Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3870542 A
Publication typeGrant
Publication dateMar 11, 1975
Filing dateSep 26, 1972
Priority dateAug 22, 1969
Also published asCA935955A1, DE2041899A1, DE2041899B2, DE2041899C3
Publication numberUS 3870542 A, US 3870542A, US-A-3870542, US3870542 A, US3870542A
InventorsHosokawa Kenjiro, Ida Syunya
Original AssigneeKanegafuchi Spinning Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process of treating fibrous articles with microcapsules containing hydrophobic treating agent
US 3870542 A
Abstract
A fibrous article such as yarn, woven and knitted fabric and non-woven fabric is treated with hydrophobic treating agent by applying microcapsules composed of a core constitutent consisting of a non-aqueous solvent solution of the hydrophobic treating agent and a wall constituent containing the core constituent and made up of a thin synthetic resin shell and having a low tenacity at break of at most 100 g/cm2, and then by breaking the applied microcapsules at a breaking force of at least 100 g/cm2 so as to impregnate the fibrous article with the non-aqueous solvent solution which flows out from the broken microcapsules.
Images(21)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent [191 Ida et a1.

1 1 PROCESS OF TREATING FIBROUS ARTICLES WITH MICROCAPSULES CONTAINING HYDROPI-IOBIC TREATING AGENT [75] Inventors: Syunya Ida, Nara; Kenjiro Hosokawa, Osaka, both of Japan [73] Assignee: Kanegafuchi Boseki Kabushiki Kaisha, Tokyo, Japan [22] Filed: Sept. 26, 1972 [21] Appl. N0.: 292,414

Related US Application Data [63] Continuation of Ser. No. 65,244, Aug. 19, 1970,

abandoned.

[30] Foreign Application Priority Data Augv 22, 1969 Japan 44-66574 Aug. 23, 1969 Japan 44-66786 Aug. 25, 1969 Japan 44-67429 Oct. 15, 1969 Japan 44-82727 [52] US. Cl l17/33.3, 8/79, 8/115.5,

[ Mar. 11, 1975 KP, 35.5 T, 33.3; 252/316; 8/115.5

Primary Examiner-William D. Martin Assistant Examiner-Theodore G. Davis Attorney, Agent, or Firm-Woodhams, Blanchard and Flynn [57] ABSTRACT A fibrous article such as yarn, woven and knitted fabric and non-woven fabric is treated with hydrophobic treating agent by applying microcapsules composed of a core constitutent consisting of a non-aqueous solvent solution of the hydrophobic treating agent and a wall constituent containing the core constituent and made up of a thin synthetic resin shell and having a low tenacity at break of at most 100 g/cm and then by breaking the applied microcapsules at a breaking force of at least 100 g/cm so as to impregnate the fibrous article with the non-aqueous solvent solution which flows out from the broken microcapsules.

18 Claims, N0 Drawings PROCESS OF TREATING FIBROUS ARTICLES WITH MICROCAPSULES CONTAINING HYDROPHOBIC TREATING AGENT This is a continuation, of application Ser. No. 65,244, filed Aug. 19, 1970, now abandoned.

The present invention relates to a process of treating fibrous articles with microcapsules containing hydrophobic treating agent and, particularly, relates to a process of treating fibrous articles such as yarn, woven and knitted fabrics and non-woven fabric with microcapsules containing a nonaqueous solvent solution of hydrophobic treating agent.

Generally, it is already known that the microcapsules containing a hydrophobic liquid are prepared by the following methods.

1. Coacer vation method in which electrolytic polymer such as gelatin and gum arabic is used as a protective colloid.

2. lnterfacial polymerization method which is utilized for preparation of synthetic resin such as polyesters, polyurethanes, polyamides and polystyrene.

3. Phase separation method which is carried out in a three component system containing cellulose derivatives such as ethyl cellulose, solvent for polymer and non-solvent.

The microcapsules prepared through the conven-- tional methods mentioned above are applied to several uses such as pressure sensitive paper which is the socalled no-carbon paper and ink for ball point pens. The conventional microcapsules prepared by the conventional process have sufficient tenacity, water proof property and stability only for the above-mentioned usual uses. When the conventional microcapsules are applied to treatment of the fibrous articles such as yarn, net, woven and knitted fabric and non-woven fabric, it is industrially very difficult to uniformly impregnate the fibrous article with the solution contained in the microcapsules because of the tenacity of the microcapsules is so great that breakage of the microcapsules is very difficult.

The conventional method for preparing the microcapsules had disadvantages such as the size of the resultant microcapsules is non-uniform and that when polyurethanes or epoxy resins are used for forming the shell of the microcapsule together with amine type hardening agent, the resultant microcapsules have a tendency to change color with lapse of time. In view of these disadvantages, it is unfavorable that the conventional microcapsules are applied to the field of treatment of fibrous articles.

On the other hand, in the field of treatment offibrous articles, the new technique using a non-aqueous solvent is the so-called non-aqueous treatment process in which the treating agent is dissolved in the nonaqueous solvent. The non-aqueous treatment is effective for obtaining dyed or finished fibrous articles having excellent qualities at a low cost and to solve problems of waste water-discharging which have been recently brought into question.

However, the following disadvantages are found in the nonaqueous treatment process.

l. The solvent has frequently high toxicity to humans or a bad smell.

2. The solvent has frequently high corrosion property for the container.

3. Thus, the solvent container and the solvent solution of the treating agent and the treating apparatus must be gas-tightly closed in order to protect workers from the toxicity or the odor.

When the fibrous article consists of two or more kinds of fibers, or when the fibrous article is subjected to two or more kinds of treatments, it is frequently required to mix two or more treating agents with each other in a treating bath. If the treating agents have no or a low miscibility with each other or if there is insufficient stability of the mixture, the treating agents should be separately applied to the fibrous articles.

An object ofthe present invention is to provide a process of treating fibrous articles with microcapsules having a low tenacity at break and containing a nonaqueous solvent solution of hyrophobic treating agent using an open treating apparatus.

Another object of the present invention is to provide a process of treating the fibrous article for two or more purposes by using the microcapsules containing the non-aqueous solvent solution of treating agent, which process can be performed easily and at low cost.

Further objects and features of the present invention will be illustrated by the detailed description set forth hereinbelow.

The term microcapsule as used herein refers to a specific capsule having a very small size and being composed of a core constituent consisting of a liquid and a wall constituent covering the liquid.

According to the present invention, the microcapsule has a tenacity at break of at most 50 g/cm and comprises a core constituent consisting of-a solution of a hydrophobic agent for treating the fibrous articles in a non-aqueous solvent and a wall constituent covering the core constituent and being composed of a thin synthetic resin shell.

The microcapsule is prepared through the following process. A non-aqueous solvent solution containing a polymerizing compound such as prepolymer, polymerizable monomer and existing polymer and a desired treating agent is dispersed in an aqueous solution containing dispersing agent or protective colloid and hardening agent for the polymerizing compound or in water. Generally, the dispersing is carried out by slowly dropping the non-aqueous solvent solution into the aqueous solution or water while vigorously stirring. In this dispersion, the polymerizing compound is interfacially polymerized at the interfaces between the dispersed particles of the non-aqueous solvent solution and the aqueous solution or water. The interfacially polymerized polymer forms the wall constituent of the microcapsules. The wall constituent contains the nonaqueous solvent solution of the treating agent forming a core constituent.

The treating agent usable for the present invention may be selected from compounds effective for treating the fibrous articles for the desired purpose. The treating agent may be adhered, absorbed or reacted with the fibrous article so as to improve or modify the chemical or physical property of the fibrous article. The treating agent may include, for example, elasticity improving agent, antipilling agent, flame proof agent, pleating agent, ultra-violet ray absorber, anti-static agent, soil proof agent, water repellent agent, crease proof agent, oil repellent agent, antishrinking agent, heat proof agent, softening agent, cross-linking agent, reactive monomer, coloring material such as dye and pigment.

The elasticity improving agent may be selected from poly-organosiloxane diols and the antipilling agent may be selected from urethane prepolymers.

The ultra-violet ray absorber may be selected from benzophenone type compounds, for example, 2,2- 4,4'-dimethoxy benzophenone, 2,2-dihydroxy-4,4'- dimethoxy benzophenone, and Z-hydroxy-octoxy benzophenone. The softening agent may be dimethyl polysiloxane and dimethyl-polysiloxane diol, and the flame proof agent may be tris-(2-bromoethyl) phosphate, tris-(2-chloroethyl) phosphate, tris-(dichloropropyl) phosphate, tris-(2,3-dibromopropyl) phosphate, bis-( 2- chloroethyl)-2-chloroethane-phosphonate, pentabromo-diphenyl ether, tetrabromo-bis-phenol A, l,2,3,4-tetrabromobutane, trimethyl phosphite, bromophthalic acid anhydride and brominated paraffins.

The water repellent agent may be, for example, methylhydrogen polysiloxane and dimethyl polysiloxane diol. The soil proof agent may be, for example, Scotchgard (trade name of a fluorine-containig resin type soil proof agent made by Minnesota Mining & Manufacturing Co., U.S.A). The heat proof agent may be, for example, dimethyl polysiloxane diol and epoxy resin prepolymer. The antishrinking agent may be selected from dimethyl polysiloxane diol, reactive polyethylene and urethane prepolymer.

The wall constituent of the microcapsule may be composed of synthetic resin selected from polyurethanes, silicone resins, polyolefins, epoxy resins, polyamides, and polyesters.

The polyurethane resin for the wall constituent may be selected from toluylene diisocyanate, dimethyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, methyl cyclohexane diisocyanate, triphenyl methane diisocyanate, diphenyl methane diisocyanate,

and polymers prepared through reacting of polyurethane prepolymer having two or more isocyanate terminal groups with a polyvalent amine such as ethylene diamine, hexamethylene diamine, triethyl tetramine, paraphenylene diamino and piperazine, or with a polyvalent hydroxide compound such as 1,5-dihydroxy naphthalene, pyrogallol, 1,4-butadiene diol, glycerin, resorcin, bisphenol A.

The silicone resin may be prepared from organosiloxane prepolymer containing a main chain of polysiloxane of the formulas:

wherein R, R, R" and R' represent, for example, alkyl, 1,1,l-trifluor propyl, cyanopolyalkyl, isocyanate, hydroxyl, methoxyl groups, same as or different from each other. The organosiloxane prepolymer preferably has a degree of polymerization of 2,000 or less so as to dissolve into hydrophobic solvent.

The epoxy resin maybe produced from epoxy compounds to which are added polyvalent amine.

4 The polyester may be prepared, for example, by reacting a halide of polycarboxylic acid such as phthaloyl chloride, l,4-cyclohexane dicarbonyl chloride, phosgene, 4,4'-biphenyl dicarbonyl chloride, adipoyl dichloride, sebacoyl chloride and terephthaloyl chloride with a phenolic compound such as resorcin, bisphenol A, 1,5-dihydroxy naphthalene, pyrogallol, phenolphthalein and primary condensation products of phenol resin.

The polyamide may be formed by reacting, for example, a halide of polycarboxylic acid such as sebacoyl chloride, 4,4-biphenyl dicarbonyl chloride, phosgene,

.terephthaloyl dichloride, isophthaloyl dichloride, 1,4-

cyclohexane dicarbonyl chloride and adipoyl dichloride with a polyamine such as ethylene diamine, hexamethylene diamine, triethyl ene tetramine, paraphenylene diamine and piperazine.

