Comparison 619 411 41 37 Example 6 Comparison 933 616 55 46 Example 7 :
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A 40 cm x 40 cm ta~eta ~ample l~etoron finished yarn woven fabric, dyed only, no re~in finish) wa~ immersed for 30 second~ in a treatment bath prepared a~ in Compari~on Example 2, removed, expre~sed with a mangle roll l;o 100%, and then dried at 105C for 10 minute The slip roaistance and ~lexural rlgidity were mea~ured by the te~t methods of Example 6, and th~se re~ults are reported in Table 2.
Compari~on Example 6 A 40 cm x 40 cm taffeta sample ~'Tetoron"finished ~arn woven fabric, dyed only, no re~in fini h) was immersed for 30 seconds in a treatment bath prepared as in Comparison Example 3, removed, expressed with a mangle roll to 100%, and then dried at 105C for 10 minutes. The ~lip resistance and flexural rigidity were measured by the test methods of Example 6, and these result~ are reported in Table 2.
Comparison ExamPle 7 *
A 40 cm x 40 cm taffeta sample ~Tetoron finished yarn woven fabric, dyed only, no re~in f~nish) wa~ immersed for 30 seconds in a treatment bath prepared a~ in Comparison Example 4, removed, expres ed with a mangle roll to 100~, and then dried at 105C for 10 minutes. The slip re~istance and ~lexural rigidity were measured by the test msthodR of Example 6, and these re ults are reported in Table 2.
Example 8 Wat~r, 660.0 parts, was combined with 20.0 part Microemulsion C prepared as in Example 3 in order to prepare a treatment bath having an or~anopolysiloxa~e fraction concentration o~ 0.5%. A 40 cm x 40 cm tafÆeta ~ample ~etoron"fi~i~hed yarn woven fabric, thinnar than the woven ~abric used in Example 6, dyed only, no resin ~inishl was immersed in this bath for 30 second~, removed, expre~sed with a mangle roll to 100%, and then dried at 105G ~or 10 ~, '.' ~ r, ~ * Trademark .
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Table 3 Slip Resistance (q~ Flexural Ri~iditY (mm) Sample WarP Fillinq ~ Fillinq Example 8 177 139 35 32 Untreated 141 122 34 31 Fabric Comparison 64 69 34 32 Example 8 Comparison 112 lll 32 31 Example 9 Comparison 159 141 50 45 Example 10 ~ ,. : , . . . .
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Comparison Example 8 A 40 cm x 40 cm taffeta sample (Tetoron finished yarn woven fabric, thinner than the woven fabric used in Example 6, dyed only, no resin finish) was immersed for 30 seconds in a treatment bath prepared as in Compari son Example 2, removed, expressed with a mangle roll to 100%, and then dried at 105C for lO minutes. The slip resistance and flexural rigidity were measured by the test methods of Example 6, and these results are reported in Table 3.
Comparison ExamPle 9 A 40 cm~x 40 cm taffeta sample (Tetoron finished yarn woven fabric, thinner than the woven fabric used in Example 6, dyed only, no resin finish) was immersed for 30 seconds in a treatment bath prepared as in Comparison Example 3, removed, expressed with a mangle roll to 100%, and then dried at 105C for 10 minutes. The slip resistance and flexural rigidity were measured by the test methods of Example 6, and these ~esults are reported in Table 3.
Comparison ExamPle lO
A 40 cm x 40 cm taffeta sample (Tetoron finished yarn woven fabric, thinner than the woven fabric used in Example 6, dyed only, no resin finish) was immersed for 30 seconds in a treatment bath prepared as in Comparison Example 4, removed, expressed with a mangle roll to 100%, and then dried at 105C for 10 minutes. The slip resistance and ~lexural rigidity were measured by the test methods of Example 6, and these results are reported in Table 3. 1~
Example 9 `
Into separate 150 mL sample bottles were placed 7 samples: 100 mL of each of the six emulsion treatment baths (0.5% organopolysiloxane concentration) prepared in Examples 6 through 8 and Comparison Examples 2 through 4, and 100 , .
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mL of a o.s% aqueous solution o colloidal 3ilica ~rom Niss~n Kagaku Kogyo Kabushikl Kai~ha, brandname: "Snowtex 20", pH 9.~, 20% 8iliCiC anhydride 801ution) ~ which is a colloidal solut~on of ultramicroparticulate 8ilicic anhydride.
Each treatment bath was adjusted to pH 5.5 by the addition of acetic acid, and each treatment bath received 5 drops ~approximately 1.0 g) of 10% aqueou~ zinc nitrate solution (catalyst for ra~in textile finishe3). These were then sealed and maintained for 3 days in a thermo~tatted bath at 70C in order to inve tigate the ~torage ~tabilitie~ of the~e fiber-treatment bath~. The~e re~ult~ are reported in -.i Table 4.
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., Table 4 Treatment Baths StabilltY of the Treatment Bath after 70UC for_3 DaYs Treatment Bath Almost transparent.
of Example 6 No change in liquid.
Treatment Bath Liquid is initially slightly brown.
of Example 7 No change occurs.
Treatment Bath Almost transparent.
of Example 8 No change in liquid.
Treatment Bath Initially slightly white.
of Comparison Oil floats to top after 3 days, Example 2 forming oil drops.
Treatment Bath Initially slightly white. o Comparison Oil floats to top after 3 days, Example 3 forming oil drops.
Treatment Bath Initially almost transparent.
of Comparison Opaque after 3 days. Example 4 White precipitate observed.
Treatment Bath Initially almost transparent. of Colloidal Gel-like precipitate after 3 days.
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Examples of the cationic surfactants are quaternary ammonium hydroxides and their salts such as octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide, dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide,and cocotrimethylammonium hydroxide.
