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 numberUSRE30450 E
Publication typeGrant
Application numberUS 06/026,380
Publication dateDec 16, 1980
Filing dateApr 2, 1979
Priority dateApr 2, 1979
Publication number026380, 06026380, US RE30450 E, US RE30450E, US-E-RE30450, USRE30450 E, USRE30450E
InventorsJoseph Iannicelli
Original AssigneeJ. M. Huber Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Surface modified pigments
US RE30450 E
Abstract
.Iadd.Finely divided particulate inorganic pigment is surface modified with from about 1% to about 15% of an amino organosilane, particularly gamma-aminopropyltriethoxy silane. Thermosetting resins incorporating such modified inorganic pigments exhibit improved physical properties.
Images(7)
Previous page
Next page
Claims(8)
I claim:
1. A .Iadd.filler comprising a .Iaddend.finely divided particulate inorganic pigment surface .Iadd.selected from the group consisting of synthetic silicas, silicates, metal oxides, calcium carbonates, zinc sulfides, and carbon blacks, said pigment surface having been .Iaddend.modified .Iadd.by treatment .Iaddend.with from about 1% to 15%, based on the weight of the dry pigment, of an amino organosilane of the formula ##STR2## wherein R1 is selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, and alkylaryl, R2 is selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl and alkylaryl, R3 is selected from the group consisting of hydrogen, lower alkyl, aryl, lower alkylaryl and lower arylalkyl, R4 is selected from the group consisting of hydrogen, lower alkyl, aryl, lower alkylaryl and lower arylalkyl, R5 is selected from the group consisting of hydrogen, lower alkyl, aryl, lower alkylaryl, and lower arylalkyl, X is selected from the group consisting of alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene containing secondary amino nitrogen, and cycloalkylene containing tertiary amino nitrogen.Iadd., the modification of said pigment surface by said organosilane comprising spray drying slurries of said pigment having one or more of the amino organosilanes dispersed therein. .Iaddend. .[.
2. A compound as in claim 1 wherein the finely divided particulate filler is selected from the group consisting of synthetic silicas, silicates, metal oxides, calcium carbonates, zinc sulfides, and carbon blacks..].
3. A compound as in claim 1 wherein the amino organosilane is gamma aminopropyltriethoxysilane.
4. A compound as in claim 1 wherein the amino organosilane is a diamino functional silane.
5. Finely divided particulate hydrated silica, surface modified with from about 1% to 15% by weight based upon the weight of the silica of gamma aminopropyltriethoxysilane.
6. Finely divided particulate sodium alumino silicate pigment, surface modified with from about 1% to 15% by weight, based upon the weight of the pigment, of gamma aminopropyltriethoxysilane.
7. Finely divided particulate carbon black, surface modified with from about 1%to 15% by weight, based upon the weight of the carbon black, of gamma aminopropyltriethoxysilane.
8. Finely divided particulate kaolin clay, surface modified with from about 1% to 15% by weight, based upon the weight of the kaolin clay, of gamma aminopropyltriethoxysilane. .Iadd. 9. A filler comprising a finely divided particulate inorganic pigment surface selected from the group consisting of synthetic silicas, silicates, metal oxides, calcium carbonates, zinc sulfides, and carbon blacks, said pigment surface having been modified by treatment with from about 1% to 15%, based on the weight of the dry pigment, of an amino organosilane of the formula
H2 N--R--Si(Or')3 
wherein R is selected from the group consisting of phenylene lower alkyl substituted phenylene, lower alkoxy substituted phenylene, and lower alkylene, R' is a monovalent hydrocarbon group free of aliphatic unsaturation selected from the group consisting of lower alkyl, aryl, lower alkaryl and lower aralkyl, wherein R' can represent the same or different groups. .Iaddend.
Description

This is application is a .Iadd.reissue of U.S. Pat. No. 3,290,165, Ser. No. 269,695 filed April 1, 1963, which is a .Iaddend.continuation-in-part of applicant's copending application Ser. No. 189,321, filed April 23, 1962, entitled "Surface Modified Pigments," and now abandoned.

This invention relates to finely divided particulate inorganic pigments modified with amino organosilanes and the process for their production.

When inorganic pigments are modified with the silanes according to this invention, the properties imparted to them are such that they can advantageously be used as fillers for thermosetting resins such as polyurethanes, epoxy polymers, melamine polymers, phenolic polymers, ureaformaldehyde polymers, unsaturated polyesters, as well as other polymers and elastomers including polyethylenes, polypropylenes, polystyrenes, saturated polyesters, polyamides, polyvinyl compounds, polyisoprenes, polybutadienes, polystyrenebutadienes, and the like.

The modified pigments can also be advantageously used as fillers for paper, paints, varnishes, inks, and paper coating compositions.

By the use of these modified finely divided particulate inorganic pigments, improved physical properties are imparted to the vehicles into which they are incorporated.

Inorganic pigments modified with amino organosilanes have affinity for direct dyes and are useful for imparting various colors to the vehicles.