The reactive polyolefin derivative has a reactive radical such as chlorosulfonyl or acid chloride radical. The polyolefin derivative containing the chlorosulfonyl radical is prepared by reacting polyethylene with chlorine and sulfurous acid gases. The chlorine atoms in the compound are effective to restriction of stereospecific property of the polyethylene chain and control of crystallization of the chain, in order to form a flexible polymer. In the chlorosulfonated polyethylene, the chlorine atoms are contained in primary or secondary form, and

the chlorosulfonyl radical exist in primary, secondary or tertiary form and form a film by salt forming, crosslinking or sulfonic acid-linking with a compound having active hydrogen atom. Additionally, the chlorine atom existing at B-position of the chlorosulfonyl radical has chemical activity. To improve the stability of the microcapsules in water, it is desirable that the wall constituent made up of the reactive polyolefin derivatives has a high elasticity. In order to meet the requirement, it is required that the derivative contains 25 to 30 percent by weight of chlorine and 1.5 percent by weight of sulphur, in other words, one atom of chlorine per 7 atoms of carbon and one unit of chlorosulfonyl group per atoms of carbon.

The reactive polyolefin derivatives containing, as the reactive group, acid chloride group are prepared by reacting, for example, homo-polymer or copolymer of olefin derivatives having carboxylic group with phosphorous pentachloride. Such derivatives contains at least 0.1 percent by mol of acid chloride group and at least 50 percent by mol of olefin group. The polymer containing the carboxylic group suitable for preparing the reactive polyolefin derivative containing the acid chloride group may be selected from, for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-itaconic acid copolymer, ethylene-methyl-hydrogen maleate copolymer, ethylene-maleic acid copolymer, ethylene-acrylic acidmethyl methacrylate copolymer, ethylene-methacrylic acid-ethyl acrylate copolymer, ethylene-itaconic acidmethyl methacrylate copolymer, ethylene-methylhydrogen maleate-ethyl acrylate copolymer, ethylenemethacrylic acid-vinyl acetate-copolymer, ethyleneacrylic acid-vinyl formate copolymer, ethylenepropylene-acrylic acid copolymer, ethylene-styrene-acrylic acid copolymer, ethylene-methacrylic acidacrylonitrile copolymer, ethylene-fumaric acid-vinyl methyl ether copolymer, ethylene-vinyl chlorideacrylic acid copolymer, ethylene-vinyl-idene chlorideacrylic acid copolymer, ethylene-vinyl fluoridemethacrylic acid polymer, ethylene-chlorotrifluoroethylenemethacrylic acid copolymer, polyethylene grafted by acrylic acid, polyethylene grafted by methacrylic acid, ethylene-propylene copolymer grafted by acrylic acid, ethylene-butene-l copolymer grafted by methacrylic acid, ethylene-vinyl acetate copolymer grafted by methacrylic acid, polypropylene grafted by acrylic acid, polypropylene grafted by methacrylic acid, polybutene grafted by acrylic acid, poly-3-methyl butene grafted by acrylic acid and polyethylene grafted by acrylic acid and methyl acrylate. These polyolefin derivatives having the acid chloride group as the reactive group have a higher activity than that of the polyolefin derivatives having the chlorosulfonyl group, and thus the derivatives having the acid chloride group can self-cross link at low temperature. This point is valuable for preparing the microcapsules of the present invention. Further, it is more effective for accelerating the forming of the core constituent that 5 to 50 percent, preferably l0 to percent byweight of active hydrogen-containing compound is added into the polymerization system.

Tha active hydrogen-containing compound may be selected from compound containing amino, imino, hydroxyl, carboxyl, or epoxy radical, particularly, benzidine, 4-4'-methylene bis-O-chloroaniline, 3'-3- dichlorobenzidine, hexamethylene diamine, 1,3- diamino propane, 1,2-diamino propane, and piperazine.

The wall constituent of the microcapsules may be composed of a synthetic resin shell formed by reaction between a prepolymer different from the hydrophobic treating agent and a hardening agent. Also, the wall constituent may be formed by interfacial polycondensation ofthe hydrophobic treating agent with a hardening agent or dispersing medium. For example, the wall constituent is formed from urethane prepolymer by interfacial polycondensation of the urethane prepolymer dispersed in water or an aqueous solution containing amine compound at interfaces between the dispersed particles and the dispersing medium.

According to the present invention, the solvent for the hydrophobic treating agent may be selected from non-aqueous solvents which are never mixcible with the dispersing medium and never swell or dissolve the synthetic resinous wall constituent. The solvent may be selected from tetrachloromethane, tetrachloroethylene. trichloroethylene, xylene, toluene, 1,1,1- trichloroethane, benzene, ethyl benzene, industrial gasoline, chloroform, methylenechloride, tetrachloroethane, tetrachlorodichloroethane and mixtures thereof.

In the preparation of the microcapsules of the present invention, the hydrophobic treating agent for the fibrous article and the polymerizing compound for forming the wall constituent are used at a ratio of 100:1 to 10,000: 1. The non-aqueous solvent solution containing the treating agent and the polymerizing compound is finely dispersed in an aqueous dispersing medium into particles having a size of at most 100 um, and then the polymerizing compound interfacially forms a polymer at interfaces between the dispersed particles and the dispersing medium.

Preferably, the polymerizing compound is selected from urethane prepolymer having at least two -NCO group at molecular terminals thereof, polyorganosiloxane diol, polysulfide prepolymer, epoxy resin obtained through reaction between bisphenol A and epichlorohydrin, and reactive polyolefin derivative having a reactive group such as an acid dhloride or thionyl chloride group.

As stated hereinbefore, the proportion by weight of chloride wall constituent with respect to the core constituent is in a range from 1 500 to l 5,000. If the proportion is lower than 1 10,000. the resultant wall constituent is insufficient due to too thin a thickness and a very low tenacity. lfthe proportion is higher than l 100, the tenacity of the resultant wall constituent is too high for breakage thereof and it is very difficult to remove the broken wall constituent from the applied fibrous article. ln view of this, the proportion of the wall constituent with respect to the core constituent must be in the abovementioned range. Only in this proportion, the microcapsules having the tenacity at break of at most 50 g/cm can be obtained. Only such microcapsules can be industrially applied to the fibrous article at favorable conditions. In order to finely and uniformly disperse the nonaqueous solvent solution, it is preferable that the proportion by weight of the nonaqueous solvent solution with respect to the dispersing medium is at least 1 5, more preferably 1 l to l 3. Further, it is desirable for the above purpose that dispersing medium contains a proper dispersing agent.

When the nonaqueous solvent solution of the treating agent has a low viscosity and is enclosed into the wall constituent by the above-mentioned process, the resultant microcapsules are desirable. However, when the non-aqueous solution has a high viscosity, it is very difficult to obtain the microcapsules having a thin wall constituent which is suitable for easily breaking at 8 small breaking force and high stability. That is, in the dispersing of the non-aqueous solvent solution, if the viscosity of the dispersed solution is too different from that of the dispersing medium, it is very difficult to form the dispersed solution into very fine and stable particles. Therefore, the proportion between these viscosities is preferably at most 1 5, more preferably 7 l to l 3.

In order to regulate the viscosity of the dispersing medium, it is effective to add a certain viscosity regulating agent. For smoothly carrying out the interfacial polymerization for forming the wall constituent, it is required that the viscosity regulating agent never participates in the interfacial polymerization and never dissolves into the dispersed non-aqueous solvent solution. For example, gelatin or gum arabic, as a viscosity regulating agent, is undesirable for the above purpose owing to its tendency to lower the velocity of the interfacial polymerization and adhering the resultant microcapsules to each other into double or multiple capsules, sometimes, large masses. This adhering is due to adhesiveness of the insufficiently polymerized wall constituent. Further, gelatin and gum arabic have the defects that they tend to adhere to the surfaces of the resultant microcapsules and those adhered tend to be insufficiently removed by washing. As stated above, the important factors for the process of the present invention are the miscibilities of the viscosity regulating agent to the dispersed solution and the dispersing medium and behavior of the viscosity regulating agent for the interfacial polymerization. In consideration of this, the viscosity regulating agent for the process of the present invention should be selected from a certain hydrophilic polymer such as sodium alginate, hydroxyethyl cellulose and carboxymethyl cellulose. Particularly, sodium alginate is most preferable for the process preparation of the microcapsules of the present invention due to its easy removing property from the surfaces of the resultant microcapsules by water rinsing.

The size of individual microcapsules produced in the polymerization system depends upon the size of the dispersed particles in the aqueous dispersing medium. In order to finely disperse the non-aqueous solvent solution, the mixture of the non-aqueous solvent solution and the aqueous dispersing medium is vigorously stirred with a stirrer such as a screw type, friction type, spiral type and homomixer type stirrers at for example, 8,000 or more, rotations per minute into very fine particles of 30 am or a lesser size. Generally, when the stirrer is driven at 200 rpm. or less, the resultant microcapsules tend to have a size of 500 #m or more. However, in the treatment of the fibrous articles, when the size of the microcapsules is too large, the size distribution is uneven and after the microcapsules applied to the fibrous article have been broken, it is difficult to remove the wall constituent residues from the fibrous article. Further, in this case, the impregnation of the fibrous article with the treating agent become uneven. Therefore, it is desirable that the size of the microcapsules is 100 1m or less, more preferably 30 .Lm or less. Accordingly, the velocity of stirring for the dispersion is preferably 200 rpm. or more, more preferably, 8,000 rpm. or more. Further, it is possible to easily obtain the superfine microcapsules of 5,u. m size or less through supplementarily utilizing an ultrasonic stirrer together with the usual stirrer.

The microcapsules of the present invention may be applied to the fibrous article in various manners such as blowing or electrostatic application of the dry microcapsules and padding or spraying application of an aqueous suspension of the microcapsules. The applied microcapsules are broken on the fibrous article by a suitable means such as a pressing roller mangle so as to impregnate the fibrous article with the content solution of the core constituents. Sometimes, the microcapsules may be broken by heating them to a temperature higher than the melting point of the wall constituent. The impregnated fabric may be heat-treated at a high temperature so as to fix the treating agent.

In this treatment of the fibrous article, it is desirable that the microcapsules are applied in an amount of to 400 percent, more preferably, to 100 percent based on the weight of the fibrous article. Also, it is allowed that two or more kinds of microcapsules which contain treating agents different from each other are applied to the fibrous article sometime within the process.

In order to break the microcapsules applied to the fibrous article, generally, the fibrous article is pressed with press rollers, squeezing rollers or a mangle at a pressure of 0.1 to 3 kg/cm If necessary, the fabric is subjected to heat treating at a temperature of 5 to 200C for 10 seconds to minutes, preferably, at 80 to 180C temperature for 30 seconds to 5 minutes.

The individual microcapsule may contain two or more kinds of treating agents. The desired microcapsules may be mixed with other kinds of microcapsules at a desired proportion.

According to the present invention, the treating agent which needs a non-aqueous solvent can be easily applied to the fibrous article by utilizing the microcapsules in dry particulate form or aqueous suspension form.