Examples of nonionic surfactants are the polyoxyalkylene alkyl ethers, the polyoxyalkylene alkylphenol ethers, the polyoxyalkylene alkyl esters, the polyoxyalkylene sorbitan alkyl esters, polyethylene glycols, polypropylene glycols, and diethylene glycol.
The surfactant may be used as the single species or a~
the combination of two or more species, with the exception of the combination of anionic surfactant with cationic surfactant. In concrete terms, it is permissible to use a single species of anionic surfactan$, or the combination of : '`, ' : .,.,~ ::
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.
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:', g ; two or more species of anionic surfactants, or a single( species of nonionic surfactant, or the combination of two or `, more species of nonionic surfactants, or a single species of cationic surfactant, or the combination of two or more i species of cationic surfactants, or the combination of two or 3 more species respectively selected from anionic and nonionic surfactants, or the combination of two or more species `~ respectively selected from cationic and nonionic surfactants.
! The surfactant comprising component (C) is used in the , crude emulsion in that quantity which provides for the 1 formation of an emulsion, and this will vary with the type of surfactant. As a consequence, this quantity of use is not specifically restricted, but is preferably about 2 - 50 wt%
~ based on 100 weight parts of components (A) and (B).
! The water comprising the component (D) in the crude emulsion is preferably used in a quantity which gives an organopoly~iloxane concentration of about 10 60 wt%.
i The crude emulsion is prepared by mixing the organo-, trialkoxysilane comprising component (A), the cyclic organo-;! polysiloxane comprising component (B), the surfactant comprising component (C), and the water comprising component ~J (D) to homogeneity, and by passing khis mixture through an emulsifying device such as an homogenizer, colloid mill, or line mixer, etc.
The organopolysiloxane microemulsion of the present invention can be obtained by means of an emulsion polymerization in which the crude emulsion prepared as above is gradually added to a separately prepared aqueous emuIsionpolymerization catalyst solution.
, These emulsion-pol~merization catalysts encompass anionic and cationic catalysts. The anionic catalysts are exemplified by mineral acids such as hydrochloric acid and sulfuric acid, and by the alkylbenzenesulfonic acids, sulfate :
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e ter~ of polyoxyethylene monoalkyl ethers, and alkylnaphthylsulfonic acids given as examples of the surfactant comprising component (C). The cationic catalysts are exemplified by alkali metal hydroxides such a~ potassium hydroxide and sodium hydroxide, and by the guaternary ammonium hydroxides and salts thereof given as examples for the surfactant comprising component (C3. However, due to the low catalytic activity of the quaternary ammonium salts, they ~hould be used in combination with an alkali m~tal hydroxide for activation.
Furthermore, with regard to the ionicitie~ of the surfactant and catalyst, when an anionic surfactant is u~ed as the component (C) in the crude emulsion, an anionic emulsion-polymerization cataly~t should be used in production of the microemulsion.
When a cationic surfactant is used a the component ~C) in the crude emulsion, a cationic emulsion-polymerization catalyst should be used for production of the microemulsion.
~ hen a nonionic surfactant i8 used as the component (C) in the crude emulsion, an anionic or cationic emulsion-polymerization catalyst should be used for production of the microemulsion.
The quantity of use of said emulsion-polymerization catalyst will vary with the type of cataly~t and o i~ not specifically restricted. However, when using a mineral acid or alkali metal hydroxide catalyst, this quantity is preferably 0.2 to 5.0 weight part and more preferably 0.5 to 3.0 weight parts for each 100 weight parts of the combined quantity of organotrialkoxysilane comprising component (A) and cyclic organopolysiloxane comprising component ~B). For the u e of alkylbenzenesul~onic acid, sulfate esters of polyoxyethylene monoalkyl ethers~ alkylnaphthylsulfonic acid9 or quaternary ammonium hydroxides or salts thereof, this "
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., guantity is preferably 0.5 to 50 weight parts and more preerably 1.0 to 30 weight parts for each 100 weight parts of the combined quantity of organotrialkoxysilane comprising component (A~ and cyclic organopolysiloxane comprising component (B). Nonionic surfactant as exemplified for component (C) may be added at this point in order to improve the stability during emulsion polymerization.
The temperature o the aqueous catalyst solution is preferably 40 to 95C when the crude emulsion is gradually added thereto, such as by dripping. The rate of addition will vary with the type and concentration of the catalyst and the temperature of the aqueous catalyst solution. Addition can be rapid at high catalyst concentrations or elevated aqueous catalyst solution temperatures. However, in order to produce microemulsions having smaller particle sizes, in general it is preferred that the crude emulsion be dripped in so as to obtain both dispersion and transparency.
After the termination of addition, the present invention's organopolysiloxane microemulsion having an average particle size not exceeding 0.15 micrometers is produced by an emulsion polymerization at O to 90C until the specified viscosity is achieved. After this emulsion polymerization, it is preferred that the catalyst be neutralized, with alkali in the case of an anionic polymerization catalyst and with acid in the case of a cationic polymerization catalyst. Furthermore, while the organopolyæiloxane concentration during emulsion polymerization is not specifically restricted, it is preferably 5 to 50 wt%. The present invention's organopolysiloxane microemulsion obtained as above can be used as a mold-releas~ agent, relea~e agent, paink additive, defoamer, lustrant, plastic coating agent, fiber-treatment agent, etc.
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~ 326577 The fiber-treatment agent of the present invention is based on a microemulsion comprising an orqanopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 30 to 95 mol% trifunctional siloxane units with the formula RSiO3/2 w:herein R is a monovalent organic group and 70 to 5 mol% difunctional siloxane units with the formula R12SiO wherein Rl is a monovalent hydrocarbon or halogenated hydrocarbon group.