Even if two kinds of treating agents are needed to treat the fibrous article being composed of two kinds of fibers or filaments and further, if the treating agents are insufficiently mixcible with each other, it is possible that the fibrous article is treated with a mixture of two kinds of microcapsules each containing one kind of treating agent through one application.

Further, if the microcapsules are applied in aqueous suspension, it is possible that desired treating agents such as a moisture absorbing agent, softening agent, soil release agent, antistatic agent, dye and other hydrophilic treating agents are added into the aqueous suspension so that the fibrous article is treated with the microcapsules together wiith the added treating agent.

For example, the microcapsules containing a crease proof agent are suspended in an aqueous solution containing a moisture absorbing agent andthe resultant suspension is applied to the fibrous article. The moisture absorbing agent may be selected from compounds prepared by addition of 2 to 50 mol of ethylene oxide or propylene oxide to e-caprolactam, compounds prepared by addition of 2 to 50 mol of ethylene oxide or propylene oxide to e-caprolactam aligomer (dimer or trimer), sodium N-acylamino acetate, sodium N-acyla-amino propionate and sodium N-acyl-B-amino propionate.

The applied fibrous article passes through a pair of rollers in order to squeeze excess suspension and break the microcapsules so as to impregnate the fibrous article with the non-aqueous solvent solution of the crease proof agent flowed out from the broken microcapsules. At the same time, the fibrous article is impregnated with the moisture absorbing agent. Needless to say, the moisture absorbing agent may be contained in microcapsules if it is soluble in the non-aqueous solvent. Also, the moisture absorbing agent may be previously applied to the fibrous article before the application of the microcapsules. However, the aqueous solution of the moisture absorbing agent is effective for suspending the microcapsules in a favorable condition and the resultant fibrous article fromthe aqueous suspension has a superior crease recovery and durability. In view of this, the suspension containing the microcapsules and the moisture absorbing agent is preferably used at a high economical advantage. The above-stated advantage is caused from the fact that in microscopic view, the crease-proof agent flowed out from the broken microcapsules is unevenly or discontinuously distributed in the fibrous article and thus the moisture absorbing agent is distributed at portions not or insufficiently occupied by the crease proof agent.

Due to the uneven or complicated distribution of' the crease-proof agent and the moisture absorbing agent, the treated fibrous article obtains the superior crease recovery property and moisture absorbing property.

However, the complicated distribution of two or more treating agents on the fibrous article are never found in the conventional application in which the treating agents are dissolved, emulsified or suspended into a bath together,

Furthermore, in order to obtain the preferable distribution of the treating agents, it is necessary that the non-aqueous solvent solution of the treating agent flowed out from the broken microcapsules does not diffuse to too wide a region. Accordingly, the nonaqueous solvent solution of the treating agent should have pertinent viscosity, diffusing coefficient and contact angle. In consideration of this, in order to achieve satisfactory crease-proof and moisture absorbing properties on the fibrous article the size of the microcapsule should be in a range of at most SOO/ m, preferably at most IOOMm and more preferably at most 30l m. In this case, the size of the microcapsules less than ll m is undesirable because of the lowering effect of the complicated distribution.

The non-aqueous solvent solution ofthe crease-proof agent preferably has a viscosity of up to 2,000 cp, more preferably, to 1,000 cp in order to have a pertinent diffusion property in the fibrous article and to keep the effect of the moisture absorbing agent. In view of this, urethane prepolymer, as a crease-proof agent, should be dissolved into a content of 5 to 60 percent by weight, preferably 20 to 50 percent by weight, acrylic resin prepolymer l to 70, preferably 5 to 50 percent by weightand silicone resin prepolymer 5 to 100, preferably, to 100 percent by weight depending on its molecular weight.

The application quantity of the microcapsules may be regulated depending on the kind of the fibrous article, kind, viscosity and concentration of the treating agent and size of the microcapsules used.

From our experiments, a proportion of the total area occupied by the microcapsules distributed on the fibrous article with respect to the area ofthe fibrous article is preferably 1 2 to l 50, more preferably 1 4 to l 30. if the proportion exceeds 1 1 2, the moisture absorbing property of the resultant fibrous article is unsatisfactory and if the proportion is less than 1 50, the

crease recovery is unsatisfactory. Actually, the content of the microcapsules in the aqueous suspension is preferably in a range from 2 to 10 percent by weight.

The fibrous fabric treated through the above-stated process is impregnated with 0.3 to 6.0 percent by 'weight of the creaseproof agent distributed discontinuously and 0.1 to 5.0 percent preferably 0.2 to 3.0 by weight of the moisture absorbing agent continuously distributed at portions between the portions occupied by the crease-proof agent.

In each treatment, the crease-proof agent contained in the microcapsules may be a mixture of two or more compounds and a mixture of two or more kinds of microcapsules each containing a crease-proof agent dif ferent from each other may be used.

The fibrous article usable for the present invention may be optionally selected from yarns, knitted fabrics,

woven fabrics, non-woven fabrics and these laminates made up of natural fibers or filaments such as wool, .silk, cotton, ramie and linen and artificial fiber or fila ments such as polyamide polyester polyacrylic polymeric, polyvinyl alcohol, polyolefin, polyvinyl chloride, polyvinyl chloridene and polyurea fiber or filaments, rayon and acetate fibers or filaments.

The process of the present invention has the following advantages.

1. The treatment can be carried out in an open apparatus although a non-aqueous volatile solvent is used, because the volatile solvent is enclosed in the microcapsules.

4. The microcapsules have uniform size and are easily broken due to their very low tenacity.

5. Color of the microcapsules never changes with lapse of time, for example, days.

6. The wall contituent residues of the broken microcapsules are not found on the treated fibrous article according to naked eye observation due to their very thin thickness.

7. The wall constituent is fused at the heat-treating temperature and effects on the fibrous article to im-' prove its treating effect and durability.

EXAMPLE 1 Microcapsules Containing a Silicone Type Elasticity Improving Agent 5 g of resorcin were dissolved in 400 cc of an aqueous solution containing 1 percent of sodium hydroxide. 0.2 g of toluylene diisocyanate, 20 g of organopolysiloxane diol prepolymer having a degree polymerization of 300 and 0.02 g of di-N-hutyl-tin-dilaurate were dissolved in 200 g of trichloroethylene. The trichloroethylene solution was slowly dropped into the aqueous solution at room temperature stirring with a stirrer at 800 rpm. in order to disperse the trichloroethylene solution into very fine particles.

After 1 hour, numerous microcapsules were formed. These composition and features were as indicated in Table 1.

The microcapsules prepared thus were distributed on an acrylic twill fabric to a content of percent based on the weight of the fabric. The fabric was pressed by a pair of rubber rollers having a hardness of 60 at a pressure of 1.0 kg/cm in order to break the microcapsules. Through the press, the fabric was substantially evenly impregnated with the core constituent solution of the microcapsules and the wall constituent residues remained on the periphery surface of the press roller. The fabric was dried at 80C temperature and then heat-treated at C temperature for 5 minutes. The resultant fabric had a preferable hand feeling and excellent compression elasticity and crease recovery as shown in Table 2.

Table 2 Item Compressive Elasticity Crease Recovery fl *2 Hand Fabric Percentage Elasticity Warp Weft Feeling Treated Highly rigid fabric 21.8 91.8 90.5 9.5 and resilient Un- Insufficienttreated 20.5 83.8 83.2 87.3 ly rigid and fabric resilient Note: *1 Compressive elasticity was determined by the following manner.

Four pieces of fabric to be tested are superimposed and compressed at a weight of glcm for 1 minute into a thickness of t. Then, the compressed testing pieces are further compressed at a weight of 300 g/cm for 1 minute into a thickness of I, followed by releasing the compression for 1 minute into a thickness of Percentage compression B-method. V

and elasticity are given by the following equations:

EXAMPLE 2 Microcapsules Containing a Flame-Proof Agent for 1 hour, numerous microcapsules having a composition and features as indicated in Table 3 were obtained.

Laundering was carried out using an aqueous solution of l g of Zabu (trade name of a detergent made by Kao Sekken Kabushiki Kaisha, Japan) in l l of water at a liquor ratio of 1 50 at C temperature for 60 minutes.

EXAMPLE 3 Microcapsules Containing an Antistatic Agent 4 g of resorcin and l g of l,5-dihydroxy naphthalene were dissolved in 200 cc of an aqueous solution of 2 percent sodium hydroxide. Into the aqueous solution, 90 g of a l,l,l-tri-chloroethane solution containing 0.l5 g of diphenylmethane diisocyanate and 5 g of an antistatic agent was slowly dropped with stirring by a stirrer at 600 rpm. at room temperature in order to disperse the l,l,l-trichloroethane solution into very fine particles.

After the 1,1,l-trichloroethane solution was uniformly dispersed, the temperature of the system was raised to C and maintained at this temperature for 2 hours with stirring. The result was numerous microcapsules having the composition and properties as illustrated in Table 5.

v T 40 Table 5 Table 3 v l,l ,l-trichloroethane Tetrachlomethylene Solution Core constituent solution containing antistatic agent Composition Core constituent of Unflame 3BP Composition Wall constituent Polyurethane 5 wall constituent Polyurethane Ratio b weight of w Ratio by weight of wall 00 to core 0 l' eiiz ii ty at break lag 2 Tenacity at break g3 gg Size 200 400 um .S'Ze pm The microcapsules were uniformly applied to a polyethylene terephthalate broad cloth to a content of 70 percent based on the weight of the cloth and then pressed with a pair of rubber rollers having a hardness of 70 at a pressure of 1.0 kg/cm The cloth was uniformly impregnated with the core constituent solution flowing out from the broken microcapsules. The cloth was dried at 70C temperature followed by heattreating at 160C temperature for 30 seconds. The resultant treated cloth had an excellent flame proof property as illustrated in Table 4 Table 4 item Frictional static voltage (volt) *4 Fabric Before laundering After laundering Treated fabric 120 3,500 Untreated fabric 12.000 l0.500

Flame Proof Property Before laundering After laundering ltem Fabric Treated cloth 5 4 Untreated cloth l l *4 Frictional static voltage was determined by means of a rotary static tester made by Kowa Shokai. Japan. using a friction element consisting of 60 cotton broad cloth.

EXAMPLE 4 Microcapsules Containing Water Repellent Agent Note:

4 g of resorcin was dissolved into 200 cc of an aqueous solution containing 0.8% by weight of sodium hydroxide and 105 g of a tetrachloroethylene solution containing 0.07 g of hexamethylene diisocyanate, 5 g of methyl-hydrogen-polysiloxane prepolymer having a degree of polymerization of 20, l g of dimethyl polysiloxane diol prepolymer having a degree of polymerization of 300 and 0.08 g of n-dibutyl tin dilaurate was prepared. The tetrachloroethylene solution was slowly dropped into the aqueous solution at room temperature stirring with a stirrer at 900 r.p.m. in order to disperse the tetrachloroethylene solution into very fine particles. After the uniform dispersion was completed, the system was heated to a temperature of 40C and remained at this temperature for 1 hour while stirring. The result was microcapsules having a composition and properties as illustrated in Table 7.