Forty-five to 90 mol% trifunctional siloxane units and 55 to 10 mol% difunctional siloxane unit~ are preferred. The slip resistance becomes unsatisfactory at below 30 mol~ of said trifunctional siloxane units.
In addition, as long as the object o the invention is not compromised, the fiber-treatment agent of the present invention may as desired contain additional water; resin finishing agents such as glyoxal resin, melamine resin, urea resin, polyester resin, and acrylic resin; rubber latexes such as styrene/butadiene latex and natural rubber latex;
organohydrogenpolysilo~ane emulsion and organoalkoxysilane emulsion; surfactants; preservatives; colorants; the salts between organocarboxylic acids and metals such as iron, lead, antimony, cadmium, titanium, calcium, bismuth, zirconium, etc.; organic amino compounds as condensation catalysts, such as triethanolamine, triethylenediamine, dimethylphenylamine, etc.; among others.
Fibrous mat~rial is treated with the fiber-treatment agent of the present inve~tion using such methods as spraying, roll application, brush coating, i~nersion, etc.
The add-on will vary with the fibrous material and so is not specifically restricted, but is generally in the range of 0.01 to 10.0 wt% as organopolysiloxane fraction based on the fibrous material. The fibrous material is then treated by, :
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`, With regard to substance, the fibrous material is 6 exemplified by natural fibers such as wool, silk, flax, cotton, angora, mohair, and asbestos; by regenerated fibers such as rayon and bemberg; by semisynthetic fibers such as acetate; by synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, and spandex; and by inorganic fibers such as glass fiber, carbon fiber, and silicon carbide fiber. In its form it is exemplified by the staple, filament, tow, top, and yarn, and in its structure it is exemplified by knits, weaves, and nonwovens.
The present invention will be explained in the following wit~ reference to illustrative examplas, in which parts =
weight parts and % = wt% unless otherwise specified, and the viscosity is the value at 25C. Me denotes the methyl group.
Example 1 Water, 158.5 parts, 1.5 parts hexadecyltrimethylammonium 6 chloride, 150.0 parts methyltrimethoxysilane, and 15.0 parts cyclic dimethylsiloxane tetramer were placed in a 500 mL
beaker and mixed to homogeneity using a propeller stirrer.
6 This mixture was then passed once through an homogeni~er at a pressure of 300 kg/cm2 to afford a crude emulsion. Water, 152.7 parts, 10 parts hexadecyltrimethylammonium chloride, and 0.8 parts sodium hydroxide were separately placed in a 500 mL four-neck flask eq~lipped with a stirrer, reflu~
condenser, addition funnel, and thermometer. After dissolution, the liquid was maintained at 85C with slow stirring. The previously prepared crude emulsion was then gradually dripped into the aqueous catalyst solution over 90 minutes. After addition, emulsion polymeri7ation was carried out by stirring for an additional 30 minutes at 85C. Ater ~, , ' 1, ' :
~i 1 326577 ;
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polymerization and cooling, 1.2 parts acetic acid was added to adjust the pH to 7, thus to afford a microemul~ion o organopolysiloxane composed of 84.4 mol% CH3SiO3/~ units and 15.6 mol% (CH3)2SiO u~its (Microemulsion A). The average particle size in this microemulsion was measured using a ~uasi-elastic light scattering instrument (Malrer, USA), and a value of 0.05 micrometers wa~ obtained. The external appearance was slightly white and tran~parent, and the transmittance at 580 nanometers was 67%. A 10 mL portion of this microemulsion was collected, and a nonvolatile fraction of 22.0% was measured at 105C. In addition, 25 mL of this microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes. There wa~ no separation of the microemul3ion. The microemulsion was also maintained at 25C
fQr 6 months and wa~ found to be ~table. with no change occurring. Finally, the microemulsion s 50-fold dilution with water was maintained at 25~C for 10 hours. This emulsion was stable, undergoing no change.
Exam~le 2 Water~ 150.0 parts, 6.7 parts polyoxyethylene (45 mol) nonylphenol ether, 50.0 parts vinylkrimethoxysilane, and 15.0 parts cyclic dimethylsiloxane tetramer were placed in a 500 mL beaker and then mixed to homogeneity using a propeller stirrer. This mixture was passed through an homogenizer once at a prescure of 300 kg/cm~ in order to prepare a crude emulsion. Water, 175.3 parts, and 10.0 parts dodecylbenzenesulfonic acid were placed in a 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, followed by dissolution and maintenance at a liguid temperature of 85C with slow stirring. The previously prepared crude emulsion was gradually dripped into thi~ aqueous catalyst solution over 120 minute~, followed by maintenance after addition at 85C
., ,' ~,i :i ;: ::: .. : :.;~ :
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~ , for an additional 60 minutes in order to carry out emulsion polymerization. After emulsion polymerization and cooling9 5 parts triethanolamine was added to adjust the pH to 7, thus affording a microemulsion of organopoly~i:Lo~ane composed of 62.5 mol% CH~=CHSiO3/2 units and 37.5 mol% (CH3)2SiO units-(Microemulsion B). The average particl~ size in this microemulsion was measured at 0.07 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 53%. A 10 mL
portion of this microemulsion was collected, and a non-volatile fraction of 23.0% was measured at 105C. When 25 mL
of the microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes, no microemulsion separation was observed. When the microemulsion was maintained at 25C for 6 months, the microemulsion was stable, undergoing no change.
When the microemulsion's 50-fold dilution with water was maintained at 25C for 10 hours, the emulsion was stable, undergoing no change.