Table 7 Tetrachloroethylene solution containing methyl hydrodion polysiloxane prepolymer and dimethyl polysiloxane diol Core constituent prepolymer Composition Wall constituent Polyurethane Ratio by weight of wall to core l:l.500 Tenacity at break ll g/cm Size I 20 30 um Table 8 Item Water-repellent property *5 Fabric Before laundering After laundering Hand feeling Treated Elegantly soft fabric l l00 & resilient Untreated 30 30 Unfabric satisfactory Note: Water repellent property was determined by AATCC,

22-1952. spray method.

EXAMPLE 5 Microcapsules Containing Oil Repellent Agent 6.0 g of bisphenol A was dissolved in 240 cc of an aqueous solution of 1 percent sodium hydroxide. Also, 0.1 g of hexamethylene diisocyanate and 10 g of Scotchgard FC-310 (trade name of an oil repellent agent made by Minnesota Mining & Manufacturing Co., U.S.A.) were dissolved into 120 g of l,l,ltrichloroethane. The trichloroethane solution was slowly dropped into the aqueous solution stirring with a stirrer at 1 1,000 r.p.m in order to disperse the trichloroethane solution into very fine particles. The dispersion was heated to 50C and maintained at this temperature with stirring. The result was microcapsules having the composition and properties as indicated in Table 9.

TABLE 9 Solution of Scotchgard FC- Core constituent 310 in l.l,l-trichloroethaue Composition Wall constituent Polyurethane Ratio by weight of wall to core Tenacity at break Size The microcapsules prepared thus were applied to a double interlock knitted fabric made up of worsted yarns and then broken in the same manner as that of Example 2. The fabric was impregnated with Scotchgard flowing out from the broken microcapsules. The impregnated fabric was dried at 40C temperature and then heat-treated at C temperature for 3 minutes.

For comparison, the same fabric as that of the present Example was impregnated with a solution of Scotchgard FC-3l0 in 1,1,l-trichloroethane at an impregnating quantity of 3.0 percent based on the weight of the fabric. The results of the present and comparison Examples had oil and water repellent properties as shown in Table 10.

The laundering was carried out by the manner as indicated in Example 2.

Table 10 shows the fact that the treated fabric of the present invention has excellent oil and water repellent properties similar to that of the comparison Example which of course is normal for Scotchgard 310.

EXAMPLE 6 Microcapsule Containing a Flame Proof Agent 20 g of 2,3-dibromopropyl phosphate, 0.2 g of dimethyl polysiloxane diol having a degree of polymerization of 500 and 0.4 g of n-dibutyl tin dilaurate were dissolved in 400 g of trichloroethylene. The solution was slowly dropped into 2,000 cc of water with stirring at 6,500 rpm. at room temperature so as to form numerous very time dispersed particles of the solution. The dispersion was heated to 60C and maintained at this temperature for 1 hour while stirring. The result was microcapsules having the composition and properties as indicated in Table l l.

Table 11 Solution of tris-2,3-dibromo- Core constituent propyl phosphate in tri- Table 14 chloroethylene 5 Composition item Frictional static voltage (volt) Wall constituent Silicone resin Fabric Before laundering After laundering Ratio by weight of wall Treated fabric 100 3.500 to core l;3 Untreated fabric 12.000 10.500 Tenacity at break 5 g/cm Size 40 50 um EXAMPLE 8 The m'crocapsules was apphed to a polyethylene Microcapsules Containing Oil Repellent Agent terephthalate broad cloth to a content of 80 percent A Solution containing 10 g Scotchgard FC 310 based on the weight of the fabric followed by breaking 05 g of dimethyl polysfloxane diol having a degree of them by Pressing at aPressure of kg/Cm Wlth a P polymerization of 800 and 0.2 g of n-dibutyl tin succin- Of rubber Toners haYmg a hardness of ate in 500 g of tetrachloroethylene was dispersed into The fabr'c was l y lmpregnated wlth h flame 3,000 cc of an aqueous solution containing 0.3 percent Proof flowing out m the bfoken f p' by weight of dispersing agent by stirring at 11,000 Sules- The lmpregnated fabrlc was dned at 70 C r.p.m. at room temperature. After stirring for 3 hours, perature and then heat-treated at 160C temperature the dispersion resulted in microcapsules suspended in for 30 seconds. The resultant fabric had an excellent the aqueous solution The microcapsules prepared thus flame proof property before and after laundering as inhad the composition and property as indicated in Table dicated in Table 12. Laundering was performed by the 15. manner as indicated in Example 1. Table 15 Table 12 Solution of Scotchgard 310 Item Flame proof property I composmon Core constituent in tetrachloroethylene Fabric Before laundering After laundering Wall constituent Silicone resin Treated fabric 5 i 4 Ratio by weight of wall Untreated fabric 1 l to core 1:1,000

Tenacity at break 10 g/cm' Size 10 30 am EXAMPLE 7 The microcapsules were applied to a double inter- MlcrocaRsules Contammg an Antlstatlc Agmt lock knitted'worsted fabric and broken in the same A solution of 5 g of antistatic agent, 1.0 g of diethyl manner as that of Example 6 Polysiloxane diol and g of Stannous ocfoate 800 The fabric impregnated with the oil repellent agent 2 tetrachloroethylene was Q y pp Into 4,900 0f 40 was dried at 40C temperature and then heat-treated at an aqueous Solutlon Contammg 1 Percent y Weight of 140C temperature for 3 minutes. The result had supedIu fllgmate stlffmg at 4,000 4 at TOOm rior oil and water repellent properties as shown in perature so as to disperse the tetrachloroethylene solu- T ble 16, tion into very fine particles. The dispersion was main- Table 16 tained for 2 hours, while stirring. The result was numerous microcapsules having the composition and properw ater Oil [16S 21 Illus r In Table ltem repellent property repellent property T bl 13 Before After Before After a e Fabric laundering laundering laundering laundering Solution of antistatic agent 523 2225 2 75 7O 96 95 Core constituent in tetrachloroethylene Composition Example 76 72 98 96 Wall constituent Silicone resin Ratio by weight of wall The comparison Example was carried out in the same core 1:800 manner indicated in Exam 1 5 Tenacity at break 20 g/cm p e Size pm Table 16 shows the fact that the oil repellent fabric of the present invention had superior oil and water repellent properties similar to that of the comparison Ex- The microcapsules prepared thus as ppl d to a 60 ample in which Scotchgard 311 was applied to the fabpolycapramide tricot fabric to a content of 100 percent rig i a t da d manner, based on the weight of the fabric followed by breaking then by pressing with a pair of rubber rollers having 70 EXAMPLE 9 hardness at a pressure of 1.5 kg/cm Microcapsules Containing a Dye The fabric was uniformly impregnated with the anti- 65 A solution of 0.5 g of a disperse dye, 0.5 g of methylstatic agent flowing out from the broken microeapsules. The impregnated fabric was air dried and then heat-treated at C for 1 minute. The resultant fabric phenyl polysiloxane diol and 0.1 g ofn-dibutyl tin dioctylate in 1 ,000 g of trichloroethylene was dispersed into 5,000 cc of an aqueous solution containing 0.2 percent 17 by weight of earboxymethyl cellulose of 40C temperature by slowly dropping while vigorously stirring at 12,000 rpm. The dispersion was heated'to 60C and Table 19 Percent of fading of dyed fabric il'illmaintained at this temperature for 1 hour while stirhem a d by Fude-O-mcmr r h ring. The dispersion formed numerous microcapsules 5 F! I having the composition and properties as shown in Dye Table 17. and con- Untreated Treated Comparison concentration fabric fabric fabric Table 17 7( l0 Supranol Brilliant Solution of disperse dye Red 65W 17 30 5 g Core constituent in trichloroethylerie Xykne Fast Blue T Composition BL 40 5 IO Wall constituent Silicone resin Kiton Green V 2.0% 90 60 60 Ratio by weight of wall 15 Rcsoiine Brilliant to core 112,000 Blue PBB 0.3% 50 l2 e y break 8 g/Cm' Diacelliton Brown Size 5 10 a 0 0.5% 60 20 20 Note: *6 Supranol Brilliant Red 6BW is trade name of an acid dye 20 (Cl Acid Violet 97) made by Bayer, Germany. accordance wlth the manner mdlcated Example Xylene Fast Blue BL is trade name of an acid dye (Cl. 6, the microcapsules were applied to a trieot fabric ACid Blue59) i by Sandoz, S itzerland. consisting of diacetate fibers and then broken in order T name of and dye 440250 I made by Ciba, Switzerland. to impregnate the fabric with the dye solution. The f b- Resoline Brilliant Blue PBB is trade name Ora disperse dye ric was dried at 60C temperature and then heate by B e t Q Diacelliton Brown (J IS trade name ofa disperse dye made treated at 170 C temperature for 1 minute. The resulby Mitsubishi Kim Japan. tant fabric had been dyed deep blue.

EXAMPLE 10 Table 19 shows the facts that the treated fabrics of the present Example had a light fastness higher than Mlcrocapsules Contammg an ultra'vlolet Ray that of the untreated fabrics, respectively, and that the Sorbet light fastness ofthe treated fabrics ofthe present Exam- A 501mm OfO-S g of z'hydroxy'fl'octoxy benzophe" ple is similar to those of the comparison fabrics which none, 1 g of y y 'p y e and g or were treated by the conventional manner stannous Octoate in 800 g of 1,1,l-tr1chloroethane was 3s dispersed into 4,000 cc of water by slowly being EXAMPLE l1 dropped at room temperature While vigorously Stirring Treatment of a Jersey Fabric Consisting of False 61000 -P- The dlspersleh heated to and Twisted Textured Polycaproamide Yarns for Improvmaintained at this temperature for 2 hours while stiri i El i i ring. The dispersion was converted to microcapsules 4O 1 Th preparation f ic s le contai i g an having the composition and properties as shown in l i i improving agent Ta 0.75 of dimethyl polysiloxane diol prepolymer having Table 18 a degree of polymerization of 800, 0.1 g of a polyurethane prepolymer and 0.01 g of di-n-butyl tin dilaurate Solution of were dissolved into 5 0 g of trichloroethylene. The tri- Core constituent oetoxybenzophenone in chloroethylene solution was dispersed into 600 cc of C I hhl'mchlmeelhahe aqueous solution containing 1 g of dispersing agent by omposltion Wu constituent Smwnc min slowlydropping while stirring at 8,000 rpm. After the dropping had been completed, the stirring was contin- Rmie by weight ued for 10 minutes. 30 cc of an aqueous solution con- 10 b ht f th] (1' b d Tenacity at break 15 g/cmz taining percent y weig o e y ene iamine ase Size 50- 60 a on the total weight of the solution were dropped into the dispersion while stirring and then stirred for 30 minutes at room temperature. Through the procedure, In accordance with the same manner as e of Exam the urethane prepolymer having diisocyanate residue P the P l PP t0 h polyca was reacted with ethylene diamine at interfaces be- Pramlde taffeta fabrics Whlch e ye Varlous colors tween water and the dispersed fine particles of the tri' wlth held or disperse y 'hdcated Table 19 and chloroethylene solution so as to produce solid polymer then broken on the fahl'les- The y fahhes l e which forms the wall constituents of the microcapsules. Hated Wlth the ultra-Violet y e was drled The resultant microcapsules contained trichloroethand then heat-treated at 150C temperature for 2 ylene solution of dimethyl polysiloxane diol prepolyhOUIS' The resultant y fahrles had a superlof hght mer and di-n-butyl tin dilaurate as the core constituent. fastness higher than that of the untreated fabrics and Th microcapsules were recovered h h i comparison treated fabrics which were treated with a benzene solution of the ultra-violet ray absorber. The results were shown in Table 19.

tation water-rinsing and filtration.