ExamPle 3 Water, 158.5 parts, 10.5 parts polyoxyethylene (40 mol) nonylphenol ether, 1.5 parts hexadecyltrimethylammonium chloride, 150.0 parts gamma-glycidoxypropyltrimethoxysilane, and 15.0 parts cyclic phenylmethylsiloxane tetramer were placed in a 500 mL beaker, and were mixed to homogeneity using a propeller stirrer. This mixture was passed through an homogenizer once at a pressure of 350 kg/cm2 to prepare a crude emulsion. Water, 152.7 parts, 10 parts hexadecyl-trimethylammonium chloride, and 0.8 parts sodium hydroxide were placed in a 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, followed by dissolution and maintenance at a li~uid temperature of 85C with slow stirring. The previously prepared crude ~mulsion was gradually dripped into this . ~ . . ..
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:i 16 :, aqueous catalyst solution over 90 minutes, followed by maintenance at 85C for an additional 30 minutesi after addition in order to carry out emulsion polymerization. After polymerization and cooling, 1.2 parts acetic acid was added to afford a microemulsion (Microemulsion C) of an organopoly-siloxane composed of 14.8 mol% C6H5(CH3)SiO units and 85.2 mol% unit~ having the following formula.
2 \ /C~H2CH2CH2CH2Si3/2 O
The average particle size in this microemulsion was measured at 0.07 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 68%. A 10 mL portion of this microemulsion i~ was collected, and a nonvolatile fraction of 20.5% was ' measured at 105~C. When 25 mL of this microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes no microemulsion separation was observed. When the microemulsion was maintained at 25C for 6 months, it was stable, without any change. When the microemulsion s 50-fold dilution with water was maintained at 25C for 10 hours, the emulsion was stable, undergoing no change.
, Example 4 , Water, 78.5 parts, 4.0 parts polyoxyethylene ~40 mol) ; nonylphenol ether, 30.0 parts methyltrimethoxysilane, and 37.5 parks cyclic dimethylsiloxane tetramer were placed in a 500 mL beaker, and were then mixed to homogeneity using a propeller stirrer. This mixturç was passed through an ~, homogenizer once at a pressure of 350 Xg/cm2 to prepare a crude emulsion. Water, 138.9 parts, 9.0 parts hexadecyltrimethylammonium chloride, and 0.7 parts sodium hydroxide were placed in a 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, followed by dissolution and maintenance at a ' ~ ' ' ' ~ 326577 liquid temperature of 85C with slow stirring. The previously prepared crude emulsicn was gradually dripped into this aqueous catalyst solution over 100 minutes. After addition, emulsion polymerization was conducted by maintenance at 85C for an additional 45 minutes. After polymerization and cooling, 1.0 part acetic acid was added to adjust the pH to 7, thus affording a microemulsion of organopolysiloxane composed of 30.4 mol% CH3SiO3/2 units and 69.6 mol% (C~3)2SiO units. The average particle size in this microemulsion was measured at 0.05 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 65%. A 10 mL
portion of this microemulsion was collected, and a nonvolatile fraction of 22.5% was measured at 105C. A 25 mL
portion ~f this microemulsion was placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes: no microemulsion separation was observed. When the micro~mulsion was maintained at 25C f~r 6 months, it was stable, without any change. When the microemulsion s 50-fold dilution with water was maintained a 25C for 10 hours, the emulsion was stable, undergoing no change.
Example 5 Water, 132 parts, 27 parts polyoxyethylene (40 mol) octylphenol ether, 133 parts methyltrimethoxysilane, and 21 parts cyclic dimethylsiloxane tetramer were placed in a 500 mL beaker, and were then mixed to homogeneity using a propeller stirrer. This mixture was then passed once through an homogenizer at a pressure of 350 kg~cm2 in order to prepare a crude emulsion. Sodium hydroxide, 0.3 parts, was dissolved in 664 parts water in a 19 500 mL four-neck flask equipped with a stirrer, reflux condenser, addition funnel, and thermometer, and this was then maintained at a liquid temperature of 85C with slow stirring. The previously !
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i~ 1 326577 prepared crude emulsion was gradually dripped uinto this aqueous catalyst solution over 100 minutes. After auddition, emulsion polymerization was conducted by maintenance at 85C
for an additional 45 minutes. After polymerization and cooling, the p~ was adjusted to 7 by adding 1.0 part acetic acid, thus to afford a microemulsion of organopolysiloxane composed of 75 mol% CH3SiO3/2 units and 25 mol% (CH3)2SiO
units. The average particle size in this microemulsion was measured at 0.08 micrometers. It was slightly white and transparent in its external appearance, and the transmittance at 580 nanometers was 63%. A 10 mL portion of this microemulsion was collected, and a nonvolatile fraction of 15.3% was measured at 105C. A 25 mL portion of this microemulsion wa~ placed in a centrifuge tube and spun at 2,500 rpm for 30 minutes: no microemulsion separation was observed. When the microemulsion was maintained at 25C for 6 months, it Was stable, without any change. When the microemulsion's 50-fold dilution with water was maintained at ', 25~C for 10 hours, the emulsion was stable, undergoing no change.
, Comparison Example 1 I Cyclic dimethylsiloxane tetramer, 40 parts, was added to I an aqueous solution of emulsifying agent composed of 2.0 I parts dodecylbenzenesulfonic acid and 55.5 parts water. After stirring to homogeneity, this was passed through an homogenizer twice at a pressure of 400 kg/cm ~ then maintained at 90C for 2 hours, cooled to 25C, and then maintained at this temperature for 4 hours in order to carry out emulsion polymerization. An emulsion-polymerized emulsion was obtained by neutralization by the addition of 2 parts 50% aqueous triethanolamine. The average particle size in this emulsion was measured at 0.4 micrometers. It was milky white in its external appearance, and the transmittance 1 326~77 .
at 580 nanometers was 0~. When this emulsion was maintai~ed at 25C for 6 months, the appearance of oil drops at tha surface wa~ ob~erved to a minor degree. When thi~ emulsion's 50-fold dilution with water was maintained at 25C for 10 hours, a small oil ~ilm appeared on the sur~ace.
Example 6 Microemulsion A as prepared in Examp:Le 1, 20.0 parts, was combined with 660.0 part~ water to prepare a treatment bath having an organopolysiloxane fraction concentration of 0.5~. A prepared 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immersed in this bath for 30 second~, removed, expressed to 100% on a mangle roll, and then dried for 10 minute~ at 105C. The ~lip resi3tance and flexural rigidity were mea~ured as specified below, and these re~u}t~ are reported in Table 1.
SliP resistance Test specimensj 2 cm x 7 cm, were taken from the woven fabric in both the warp and filling directions. U ing a raæor blade, 2 cm of fabric was cut off from one end of the longer dimension, leaving 2 yarns at the center. A 0.5 cm wide strip which included these residual yarn~ was excised for a length o 2 cm from the other end. The test æpecimen was then installed in an"Instron"tensile tester using a ~rip distance of ~ cm, and was pulled at 1 cm/minute. The maximum load registered in pulling the 2 yarns out by 3 cm wa~
designated as the slip r~sistance (g).
Elexural r1qidity Thls was measured according to JIS L-1096, "General Woven Fabric Test Me~hods'l, Method C (Clark method). The flexural rigidity i8 expressed in millimeter~.
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: 20 Table 1 Slip Resistance (q~ Flexural Ri~idity (mm) Sample WarpFillinqWarp Fillina Example 6 976 576 41 37 :' Untreated 832 520 42 37 .~ Fabric `, Comparison 251 146 43 39 :. Example 2 Comparison 619 411 41 37 Example 3 . Comparison 933 616 55 46 Example 4 :. .
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Comparison ExamPle 2 `~ An emulsion was prepared by ~tirring 15 parts amino-modified dimethylpolysiloxane ~viscosity = 1,100 centistoke~) having the following formula.
(Me2Sil)400(MeSiO)8SiMe3 (C~2)3NHCH2CH2NH2 ; One part emulsifying agent with the formula C12H250(C2H40)6H, 3 parts emulsifying agent with the formula C12H250(~2H~0)8H, and 81.75 parts water to homogeneity and by then adding 0.25 parts acetic acid. This was diluted 250-fold with water to prepare a treatment bath having a silicone fraction concentration of 0.5%. A 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immersed in ; this bath for 30 seconds, removed, expre~sed to 100% on a '~ mangle roll, and then dried for 10 minutes at 105C. The slip resi tance and flexural rigidity were measured as specified in Example 6, and these results are reported in Table 1.
Com~arison Exam~le 3 3 Trimethylsilyl-terminated dimethylpolysiloxane having a viscosity of 350 centistokes, 40 parts, 4.0 parts polyoxyethylene nonylphenol ether (8.5 mols EO~, and 56 parts water were stirred to homogeneity. An emulsion was prepared by passing this mixture through a colloid mill. This w~s diluted 50-fold with wa-ter in order to prepare a treatment bath having a silicone fraction concentration of 0.5%. A 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immersed in this bath for 30 seconds, removed, expressed to 100% on a mangle roll, and then dried for lO minutes at 105~C. The slip resistance and flexural rigidity were measured as specified in Example 6, and these results are reported in Table 1.
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"Sumitex Resin M-3"*~melami~e resin from Sumitomo Kagaku Kogyo Kabushiki Kai~ha~, used with 10% Accelerator ACX as catalyst, wa~ diluted with water to prepare a treatment bath having a resln ~raction concentration o 0.5%. A 40 cm x 40 cm taffeta sample (nylon filament weave, dyed only, no resin finish) was immer~ed in thi~ bath ~or 30 ~econd , removed, expre~sed to 100% on a mangle roll, a~d the~ dried for 10 minutes at 105C. The ælip resistance and ~lexural rigidity were measured a~ specified in Example 6, and the~e re~ults are reported in Table 1.
Example_7 Water, ~60.0 parts, was combined with 20.0 parts Microemulsion B prepared as in Example ~ in order to prepare a treatment bath having an organopoly~iloxane fractlon concentration of 0.5%. A 40 cm x 40 cm taff2ta 3ample (~etoron finished yarn woven fabric, dyed only, no re~in i~ finish) wa~ immersed in this bath for 30 econds, removed, expre~sed with a mangle roll to 100%, and th~n dried at 105C
for 10 minute~. The sllp re3istan~e and flexural rigidity were mea~ured by the te~t methods of Example 6, and these results are reported in Table 2.
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Table_2 Slip Resistance (a) Flexural Ri~iditY (mm) Sample Warp FillinqWarP Fillinq Example 7 970 576 41 37 Untreated 832 520 42 37 Fabric Comparison 251 146 43 39 Example 5 Comparison 619 411 41 37 Example 6 Comparison 933 616 55 46 Example 7 :
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A 40 cm x 40 cm ta~eta ~ample l~etoron finished yarn woven fabric, dyed only, no re~in finish) wa~ immersed for 30 second~ in a treatment bath prepared a~ in Compari~on Example 2, removed, expre~sed with a mangle roll l;o 100%, and then dried at 105C for 10 minute The slip roaistance and ~lexural rlgidity were mea~ured by the te~t methods of Example 6, and th~se re~ults are reported in Table 2.
Compari~on Example 6 A 40 cm x 40 cm taffeta sample ~'Tetoron"finished ~arn woven fabric, dyed only, no re~in fini h) was immersed for 30 seconds in a treatment bath prepared as in Comparison Example 3, removed, expressed with a mangle roll to 100%, and then dried at 105C for 10 minutes. The ~lip resistance and flexural rigidity were measured by the test methods of Example 6, and these result~ are reported in Table 2.