The resultant microcapsules had the composition and properties as indicated in Table 20.

Table 20 Solution of 1.57: by weight of dimethyl-polysiloxane diol Core constituent of di n-butyl tin dilaurate in trichloroethylene Composition Wall constituent Polyurethane Ratio by weight of wall to core 1:500 Tenacity at break 12 g/cm Size 20 30 um 2. Treatment of the fabric The microcapsules prepared thus were uniformly applied to a triple interlock jersey fabric prepared from false twisted textured polycapramide yarns of 70 deniers/l8 filaments/2P, to a content of 110 percent based on the weight of the fabric. The fabric was pressed with a pair of rubber rollers having a hardness of 60 at a pressure of 1.5 kg/cm in order to break the microcapsules. The wall constituents of the broken microcapsules maintained on the peripheral surface of the roller and the core constituent flowed out from the broken microcapsules and impregnated the fabric. The impregnated fabric was dried at 80C and heat-treated at 150C for 3 minutes. The treated fabric contained 1.6 percent organopolysiloxane based on the weight of the fabric and had the properties as shown in Table 21.

The comparison fabric was prepared by impregnating the same fabric as that of the present Example with 1.6 percent of organapolysiloxane based on the weight of the fabric and then heat-treating the impregnated fabrrc.

EXAMPLE 12 Shrink-Proof Treatment of Worsted Jersey Fabric 1. Preparation of microcapsules 0.15 g of Zeset T (trade name of a reactive polyethylene type shrink proofing agent for W001 fiber made by Du Pont, U.S.A.') and 0.2 g of hexamethylene diisocyanate were dissolved into 100 cc of tetrachloroethylene. The solution was slowly dropped into 170 cc of an aqueous solution containing 4 g of bisphenol A and 1 percent by weight of potassium hydroxide while stirring at 6,500 rpm. so as to disperse the tetrachloroethylene solution into very fine particles. Through this procedure, the hexamethylene diisocyanate reacted with the bisphenol A at interfaces between water and the dispersed particles of the tetrachloroethylene so as to produce a solid polymer forming the wall constituents of numerous microcapsules which contained the core constituent.

The microcapsules prepared thus had the composition and properties as shown in Table 22.

prepolymer and 0.02% by weight 5 Composition Table 22 Solution of Zeset T in Core constituent tetrachloroethylene Wall constituent Polyurethane Ratio by weight of wall to core 1:800 Tenacity at break 12 g/cm Size 30 50 am 2. Treatment of fabric The microcapsules were uniformly applied to a dou ble interlock jersey fabric consisting of H44 worsted yarns to a content of percent based on the weight of the fabric. The fabric was pressed with a pair of rubber rollers having a hardness of 40 at a pressure of 1.0 kg/cm in order to break the microcapsules. The wall constituents of the broken microcapsules remained on the peripheral surface of the rollers and the content solution of the core constituent evenly penetrated into the fabric. The fabric was dried at 70C temperature followed by heat treating at 130C temperature for 1.5 minutes.

The resultant fabric contained 2.4 percent of the shrink proof agent based on the weight of the fabric, and had a shrinkage as shown in Table 23. For comparison, the same fabric as that of the present Example was impregnated with tetrachloroethylene solution of Zeset T to a content of 2.4 percent based on the weight of the fabric and treated in the same manner as stated above.

Table 23 shows the fact that the fabric treated in the present, Example had superior shrink proof properties similar to that of the comparison fabric which was treated by the conventional manner.

EXAMPLE 13 Crease Proof and Water Repellent Treatment for a Polyethylene Terephthalate Fiber/Cotton Blend Fabric l. Preparation of microcapsules containing crease proof and water repellent agents 4 g of methyl-hydrogen polysiloxane prepolymer having a degree of polymerization of 20, 1 g of dimethyl polysiloxane diol prepolymer, 0.06 g of stannous octoate and 0.2 g of Epikote 828 (trade name of an epoxy resin made by Shell Oil Co., USA.) were dissolved into cc of 1,1,1-trichloroethane. The solution was dispersed into 600 cc of an aqueous solution containing 1 g of dispersing agent by slowly dropping while stirring at 8,000 rpm. After the dispersing was completed, 10 cc of a solution of an amine type hardening agent T (trade name of a hardening agent for epoxy resin made by Shell Oil Co.) was dropped into the dispersion. The dispersion was heated to 40C temperature. Through the procedure, Epikote 828 was hardened by action of the hardening agent T at interfaces between water and the dispersed fine particles of 1,1,1-trichloroethane Table 24 Solution of methyl hydrogen polysiloxane prepolymer, dimethyl polysiloxanc diol prepolymer and stannous Core constituent octoate in 1,1,1- trichlorocthane Composition Wall constituent Epoxy resin Ratio by weight of wall to core 1:800 Tenacity at break g/cm Size 30 am capsules remained on the peripheral surface of the press roller and the core constituent flowed out onto the fabric so as to uniformly impregnate the fabric. The impregnated fabric was dried at 60C temperature followed by heat-treating at 130C temperature for 3 minutes.

The treated fabric contained 1.2 percent organo polysiloxane based on the weight of the fabric and had the superior crease recovery and water repellent property as shown in Table 25. For comparison, a same fabric as that of the present Example was impregnated with the l,l,l-trichloroethane solution of the same treating agents as those of the present Example so that the content of the organo polysiloxane produced on the fabric was 1.2 percent based on the weight of the fabric, and dried followed by heat-treating at the same temperatures as those of the present Example.

Table shows the fact that the treated fabric had a crease recovery and water repellent property similar to the comparison fabric which was treated in the conventional manner.

EXAMPLE 14 Treatment for Light-Fade Proofing of Dyed Fabric 1. Preparation of microcapsules l g of 2-hydroxy-4-octoxy benzophenone and 0.1 g of terephthaloyl chloride were dissolved in 100 g of benzene. The solution was uniformly dispersed in 1,200

cc of an aqueous solution containing 1.0 g of hexamethylene diamine by slowly dropping while stirring at 4,800 r.p.m. After the dispersion was maintained at room temperature from 2 hours, a solid polymer was produced at interfaces between water and the dispersed particles of the benzene solution so as to form numerous microparticle wall constituents.

The microcapsules thus obtained had the composition and properties as illustrated in Table 26.

Table 26 Solution of 2-hydroxy-4- Core constituent. octoxy benzophenone in benzene Composition Wall constituent Polyamide Ratio by weight of wall to core 1:500 Tenacity at break 7 g/cm Size 40 60 pm 2. Treatment of fabric The microcapsules were applied to fine polycapramide taffeta fabrics dyed with various disperse or acid dyes to a content of 50 percent based on the weight of the fabric in such a static electrical manner that the microcapsules were distributed on the fabric by brushing through a metallic mesh plate between which and an electrode facing the mesh plate, a voltage of 1,000 to 12,000 volts was applied. The fabric was pressed with a metallic roller at a pressureof 1.0 kg/cm in order to break the microcapsules. Through this procedure, the fabric was uniformly impregnated with the core constituent solution flowing out from the broken microcapsules. The fabric was dried at C temperature for 1 minute.

The treated fabric had superior fed proof properties as shown in Table 27. For comparison, the same fabric as that of the present Example was impregnated with the benzene solution of 2-hydroxy-4-octoxy benzophenone the same as that ofthe present Example and dried at 120C temperature for 1 minute.

Table 27 Percent of fading of dyed fabric As is clearly shown in Table 27, the treated fabric of the present Example had an improved high fastness.

EXAMPLE l5 Flame Proof Treatment of Lace Curtain Made Up of 20 percent by Weight of Polyethylene Terephthalate Filament and 20 percent by Weight of Rayon Filament 1. Preparation of microcapsules A 15 g of Bigol 40BXE (trade name of a halogenated organic phosphorous compound type flame proof agent made by Daikyo Kagaku Kabushiki Kaisha, Japan) and 0.1 g of Desmodur L (trade name of an urethane prepolymer made by Bayer, Germany) were dissolved in 85 g of toluene. The solution was dispersed in' 1,000 cc of an aqueous solution containing 1 g of dispersing agent by slowly dropping while stirring at 6,500 rpm. After the dropping had been completed, the stirring was maintained for 30 minutes and then cc of an aqueous solution containing 10 percent by weight of ethylene diamine was added so as to form numerous microcapsules A from Desmodur L. The resultant microcapsules A had the composition and properties as shown in Table 28.

Table 28 Solution of by weight Core constituent of Bigol 40BXE in toluene Composition 2. Preparation of microcapsules B 10 g of Flame Proof MC trade name of a polyammonium phosphate type flame proof agent made by Nihon Senka Kabushiki Keisha, Japan) and 0.5 g of hexamethylene diamine were dissolved in 90 g of water. The aqueous solution was dispersed in 800 g of trichloroethylene solution containing 0.3 gof Desmodur L by dropping slowly while vigorously stirring at 6,500 rpm. After the dropping was completed, the stirring was continued for 30 minutes so as to produce a solid polymer for forming the wall constituent of the microcapsules at interfaces between the trichloroethylene solution and the dispersed'particles of the aqueous solution. The resultant microcapsules B had the composition and properties as shown in Table 29.

Table 29 Solution of 10% by weight of Core constituent Flame Proof MC in water Composition 3. Treatment of fabric An aqueous suspension containing the microcapsules A and the microcapsules B in a proportion of l to 1 was sprayed onto the lace curtain which consisted of percent by weight of rayonfilaments located at edge portions of the curtain and 80 percent by weight of polyethylene terephthalate located at ground portion thereof and having a weight of 750 g/m The sprayed fabric contained 15 percent of the microcapsules A and 15 percent of the microcapsules B based on the weight of the fabric. The fabric was dried at 50C temperature and then pressed with a mangle having a hardness of 70 at a pressure of 1.3 kg/cm so as to break the applied microcapsules. Through this procedure, the fabric was uniformly impregnated with the flame proof agents flowing out from the broken microcapsules. The fabric was heattreated at C temperature for 3 minutes. Whereas Bigol 40BXE is effective for flame proofing the polyethylene terephthalate fibers and Flame Proof MC is effective for rayon fibers, they cannot be dissolved in each other. Therefore, in the conventional method, these flame proof agents cannot be used together. However, the method of the present invention can resolve the difficulty. The resultant fabric had a superior flame proof property as shown in Table 30. For comparison, the same lace curtain as that of the present Example was treated in such a manner that firstly, the fabric was impregnated with an aqueous emulsion containing Bigol 40BXE at a pickup of 50 percent and then dried followed by heat-treating at 150C temperature and secondly, the fabric was further impregnated with an aqueous solution of Flame Proof MC at a pick-up of r 50 percent and then dried followed by heat-treating.