Comparison ExamPle 7 *
A 40 cm x 40 cm taffeta sample ~Tetoron finished yarn woven fabric, dyed only, no re~in f~nish) wa~ immersed for 30 seconds in a treatment bath prepared a~ in Comparison Example 4, removed, expres ed with a mangle roll to 100~, and then dried at 105C for 10 minutes. The slip re~istance and ~lexural rigidity were measured by the test msthodR of Example 6, and these re ults are reported in Table 2.
Example 8 Wat~r, 660.0 parts, was combined with 20.0 part Microemulsion C prepared as in Example 3 in order to prepare a treatment bath having an or~anopolysiloxa~e fraction concentration o~ 0.5%. A 40 cm x 40 cm tafÆeta ~ample ~etoron"fi~i~hed yarn woven fabric, thinnar than the woven ~abric used in Example 6, dyed only, no resin ~inishl was immersed in this bath for 30 second~, removed, expre~sed with a mangle roll to 100%, and then dried at 105G ~or 10 ~, '.' ~ r, ~ * Trademark .
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Table 3 Slip Resistance (q~ Flexural Ri~iditY (mm) Sample WarP Fillinq ~ Fillinq Example 8 177 139 35 32 Untreated 141 122 34 31 Fabric Comparison 64 69 34 32 Example 8 Comparison 112 lll 32 31 Example 9 Comparison 159 141 50 45 Example 10 ~ ,. : , . . . .
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Comparison Example 8 A 40 cm x 40 cm taffeta sample (Tetoron finished yarn woven fabric, thinner than the woven fabric used in Example 6, dyed only, no resin finish) was immersed for 30 seconds in a treatment bath prepared as in Compari son Example 2, removed, expressed with a mangle roll to 100%, and then dried at 105C for lO minutes. The slip resistance and flexural rigidity were measured by the test methods of Example 6, and these results are reported in Table 3.
Comparison ExamPle 9 A 40 cm~x 40 cm taffeta sample (Tetoron finished yarn woven fabric, thinner than the woven fabric used in Example 6, dyed only, no resin finish) was immersed for 30 seconds in a treatment bath prepared as in Comparison Example 3, removed, expressed with a mangle roll to 100%, and then dried at 105C for 10 minutes. The slip resistance and flexural rigidity were measured by the test methods of Example 6, and these ~esults are reported in Table 3.
Comparison ExamPle lO
A 40 cm x 40 cm taffeta sample (Tetoron finished yarn woven fabric, thinner than the woven fabric used in Example 6, dyed only, no resin finish) was immersed for 30 seconds in a treatment bath prepared as in Comparison Example 4, removed, expressed with a mangle roll to 100%, and then dried at 105C for 10 minutes. The slip resistance and ~lexural rigidity were measured by the test methods of Example 6, and these results are reported in Table 3. 1~
Example 9 `
Into separate 150 mL sample bottles were placed 7 samples: 100 mL of each of the six emulsion treatment baths (0.5% organopolysiloxane concentration) prepared in Examples 6 through 8 and Comparison Examples 2 through 4, and 100 , .
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mL of a o.s% aqueous solution o colloidal 3ilica ~rom Niss~n Kagaku Kogyo Kabushikl Kai~ha, brandname: "Snowtex 20", pH 9.~, 20% 8iliCiC anhydride 801ution) ~ which is a colloidal solut~on of ultramicroparticulate 8ilicic anhydride.
Each treatment bath was adjusted to pH 5.5 by the addition of acetic acid, and each treatment bath received 5 drops ~approximately 1.0 g) of 10% aqueou~ zinc nitrate solution (catalyst for ra~in textile finishe3). These were then sealed and maintained for 3 days in a thermo~tatted bath at 70C in order to inve tigate the ~torage ~tabilitie~ of the~e fiber-treatment bath~. The~e re~ult~ are reported in -.i Table 4.
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., Table 4 Treatment Baths StabilltY of the Treatment Bath after 70UC for_3 DaYs Treatment Bath Almost transparent.
of Example 6 No change in liquid.
Treatment Bath Liquid is initially slightly brown.
of Example 7 No change occurs.
Treatment Bath Almost transparent.
of Example 8 No change in liquid.
Treatment Bath Initially slightly white.
of Comparison Oil floats to top after 3 days, Example 2 forming oil drops.
Treatment Bath Initially slightly white. o Comparison Oil floats to top after 3 days, Example 3 forming oil drops.
Treatment Bath Initially almost transparent.
of Comparison Opaque after 3 days. Example 4 White precipitate observed.
Treatment Bath Initially almost transparent. of Colloidal Gel-like precipitate after 3 days.
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Claims (11)
1. A process for the production of a microemulsion composition comprising an organopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 10 to 95 mol% trifunctional siloxane units with the formula RSiO3/2 wherein R is a monovalent organic group selected from the group consisting of alkyl, alkenyl, phenyl, tolyl, 2-phenylethyl, 2-phenylpropyl, 3,3,3-trifluoropropyl, gamma-aminopropyl, gamma-(N-ethylamino)propyl, gamma-(N-butylamino)propyl, 4-(N-cyclohexylamino)butyl, 4-(N-phenylamino)butyl, N-aminoethylaminopropyl, beta-(N,N-dimethylamino)ethyl, gamma-glycidoxypropyl, 3,4-epoxycyclohexylpropyl,gamma-mercaptopropyl, and gamma-methacryloxypropyl groups; and 90 to 5 mol%
difunctionai siloxane units with the formula R'2SiO wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group, said process comprising the steps of:
(1) preparing a crude emulsion by mixing to homogeneity (A) 10 to 95 mol% of an organotrialkoxysilane having the formula RSi(OR')3 wherein R is a monovalent organic group as defined above and R1 is a monovalent hydrocarbon or halogenated hydrocarbon group, (B) 90 to 5 mol% as R12SiO units of a cyclic organopolysiloxane having the formula (R12SiO)n wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group and n is an integer having a value of 3 to 10, (C) surfactant, and (D) water, and passing this mixture through an emulsifying device;
(2) dripping said crude emulsion into an aqueous emulsion polymerization catalyst solution containing an anionic or cationic catalyst; and (3) maintaining the resulting mixture of aqueous emulsion polymerization catalyst solution and crude emulsion at 0° to 90°C. until said microemulsion has been achieved.