Table 30 Item Flame Proof Property Polyethylene terephthalate Fabric Original Ater laundering Rayon Untreated fabric 1 l Burnt Non-burnt but Treated fabric 6 5 fall due to melting of polyester Comparison fabric 6 5 portion Table 30 clearly shows the fact that the fabric treated by one spray in accordance with the method of the present invention had a superior flame proof properties same as that of the comparison fabric which was treated through two padding operations.

EXAMPLE 16 while stirring at 6,500 rpm. at room temperature.

After stirring for 20 minutes, 20 cc of an alkalin solution containing 10 percent by weight of bis-phenol A was added to the dispersion and then the dispersion was heated to 30C temperature for 30 minutes. Through the procedure, numerous microcapsules were obtained. The resultant microcapsules had the composition and properties as shown in Table 31,

Table 31 Solution of urethane pro- Core constituent polymer in trichloroethylene Composition Wall constituent Polyurethane Ratio by weight of wall to core 1:1.200 Tenacity at break 8 g/cm" Size 30 40 pm 2. Treatment of fabric The microcapsules prepared thus was applied to a twill fabric made up of Cashimilon fibers (trade name of an acrylic fiber made by Asahi Kasei Kabushiki Kaisha, Japan) so as to contain 100 percent of the microcapsules based on the weight of the fabric and in accordance with the manner indicated in Example 11. The fabric was pressed in the same method as stated in Example 1 l. The pressed fabric was dried at 50C temperature and then heat-treated at 120C temperature for minutes. The resultant fabric contained 1.6 percent of polyurethane based on the weight of the fabric and had the superior properties as shown in Table 32.

Table 32 Crease recovery Treatment for Coloring and Water and Oil Proofing Acetate Fabric 1. Preparation of microcapsules In accordance with the same process as indicated in Example 1 l. numerous microcapsules containg a solution of Scotchgard FC-3l0 and Foron Red FL (trade name of a disperse dye made by Sandoz, Switzerland) were prepared. The resultant microcapsules had the composition and properties as shown in Table 33.

Table 32 Crease recovery ltem Compressive elasticity (original) (/r) Percentage Elasticity Fabric (71 ('71 Warp Weft Untreated fabric 20.5 83.8 85.5 87.3 Treated fabric 23.0 90.0 90.2 93.2 Comparison fabric 22.8 90.2 89.9 93.1

2. Treatment of fabric The resultant microcapsules were applied to a tricot fabric made up of diacetate filaments and the fabric was pressed in accordance with the same method as stated in Example 11. The fabric was dried at 60C temperature and then heat-treated at C temperature for 1 minute.

The resultant fabric was colored red and had superior oil and water repellent properties as shown in Table 34.

an infinitely thick pad of the fabric, K is the absorption coefficient of the fabric, and S is the scattering coefficient. For comparison, the same fabric as that of the present Example was treated by the same solution as that contained in the microcapsules of the present Example.

Table 34 clearly shows that the dyed fabric of the present Example had superior oil and water repellent properties and color depth similar to those of the comparison fabric which was treated by the conventional method.

EXAMPLE l8 Dyeing of Cotton Fabric 1. Preparation of microcapsules Microcapsules A containing a benzene solution of cyanuric chloride were prepared by the process as stated in Example 1 1, and microcapsules B containing an aqueous solution of Erio chrome Brown BR (trade name of an acid mordant dye made by Geigy. Switzerland C.1. 11290) were prepared by the process as indicated in Example 15. These microcapsules A and B had the compositions and properties as show in Table 35.

Table 35 Microcapsules A B ltem Solution containing Aqueous solution Core 371 by weight of of 2% by weight constituent cyanuric chloride 30 ,uErio chrome Comin benzene Brown BR p sition Wall constituent Polyurethane Polyurethane Ratio by weight of wall to core 1:200 1:200 Tenacity at break 15 g/cm' 16 g/cm Size 40 50 pm 20 30 am 2. Treatment of fabric The resultant microcapsules A and B were applied to a 60 s cotton broad cloth by the static electrical method as indicated in Example 14 so that the microcapsules A and B were contained in the fabric at a content of 50 percent based on the weight of the fabric, respectively. The fabric was pressed in accordance with the method of Example 14 and dried at 100C temperature followed by heat-treating at 150C temperature for 3 minutes. The result is indicated in Table 36. For comparison, the same fabric as that of the present Example was treated only by the content solution of the microcapsules B (Comparison fabric A) and then half of the treated fabric was treated by the content solution of the microcapsules A (Comparison fabric B).

Table 36 Item Colorfastness for washing Fabric Removed by washing Washable brown Washable brown Comparison fabric A Comparison fabric B Fabric of the present Example EXAMPLE 19 Table 37 Solution of organo polysiloxane prepolymer in Core constituent Tetrachloroethylene Composition Ethylene-vinyl acetate-meth- Wall constituent aryloyl chloride copolymer Ratio by weight of wall to core 1:500 Tenacity at break 12 g/cm Size 20 30 p.m

The microcapsules were uniformly applied to a twill fabric made up of Toraylon fibers (trade name of an acrylic fiber made by Toray Industries Inc., Japan) to a content of 100 percent based on the weight of the fabric, and the fabric was pressed with a pair of rubber rollers having a hardness of 70 at a pressure of 1.2 kg/cm Through breaking the microcapsules, while the fabric was uniformly impregnated with the content solution of the microcapsules, the broken core constituents were not formed on the fabric according to the naked eye. The impregnated fabric was dried at 80C temperature and then heat-treated at 120C temperature for 5 minutes. The resultant fabric had superior elasticity and crease recovery and preferable hand feeling as shown in Table 38.

0.2 g of ethylene-methacryl chloride (97/3) copolymer and 20 g oftris-2,3-dibromopropyl phosphate were dissolved in 8.8 g of toluene. The solution was dispersed in 1,000 cc of an aqueous solution containing 0.5 percent by weight of sodium alginate by slowly dropping at room temperature while stirring at 7,200 rpm. The dispersion was heated to C temperature and maintained at this temperature for 40 minutes. Numerous microcapsules having the composition and properties as shown in Table 39 were obtained.

Table 39 Solution of tris-2,3-dibromo- Core constituent propyl phosphate in toluene Composition Ethylene-methacryl chloride Wall constituent copolymer Ratio by weight of wall to core 1:600 Tenacity at break 1 l g/cm Size 30 40 am The microcapsules prepared thus were applied to a broad cloth consisting of polyethylene terephthalate yarns to a content of 80 percent based on the weight of the fabric. The fabric was pressed in the same manner as indicated in Example 11. The fabric was impregnated with the core constituent solution. The impregnated fabric was dried at 50C temperature and then heat-treated at C temperature for 2 minutes. The resultant fabric contained 15.5 percent by weight of tris-2,3-dibromopropyl phosphate as a flame proof agent and had superior flame resisting properties. The wall constituents of the broken microcapsules were not found on the pressed fabric according to the naked eye.

For comparison, the same fabric as that of the present Example was treated with the same solution as contained in the microcapsules of the present Example by the padding manner so as to pick up 15.5 percent of the flame proof agent based on the weight of the fabric.

The results are shown in Table 40.

Table 40 Item Flame proof property Table 40 shows the fact that the treated fabric of the present Example had a superior flame proof property and high durability similar to those of the comparison 29 fabric which was treated by the conventional method.

EXAMPLE 21 A solution in 98 g of l,l,l-trichloroethane was prepared from 0.07 g of chlorosulfonated polyethylene of the formula:

y so c and 2 g of Teracyl Navy Blue RL (trade name of a disperse dye made by Ciba, Switzerland) and 0.01 g of hardening agent. The solution was dispersed in 700 cc of an aqueous solution containing 1% by weight of a dispersing agent by slowly dropping at room temperature while vigorously stirring at 5,000 r.p.m. The dispersion was heated to 50C temperature and maintained at this temperature for 1 hour while stirring. Numerous microcapsules having the composition and properties as shown in Table 41 were prepared.

Table 41 Solution of Teracyl Navy Blue Core constituent RL in 1.] ,l-trichloroethane Composition Wall constituent Chlorosulfonated polyethylene Ratio by weight of wall to core 1:1.500 Tenacity at break g/cm Size 5 pm The microcapsules prepared thus were uniformly applied to a tricot fabric made up of diacetate filament in the same manner as indicated in Example ll to a content of 50 percent based on the weight of the fabric. The fabric impregnated with the core constituent solution of the microcapsules was air dried and then heattreated at 160C temperature for 5 minutes. The resultant fabric was colored deep blue and its colorfastness and color tone were similar to those of the fabric dye in an aqueous dyeing bath by the conventional method.

EXAMPLE 22 Table 42 Solution of 2-hydroxy- 4octoxy benzophenone in tetrachloromethane Core constituent Composition Wall constituent Ethylene-mcthacryl chloride copolymer Ratio by weight of wall to core 1 [.000 Tenacity at break 2 g/cm Size 40 ,um

The microcapsules prepared thus were applied to several fabrics made up of polycapramide or polyethylene ter'ephthalate fibers which fabrics have been dyed with acid or disperse dye having a low light-fastness, respectively, to a content of percent based on the weight of each fabric. These applications were carried out in the same manner as indicated in Example 11. The fabrics impregnated with the core constituent solution containing 2-hydroxy-4-octoxy benzophenone which is an ultra-violet ray absorber were heat-treated at 170C temperature for 2 minutes. The dyed fabrics treated thus had the improved light fastness as shown in Table 43.

Table 43 Percent of fading of dyed fabric irradiated by fade-O-meter for 20 hours Mitsubishi Kasei, Japan. Miketon Polyester Brown 2R is trade name of a disperse dye made by Mitsui Toatsu Kagaku, Japan. Samaron Red HF is trade name of a disperse dye made by Hoechst, Germany.

For comparison, the same fabrics as those of the present Examples were sprayed with the same solution as contained in the microcapsules of the present Examples.

Table 43 shows the fact that the dyed fabric treated in the present Example had improved high-fastnesses similar to those of the comparison fabrics.

EXAMPLE 23 0.13 g of ethylene-methacryl chloride-vinyl acetate (/5/15) copolymer 4 g of methyl-hydrogenpolysiloxane prepolymer, l g of dimethyl polysiloxane diol prepolymer and 0.06 g of stannous octoate were dissolved into g of tetrachloroethylene. The solution was finely dispersed into 500 cc of an aqueous solution containing 1.0 percent by weight of hydroxyethyl cellulose by slowly dropping at room temperature while stirring at 8,500 r.p.m. The dispersion was heated to 45C temperature and maintained at this temperature while stirring for 1 hour. Thus, numerous microcapsules having the composition and properties as shown in Table 44, were obtained.

Table 44 Core constituent Composition Wall Constituent Ethylene-methacryl chloride-vinyl acetate The microcapsules prepared thus were uniformly applied to a broad cloth consisting of polyester fibercotton (65 35 by weight) blend yarns to a content of 110% based on the weight of the fabric. The application and the breaking of the microcapsules were performed in accordance with the same method as indicated in Example 1 1 except the hardness of the rubber rollers is 50. The fabric impregnated with the core constituent solution of the microcapsules which contained water repellent agents was dried at 100C temperature and then heat-treated at 160C temperature for 5 minutes. The resultant fabric had a superior water repellent property and a preferable had feeling as illustrated in Table 45.

40 parts of urethane prepolymer having a molecular weight of 18,000 and containing 1.8 percent by mol of NCO group were dissolved in 60 parts of tetrachloroethylene. The urethane prepolymer was prepared from polypropylene glycol having a molecular weight of 2,000, tolylene diisocyanate and polyprene triol. 200 g of this solution were dispersed in 600 g of an aqueous solution containing 0.85 percent by weight of sodium alginate by slowly dropping at room temperature-for minutes while stirring with a homomixer at 7,000 rpm.

After the dispersing was completed, 2 cc of an aqueous solution containing 10 percent by weight of ethylene diamine was added to the dispersion while stirring at 3,000 rpm. and then the dispertion was left to stand for 24 hours. Through this procedure, numerous microcapsules having the composition and properties as shown in Table 46. The obtained microcapsules were recovered from the dispersion by decantation, rinsed with water and then dried.

Table 46 Solution of urethane Core constituent prepolymer in trichloro- Table 46-Continued Solution of urethane Core constituent prepolymer in trichloroethylene Composition Wall constituent Polyurethane Tenacity at break 5 g/cm Size 10-30 pm An amount of the microcapsules having a total apparent volume of ml were suspended in 2,000 cc of an aqueous solution containing 40 g of perspiration absorbing agent for fibrous articles so as to obtain a treating suspension for fibrous articles.

The treating suspension was applied to a tricot fabric consisting of polycapramide filament yarn of 45 de nier/7 filaments, and then the fabric was squeezed with a roller mangle having a hardness of 50 in the same manner indicated in Example 1 l in order to break temperature microcapsules. The fabric was dried at 100C temperatue and heat-treated at C temperature for 3 minutes.

The resultant fabric'had a superior crease recovery and water absorbency as indicated in Table 47. For comparison, the same fabric as that of the present Example was treated only with the same solution as that contained in the microcapsules of the present Example.

manner that 0.03 cc of an aqueous solution of 1% by weight of potassium permanganate were dropped down to a center of a circle of 3 cm diameter marked on the fabric to be tested, and then the time in second consumed for diffusing the dropped solution to the circle is determined.

EXAMPLE 25 A trichloroethylene solution containing 100 parts of organo polysiloxane propolymer, 1 part of Catalyst for polymerizing silicone resin, 1 part of Catalyst PD and 0.4 parts of the same urethane prepolymer as used in Example 24 was dispersed in an aqueous solution containing 5 percent by weight of hydroxyethyl cellulose in accordance with the method as indicated in Example 24.

The resultant microcapsules had the composition and properties as indicated in Table 48.

Table 48 Solution of organo polysiloxane prepolymer, and Catalyst Core constituent in trichloroethylene Composition Wall constituent Polyurethane Ratio by weight of wall Table 48-Continued Table 50-Continued Solution of organo polysiloxane Microcapsule A B prepolymer, and Catalyst Core constituent in trichloroethylene 5 Item Composition Core constituent Solution of Solution of Wall constituent Polyurethane acrylic preurethane prepolymer In polymer in to core :800 trichlorotrichloro' Tenacity at break 3 g/Cm? compmition eth \.|ene ethylene Size '0 30 pm Wall constituent Polyurethane Polyurethane An amount of the resultant microcapsules having a break 1 9 total apparent volume of 300 ml were suspended in 10- Size iii-50 m hi iiiltm liters of aqueous solution containing 1 Kg ofa perspiranon absorbing. agent f 15 500 ml apparent volume of the microcapsules A and The suspension was applied a meet abnc made up 200 ml apparent volume of the microcapsules B were f polyethylene terepthalate filameni yam of 100 suspended in 5 litres of an aqueous solution containing niers/32 filaments and then the fabric was pressed 1n 75 g of Lurotex P g gzlg l z g 1 A tricot fabric consisting of polycapramide filament was me a oempera me or es an 20 yarns of 45 deniers/lO filaments was impregnated with then heat-treated at 160 C temperature for 30 seconds. the Suspension Squeezed dried at 80C temperature The resultant fabric had superior crease recovery and for 5 minuws then heat treated at 140C tempem water'abS0rbeI.1cy.aS f Table Compan' ture for 5 minutes. The resultant fabric had a superior the Same tabnc as the prewm f i was crease recovery and water absorbency as shown in treated with the same solution as that contained in the Table 51 mlcmcapsules of the present Example For comparison. the same fabric as that of the pres- Table 49 ent Exam le was im re nated with the same solution p p g as that contained in the mlcrocapsules A and then with Item Water absorbency the same solution as that contained in the microcap- Crease recovery (71) (second) sules Original After After laundering launder- Table 5 1 Fabric Warp Weft Warp Weft Original ing Untreated 550 82.5 55.1 80.5 O\5/1' ()ier wff igzf min mins Original After Origi- After Treated 85.1 90.6 83.0 89.2 15 38 mil Comparison 86.2 91.8 83.1 90.2 Over Over lau nderlaunder- 5 5 111g mg mins. mins. Fabric Warp Weft Warp Weft 40 Untreated 63.9 76.9 63.2 75.8 135 60 Treated 82.9 84.6 80 2 80.1 7 l3 7 4 EXAMPLE 26 Comparison 83.0 86.7 8-5 85.6 Ovjer OvSer Microcapsules A were prepared from a solution of 5 parts of butyl acrylate-acrylonitrile-acrylic acid copolymer and 0.2 parts of urethane prepolymer containing 13.0 percent of -NCO group which was prepared EXAMPLE 27 from diisocyanate andfilmethylol propane (3 0.2 part of urethane prepolymer which was obtained 1 1 by mol) l f tnchloroethylenej and an from 1 mol of copolyester having a molecular weight of aqueQus cfmtammg percent by weght f a 2,000 and prepared from a mixture of buthylene glycol perspiration absorbing agent in the same manner as mand propylene glycol (90 10) and adipic acid, 4 mol dlcaled m Example of hexamethylene diisocyanate and 4 mol of 1.4 butane Microcapsules B were prepared from the same soludie], 50 parts of organo polysiloxane prepolymer 0'5 mom and m the same method as those indicated in Exparts of Catalyst for polymerizing Silicone resin, and ample 0.5 parts of Catalyst for polymerizing silicone resin These P and B had the composmon were dissolved in 44.8 parts of trichloroethylene. and propernes as shown In Table 50, respectively. The solution was finely dispersed in an aqueous solu- Table 50 tion of 2.55 parts of sodium alginate in 300 parts of water mto 20 to 30 um particles, by slowly dropping at Microcapsule A B room temperature while stirring with a homomixer at I 7,000 rpm. After stirring for 20 minutes, 2 cc of an tern Core constituent Solution of Solution of fl f Solutlon of 10 percnt welgh? of E y acrylic preurethanc predtamme were added to the dispersion while stirring at 3,000 rpm. in order to form microcapsules containing, ethylene ethylene as the core constituent, trichloroethylene solution of Com osition or ano o1 siloxane re 01 mer and Catal st. The mip Wall constituent Polyurethane g p y p p y y Polyurethane Ratio by weight of wall crocapsules obtained thus were rinsed with water so as to sufficiently eliminate sodium alginate. The resultant microcapsules had the composition and properties as shown in Table 52.

Table 52 Solution organo polysiloxane prepolymer. and

Core constituent Catalyst PD in trichloroethylene Composition Wall constituent Polyurethane Ratio by weight of wall to core l:l,000 Tenacity at break g/cm Size 20 30 pm EXAMPLE 28 A solution of 0.3 part of terephthaloyl chloride and 40.0 parts of Scotchgard FC-3l0 in 59.5 parts of trichloroethylene was finely dispersed into an aqueous solution of 0.8 part of carboxymethyl cellulose in 400 parts of water into to 30pm particles by slowly dropping at room temperature while stirring with a homomixer at 8,000 r.p.m. After stirring for minutes, 0.5 part of hexamethylene diamine was added to the dispersion soas to form microcapsules. The obtained microcapsules. were sufficiently washed with water in order to remove carboxymethyl cellulose. The resultant microcapsules had the composition and properties as shown in Table 53.

Table 53 Solution of Scotchgard FC-3l0 in trichloro- Core Constituent ethylene Composition Wall constituent Polyamide Ratio by weight of wall to core 1:1,000 Tenacity at break 3 g/cm Size 20 30 um EXAMPLE 29 A non-aqueous solvent solution was prepared by dissolving 30 parts of urethane prepolymer which was obtained through a reaction between 1 mol of polycarprolactone diol having a molecular weight of 1,500 consisting of e-caprolactone, methyl e-caprolactone and methyl diethanol amine, 2 mol of hexamethylene diisocyanate and 1 mol of 1.3-propylene diamine into 70 parts of trichloroethylene. i

The solution was dispersed into an aqueous solution containing 5 percent by weight of hydroxyethyl cellulose by slowly being dropped at room temperature while stirring at 8,000 r.p.m. into 20 to 30 mi size'particles. After completing the dispersing, 8 cc of an aqueous solution containing 10 percent by weight of ethylene diamine was added to the dispersion while stirring at 3,000 r.p.m. for 10 minutes.

The resultant microcapsules had the composition and properties as shown in FIG. 54.

Table 54 Core constituent v chlorocthylene Composition Wall constituent Polyurethane Ratio by weight of wall to core l:l,000 Tenacity at break 5 g/cm" Size 20 30 um The microcapsules thus prepared was washed to completely remove hydroxyethyl cellulose. V

For comparison, the trichloroethylene solution as stated above, was dispersed into an aqueous solution containing 2 percent by weight of gelatin.

However, the trichloroethylene solution was so insufficiently dispersed as to obtain no microcapsules.

The microcapsules of the present Example were applied to a polycapramide tricot fabric from an aqueous suspension thereof through a padding process. The fabric was pressed by a pair of rubber rollers in the same manner as that of the Example 24. The impregnated fabric with the urethane prepolymer was dried at C temperature and then heat-treated at C temperature for 2 minutes. The resultant fabric had a superior crease recovery.

What we claim is:

1. A process for treating a fibrous article selected from yarns, knitted fabrics, woven fabrics or nonwoven fabrics consisting of at least one kind of natural or artifical fibers, comprising the steps of:

1. forming a suspension, in water, of a multitude of discrete microcapsules having particle sizes in the range of 100 to 1 gm, each microcapsule consisting essentially of:

a. a liquid core consisting essentially of a solution of at least one hydrophobic fiber treating agent dissolved in a non-aqueous solvent which is not miscible with water, said fiber treating agent comprising elasticity-improving agents, antipilling agents, ultra-violet ray absorbers, softening agents, flame proof agents, anti-static agents, water repellent agents, soil-releasing agents, heat proof agents, shrink proof agents, crease proof agents, cross-linking agents, dyes or pigments and being capable of being adhered. absorbed or reacted with said fibers upon contact therewith, and I b. a solid, thin synthetic resin shell deposited on and completely surrounding said core, said resin being selected from the group consisting of polyurethane resins, silicone resins, polyolefins. epoxy resins, polyamides and polyesters, said shell having a breaking tenacity of not in excess of 50 g/cm the weight ratio of (b) to (a) being in the range of l :500 to l 5,000;

2. applying the suspension of said microcapsules in water onto said fibrous article; and

3. breaking the microcapsules on said fibrous article to impregnate said article with said solution whereby said fibrous article is treated by said fiber treating agent.