difunctionai siloxane units with the formula R'2SiO wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group, said process comprising the steps of:
(1) preparing a crude emulsion by mixing to homogeneity (A) 10 to 95 mol% of an organotrialkoxysilane having the formula RSi(OR')3 wherein R is a monovalent organic group as defined above and R1 is a monovalent hydrocarbon or halogenated hydrocarbon group, (B) 90 to 5 mol% as R12SiO units of a cyclic organopolysiloxane having the formula (R12SiO)n wherein R1 is a monovalent hydrocarbon or halogenated hydrocarbon group and n is an integer having a value of 3 to 10, (C) surfactant, and (D) water, and passing this mixture through an emulsifying device;
(2) dripping said crude emulsion into an aqueous emulsion polymerization catalyst solution containing an anionic or cationic catalyst; and (3) maintaining the resulting mixture of aqueous emulsion polymerization catalyst solution and crude emulsion at 0° to 90°C. until said microemulsion has been achieved.
2. A process according to claim 1 wherein R1 is the methyl group.
3. A process according to claim 1 wherein R is the methyl group.
4. A process according to claim 1 wherein R1 and R are methyl groups.
5. A process according to claim 1 wherein the crude emulsion is composed of (A) 30 to 95 mol% of the organotrialkoxysilane having the formula RSi(OR1)3 and (B) 70 to 5 mol% as R12SiO units of the cyclic organopolysiloxane having the formula (R12SiO)n.
6. A process according to claim 1 wherein Component (C) is a non-ionic surfactant.
7. A process according to claim 6 wherein R1 is the methyl group.
8. A process according to claim 6 wherein R is the methyl group.
9. A process according to claim 6 wherein R1 and R are methyl groups.
10. An aqueous microemulsion composition comprising an organopolysiloxane having an average particle size not exceeding 0.15 micrometers and composed of 30 to 95 mol% of an organotrialkoxysilane having the formula RSi(OR1)3/2 wherein R is a monovalent organic group selected from the group consisting of alkyl, alkenyl, phenyl, tolyl, 2-phenylethyl, 2-phenylpropyl, 3,3,3-trifluoropropyl, gamma-aminopropyl, gamma-(N-ethylamino)propyl, gamma-(N-butylamino)propyl, 4-(N-cyclohexylamino)butyl, 4-(N-phenylamino)butyl, N-aminoethylaminopropyl, beta-(N,N-dimethylamino)ethyl, gamma-glycidoxypropyl, 3,4-epoxycyclohexylpropyl,gamma-mercaptopropyl, and gamma-methacryloxypropyl groups; and 70 to 5 mol%
as R12SiO units of a cyclic organopolysiloxane having the formula R12SiO)n wherein R
is a monovalent hydrocarbon or halogenated hydrocarbon group.
as R12SiO units of a cyclic organopolysiloxane having the formula R12SiO)n wherein R
is a monovalent hydrocarbon or halogenated hydrocarbon group.
11. A fiber-treatment agent based on an aqueous microemulsion composition as defined in claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10758087A JPH0681807B2 (en) | 1987-03-12 | 1987-04-30 | Organopolysiloxane micro emulsion, method for producing the same and use thereof |
| JP107580/87 | 1987-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1326577C true CA1326577C (en) | 1994-01-25 |
Family
ID=14462770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000565500A Expired - Fee Related CA1326577C (en) | 1987-04-30 | 1988-04-29 | Organopolysiloxane microemulsion, process for its production and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4935464A (en) |
| EP (1) | EP0291213A3 (en) |
| CA (1) | CA1326577C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111286029A (en) * | 2020-03-15 | 2020-06-16 | 华中师范大学 | High-stability organic silicon emulsion and preparation method and application thereof |
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| CA1328139C (en) * | 1985-12-12 | 1994-03-29 | Daniel Graiver | Methods for making polydiorganosiloxane microemulsions |
| CA2004297A1 (en) * | 1988-12-02 | 1990-06-02 | Hiroshi Kimura | Polyorganosiloxane fine particles |
| JP2750899B2 (en) * | 1989-06-19 | 1998-05-13 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing cyclohexylamino group-containing organopolysiloxane microemulsion |
| DE3920269A1 (en) * | 1989-06-21 | 1991-01-17 | Bayer Ag | COATING AGENTS FOR PRODUCING LIABILITY-REDUCING COATINGS |
| CA2041599A1 (en) * | 1990-06-01 | 1991-12-02 | Michael Gee | Method for making polysiloxane emulsions |
| US5258451A (en) * | 1990-06-07 | 1993-11-02 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of an aqueous emulsion of organopolysiloxane |
| US5310772A (en) * | 1990-09-07 | 1994-05-10 | Alliedsignal Inc. | Coemulsification of oxidized polyethylene homopolymers and amino functional silicone fluids |
| CN1058274C (en) * | 1990-09-07 | 2000-11-08 | 联合信号股份有限公司 | Coemulsification of oxidized polyethylene homopolymers and amino functional silicone fluids |
| US5262088A (en) * | 1991-01-24 | 1993-11-16 | Dow Corning Corporation | Emulsion gelled silicone antifoams |
| DE4128893A1 (en) * | 1991-05-03 | 1992-11-05 | Wacker Chemie Gmbh | COATINGS BASED ON SILICONE RESIN |