2. A process as claimed in claim 1, wherein said nonaqueous solvent is selected from the group consisting of tetrachloromethane, tetrachloroethylene, trichloro ethylene, xylene, toluene, l,1,l,-trichloroethane, benzene, ethylbenzene, industrial gasoline, chloroform, methylene chloride and tetrachloroethane and mixtures thereof.

3. A process as claimed in claim 1, wherein the maximum size of said microcapsule is not in excess of 30 4. A process as claimed in claim 1, wherein said microcapsules contain two or more kinds of treating agents.

5. A process as claimed in claim 1, wherein said aqueous suspension of said microcapsules contains in addition at least one member selected from moistening agents, antistatic agents or dyes.

6. A process as claimed in claim 1, wherein said microcapsules are applied in an amount in the range of 5 to 400 percent based on the weight of said fibrous articlev 7. A process as claimed in claim 1, wherein after said microcapsules are subjected to breaking, the treated fibrous article is subjected to heat treatment.

8. A process as claimed in claim 1, in which said fiber treating agent is a urethane prepolymer effective to improve the antipilling or the crease proof properties of the fibrous article.

9. A process as claimed in claim 1, in which the fiber treating agent is an organosiloxane prepolymer effective to improve the elasticity or the crease recovery of the fibrous article.

10. A process as claimed in claim 1, in which the fiber treating agent is dimethyl polysiloxane effective to improve the softness of the fibrous article.

11. A process as claimed in claim 1, in which the fiber treating agent is dimethyl polysiloxane diol effective to improve the softness, elasticity, water repellency, heat proofness or anti-shrinking properties of the fibrous article.

12. A process as claimed in claim I, in which the fiber treating agent is methylhydrogen polysiloxane effective to improve the water repellency of the fibrous article.

13. A process as claimed in claim 4, wherein said microcapsules in said suspension consist of a mixture of two or more kinds of microcapsules containing different treating agents.

14. A process as claimed in claim 4, wherein all said microcapsules contain a mixture of two or more treating agents.

15. A process as claimed in claim 5, wherein said moistening agent is selected from the group consisting of addition compounds in which 2 to 50 mols of ethyl ene oxide is added to e-caprolactam, addition com pounds in which 2 to' 50 mols of propylene oxide is added to e-caprolactam, addition compounds in which 2 to 50 mols of propylene oxide is added to oligomer of e-caprolactam, sodium N-acyl aminoacetate, sodium N-acyl-a-aminopropionate and sodium N-acyl-fiaminopropionate.

16. A process as claimed in claim 6, wherein said microcapsules are applied in an amount in the range of from 10 to l00 percent based on the weight of said fibrous articles.

17. A process as claimed in claim 7, wherein said heat treatment is carried out at a room temperature of 50 to 200C.

18. A process as claimed in claim 17, wherein said temperature of said heat treatment is in a range of from to 180C.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3041288 *Dec 22, 1958Jun 26, 1962Ncr CoMethod of manufacturing microscopic capsules having walls of alcohol-fractionated gelatin
US3257267 *May 19, 1965Jun 21, 1966Hay Harold RRetarding liberation of an additament in forming a fibrous web by embedding the additament in a gel matrix prior to addition to the fibers
US3415758 *May 3, 1962Dec 10, 1968Ncr CoProcess of forming minute capsules en masse
US3632296 *Apr 12, 1968Jan 4, 1972Cluett Peabody & Co IncApplication of reactants and/or catalysts to textile fabrics in microencapsulated form
US3660321 *Sep 22, 1969May 2, 1972Hans Eberhard PraetzelShaped articles comprising self-extinguishing compositions of plastics and microcapsules containing flame-abating compounds and process for producing the same
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4018688 *Jul 21, 1975Apr 19, 1977The Procter & Gamble CompanyCapsules, process of their preparation and fabric conditioning composition containing said capsules
US4081384 *Apr 8, 1976Mar 28, 1978The Proctor & Gamble CompanySolvent-free capsules and fabric conditioning compositions containing same
US4136218 *Aug 27, 1975Jan 23, 1979Hoechst AktiengesellschaftModified cellulose ethers
US4145184 *Nov 28, 1975Mar 20, 1979The Procter & Gamble CompanyDetergent composition containing encapsulated perfume
US4221862 *Jun 28, 1976Sep 9, 1980Fuji Photo Film Co., Ltd.Method of producing finely divided polymer particles
US4234627 *Feb 4, 1977Nov 18, 1980The Procter & Gamble CompanyFabric conditioning compositions
US4880851 *Feb 26, 1988Nov 14, 1989Tohru YamamotoAromatic composition and method for the production of the same
US4980392 *Aug 23, 1989Dec 25, 1990Tohru YamamotoPolymer encapsulation
US4987161 *Aug 23, 1989Jan 22, 1991Tohru YamamotoAromatic composition and a method for the production of the same
US4988744 *Aug 23, 1989Jan 29, 1991Tohru YamamotoPerfume compositions produced by sol-gel methods
US5021267 *Mar 6, 1990Jun 4, 1991Cogent LimitedTreatment of cords, threads and filaments
US5075350 *Nov 26, 1990Dec 24, 1991Tohru YamamotoEncapsulated by acid hydrolysis of alkoxide, followed by base catalyzed polymerization
US5387622 *Jun 28, 1991Feb 7, 1995Yamamoto; TohruEncapsulated or clathrated in a matrix of conjugated polymer produced from an alkoxide and a silane coupling agent
US6165615 *Jul 30, 1998Dec 26, 2000Takasago International CorporationGradual-releasing capsule and method for manufacturing the same
US6491745May 7, 1999Dec 10, 20023M Innovative Properties CompanyComposition comprising water/oil repellent fluorochemical component and plurality of dispersed microcapsules containing polishing agent, in which repellent is absorbed by porous substrate leaving microcapsules as separated surface layer
US6620777Jun 27, 2001Sep 16, 2003Colgate-Palmolive Co.Fabric care composition comprising fabric or skin beneficiating ingredient
US6756076Oct 11, 2001Jun 29, 2004Michael BrierBleaching cotton fabric with whitener, affixing to conveyor, applying water resistant substance, and conveying through a heater
US7105064Nov 20, 2003Sep 12, 2006International Flavors & Fragrances Inc.Of treated fabrics, hair and skin; pellets of a copolymer of ethylene-vinyl acetate with a liquid phase fragrance material removably entrapped in the polymer infrastructure, extruding, cooling, grinding to form cryoground particles; applying to surface, then removal of polymeric particles
US7119057Nov 24, 2003Oct 10, 2006International Flavors & Fragrances Inc.Encapsulated fragrance chemicals
US7122512Nov 24, 2003Oct 17, 2006International Flavors & Fragrances IncEncapsulated fragrance chemicals
US7125835Oct 10, 2002Oct 24, 2006International Flavors & Fragrances IncEncapsulated fragrance chemicals
US7196049Jun 12, 2003Mar 27, 2007International Flavors & Fragrances, IncFragrance material encapsulated by a polymer to provide a polymer encapsulated fragrance; the polymer encapsulated fragrance is coated by cationic polyamine which is the reaction product of a polyamine and haloalkyloxiran
US7211556Apr 15, 2004May 1, 2007Colgate-Palmolive CompanyFabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient
US7304026Apr 15, 2004Dec 4, 2007Colgate-Palmolive CompanyFabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient
US7491687Nov 5, 2004Feb 17, 2009International Flavors & Fragrances Inc.Encapsulated materials
US7585824Jun 12, 2003Sep 8, 2009International Flavors & Fragrances Inc.Polymer encapsulated fragrance further coated with cationic polymer of cationic starch or guar; hygiene, cleaning compounds
US7594594Nov 17, 2004Sep 29, 2009International Flavors & Fragrances Inc.Multi-compartment storage and delivery containers and delivery system for microencapsulated fragrances
US7833960Dec 15, 2006Nov 16, 2010International Flavors & Fragrances Inc.Encapsulated active material containing nanoscaled material
US7855173Jun 26, 2009Dec 21, 2010Amcol International CorporationDetersive compositions containing hydrophobic benefit agents pre-emulsified using sub-micrometer-sized insoluble cationic particles
US7871972Dec 3, 2008Jan 18, 2011Amcol International Corporationcationic polymer, a surface-active, anionic polymer such as a copolymer of castor oil phosphate and 3-isocyanatomethyl-3,5,5-trimethyl cyclohexyl isocyanate, a hydrophobic benefit agent, and a smectite organoclay; increased deposition of benefit agent
US7888306May 14, 2008Feb 15, 2011Amcol International CorporationCompositions containing benefit agent composites pre-emulsified using colloidal cationic particles
US7977288Mar 3, 2009Jul 12, 2011Amcol International CorporationMicroparticle coated with two types of cationic polymers, the first having a lower molecular weight than the second; e.g. polydiallyldimethylammonium chloride and a cationic cellulose; increased deposition of benefit agent; shampoos, cleansers
US8188022Apr 13, 2009May 29, 2012Amcol International CorporationMultilayer fragrance encapsulation comprising kappa carrageenan
US8546509Jul 25, 2005Oct 1, 2013Huntsman Textile Effects (Germany) GmbhFunctionalized particles
US20090036568 *Oct 17, 2007Feb 5, 2009Philippe MerleSelf healing composite material and method of manufacturing same
US20100310798 *Aug 10, 2006Dec 9, 2010Saint-Gobain IsoverInsulation packaged with additive
CN100577278CJul 25, 2005Jan 6, 2010西巴特殊化学制品控股公司Functionalized particles
EP1935483A2Dec 12, 2007Jun 25, 2008International Flavors & Fragrances, Inc.Encapsulated active material containing nanoscaled material
EP2545988A2Dec 12, 2006Jan 16, 2013International Flavors & Fragrances, Inc.Encapsulated active material with reduced formaldehyde potential
WO1999058728A1 *May 7, 1999Nov 18, 1999Ashizawa MasahiroWater/oil repellant composition
WO2002076605A1 *Mar 21, 2002Oct 3, 2002Eilers JoergMethod for producing encapsulations
WO2006013165A1 *Jul 25, 2005Feb 9, 2006Ciba Sc Holding AgFunctionalized particles
WO2007091223A1Feb 9, 2007Aug 16, 2007Procter & GambleFabric care compositions comprising formaldehyde scavengers
WO2009100464A1Mar 3, 2009Aug 13, 2009Amcol International CorpCompositions containing cationically surface-modified microparticulate carrier for benefit agents
WO2009126960A2Apr 13, 2009Oct 15, 2009Amcol International CorporationMultilayer fragrance encapsulation
WO2011123737A1Apr 1, 2011Oct 6, 2011The Procter & Gamble CompanyCare polymers
WO2011143321A1May 11, 2011Nov 17, 2011The Procter & Gamble CompanyCare polymers
WO2011143322A1May 11, 2011Nov 17, 2011The Procter & Gamble CompanyFabric and home care product comprising care polymers
Classifications
U.S. Classification427/189, 8/526, 427/389.9
International ClassificationB01J13/16, B01J13/02, B01J13/06, D06M23/12
Cooperative ClassificationB01J13/16, D06M23/12, B01J13/025
European ClassificationD06M23/12, B01J13/16, B01J13/02M