| US5371139A (en) * | 1991-06-21 | 1994-12-06 | Dow Corning Toray Silicone Co., Ltd. | Silicone rubber microsuspension and method for its preparation |
| US5556629A (en) * | 1991-09-13 | 1996-09-17 | General Electric Company | Method of preparing microemulsions |
| DE4238290C1 (en) * | 1992-11-13 | 1993-12-16 | Goldschmidt Ag Th | Release agent for molds for the production of moldings from plastics |
| JP3556259B2 (en) * | 1993-12-24 | 2004-08-18 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane emulsion and fibers treated with the emulsion |
| US5504149A (en) * | 1994-08-25 | 1996-04-02 | Dow Corning Corporation | Method of emulsion polymerization |
| US5616646A (en) * | 1994-11-07 | 1997-04-01 | Genesee Polymers Corporation | Restructuring silicone rubber to produce fluid or grease |
| US5674937A (en) * | 1995-04-27 | 1997-10-07 | Dow Corning Corporation | Elastomers from silicone emulsions having self-catalytic crosslinkers |
| US5661215A (en) * | 1995-07-26 | 1997-08-26 | Dow Corning Corporation | Microemulsions of gel-free polymers |
| US5684085A (en) * | 1996-01-05 | 1997-11-04 | Dow Corning Corporation | Microemulsions of gel-free polymers |
| US5785977A (en) * | 1996-02-07 | 1998-07-28 | Breithbarth; Richard | Non-metallic microparticle carrier materials |
| WO2000034359A1 (en) * | 1998-12-07 | 2000-06-15 | General Electric Company | Emulsion polymerized silicone rubber-based impact modifiers, method for making, and blends thereof |
| ES2158763B1 (en) * | 1998-12-15 | 2002-06-16 | Relats Sa | TEXTILE ELEMENT OF FIBERS CONTAINING SILICON AND PROCEDURE TO IMPROVE YOUR THERMAL STABILITY. |
| US6214927B1 (en) * | 1999-11-02 | 2001-04-10 | General Electric Company | Method for making aqueous emulsions of functionalized organopolysiloxanes |
| US6475974B1 (en) * | 2000-09-01 | 2002-11-05 | Dow Corning Corporation | Mechanical microemulsions of blended silicones |
| US6632420B1 (en) | 2000-09-28 | 2003-10-14 | The Gillette Company | Personal care product |
| FR2821282A1 (en) * | 2001-02-23 | 2002-08-30 | Univ Paris Curie | MONODISPERSED MICROEMULSIONS AND EMULSIONS BASED ON POLYOSILOXANES, PREPARATION METHOD AND COMPOSITIONS COMPRISING SAME |
| IL148350A0 (en) * | 2002-02-25 | 2002-09-12 | J G Systems Inc | Processing and repairing emulsions and microemulsions for use in optical fibers |
| US7875673B2 (en) * | 2004-07-07 | 2011-01-25 | Dow Corning Corporation | Emulsions of organopolysiloxane resins produced by emulsion polymerization |
| CN1297592C (en) * | 2005-03-07 | 2007-01-31 | 华明扬 | Process for preparing cation composite modified organosilicon emulsion |
| WO2007099814A1 (en) * | 2006-03-02 | 2007-09-07 | Kaneka Corporation | Process for production of hollow silicone fine particles |
| DE602006010817D1 (en) | 2006-05-05 | 2010-01-14 | 3M Innovative Properties Co | Tubular cable connection |
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| BRPI1005347B1 (en) * | 2009-02-05 | 2021-02-17 | 3M Innovative Propereties Company | set and item |
| CN103003333A (en) | 2010-07-22 | 2013-03-27 | 道康宁公司 | Process for making polysiloxane emulsions |
| PT2608338E (en) | 2011-12-21 | 2014-02-21 | 3M Innovative Properties Co | Terminal connection device for a power cable |
| US9234105B2 (en) | 2012-01-10 | 2016-01-12 | 3M Innovative Properties Company | Aqueous fluorinated silane dispersions |
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| NL133796C (en) * | 1965-01-21 | 1900-01-01 | ||
| FR2205358B1 (en) * | 1972-11-03 | 1976-04-23 | Rhone Poulenc Ind | |
| JPS54131661A (en) * | 1978-04-05 | 1979-10-12 | Toray Silicone Co Ltd | Organopolysiloxane latex composition |
| GB2092608B (en) * | 1981-01-28 | 1985-02-27 | Gen Electric | Water-based resin emulsions |
| DE3216585C2 (en) * | 1982-05-04 | 1984-07-26 | Th. Goldschmidt Ag, 4300 Essen | Process for the production of finely divided, stable O / W emulsions of organopolysiloxanes |
| US4620878A (en) * | 1983-10-17 | 1986-11-04 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
| US4696969A (en) * | 1984-07-27 | 1987-09-29 | General Electric Company | Emulsion polymerized silicone emulsions having siloxane-bonded UV absorbers |
| CA1328139C (en) * | 1985-12-12 | 1994-03-29 | Daniel Graiver | Methods for making polydiorganosiloxane microemulsions |
| US4784665A (en) * | 1986-07-24 | 1988-11-15 | Toray Silicone Co., Ltd. | Agent for the treatment of fibers |
-
1988
- 1988-04-28 US US07/187,610 patent/US4935464A/en not_active Expired - Fee Related
- 1988-04-29 EP EP88303951A patent/EP0291213A3/en not_active Withdrawn
- 1988-04-29 CA CA000565500A patent/CA1326577C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111286029A (en) * | 2020-03-15 | 2020-06-16 | 华中师范大学 | High-stability organic silicon emulsion and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0291213A2 (en) | 1988-11-17 |
| EP0291213A3 (en) | 1989-07-26 |
| US4935464A (en) | 1990-06-19 |
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