An object of this invention is to provide modified pigments especially useful as fillers.

Another object of this invention is to provide modified pigments which are dyeable with direct dyes and are useful as color-imparting fillers.

A further object of this invention is to provide modified pigments which can be used as fillers in applications where they had heretofore been unsatisfactory.

A still further object of the invention is to provide cross-linkable fillers capable of imparting improved abrasion resistance among other improved properties to elastomers.

Other objects and advantages will be apparent from the following specification.

I am aware of extensive efforts in the prior art to improve properties of filler pigments by modification with organosilanes. Hydrocarbon silane modifications of pigments do impart improved dispersions in organic vehicles but such modifications do not normally increase reinforcement in vinyl addition polymers unless the hydrocarbon silane carries specific types of unsaturation which serves to promote a more tenacious bridge between the filler and the vehicle. In any case, all these prior art modified pigments are rendered hydrophobic by modification with either saturated or unsaturated hydrocarbon silanes and, furthermore, such silane modified pigments are not valuable reinforcing fillers in saturated thermosetting resins.

I have discovered that modification of filler pigments with saturated amino organosilanes improves reinforcement in a wide variety of vinyl addition as well as thermosetting polymers in that a strong chemical bridge between filler pigment and polymer results. Bridging is accomplished through the amino modified surface of the pigments. Surprisingly, amino organosilane modification improves reinforcement in both vinyl addition and thermosetting polymers, whereas unsaturated organosilane fillers are generally only effective in vinyl addition polymers where unsaturation is present. Another important advantage of amino organosilane modified fillers is that they are usually hydrophilic whereas prior art silane modified fillers are hydrophobic.

The modified pigments of this invention can be prepared by dissolving the desired amount of amino organosilane in a suitable solvent, adding the pigment and heating until the reaction is complete. The amount of modifier added depends upon the particular pigment being modified and the use for which it is intended. Generally up to about 15% by weight of the modifier is sufficient for most purposes.

A particularly useful process of modifying pigments according to this invention involves spray drying pigment slurries having one or more of the amino organosilanes dispersed therein. The spray drying process effects a uniform distribution of the modifier on the pigment and virtually instantaneously cures the modifier on the pigment.

The compounds used to modify the pigments can be depicted by the formula: ##STR1## wherein R1 is hydrogen, alkyl, aryl, cycloalkyl, or alkylaryl; R2 is hydrogen, alkyl, aryl, cycloalkyl or alkylaryl; R3 is hydrogen, lower alkyl, aryl, lower alkylaryl, or loer arylalkyl; R4 is hydrogen, lower alkyl, aryl, lower alkylaryl or lower arylalkyl; R5 is hydrogen, lower alkyl, aryl, lower alkylaryl or lower arylalkyl; and X is alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene having secondary and/or tertiary nitrogen present in the chain, and/or primary, secondary, and/or tertiary nitrogen pendant from the chain. Some of these amino organosilanes are disclosed along with methods for their preparation in U.S. Pat. Nos. 2,832,754; 2,930,809; 3,007,957; and 3,020,302. Commercially available amino organosilanes include "A-1100" (gamma aminopropyltriethoxysilane) and "Y-2967" (an amino silane which is a modified gamma aminopropyltriethoxysilane) sold by Union Carbide Corporation, N.Y., N.Y., and "Z-6020" (a diamino functional silane) sold by Dow Corning Corporation, Midland, Michigan.

.Iadd.Preferred compounds to modify the pigments are amino organosilanes of the formula:

H2 N--R--Si(OR')3 

wherein R is selected from the group consisting of phenylene, lower alkyl substituted phenylene, lower alkoxy substituted phenylene, and lower alkylene, R' is monovalent hydrocarbon group free of aliphatic unsaturation selected from the group consisting of lower alkyl, aryl, lower alkaryl and lower aralkyl, wherein R' can represent the same or different groups. .Iaddend.

Pigments advantageously modified in the practice of this invention are finely divided particulate inorganic pigments such as, for example, inorganic compounds of silicon, including hydrated or anhydrous silicas, calcium silicates, magnesium silicates, calcium-magnesium silicates, barium silicates, aluminum silicates, sodium-alumino-silicates, calcium-alumino-silicates, calcium-sodium alumino silicates; clays such as kaolins which include dickite, kaolinite and nacrite, halloysite, montmorillonites including sodium and magnesium bentonites, synthetic or natural zeolites; various metal oxides and carbonates such as zinc oxide, alumina, titania or magnesia, calcium carbonate; and various non-white pigments like carbon blacks, zinc sulfide, ferric oxide and the like.

All the above fillers are available on a commercial scale and include the following, all of which are finely divided, particulate substances.

Zeolex®, very finely divided precipitated sodium alumino silicate pigments of submicron particle size and disclosed in U.S. Pat. Nos. 2,739,073 and 2,848,346.

Zerosil®, very finely divided precipitated hydrated silicas of submicron particle size and disclosed in copending U.S. Pat. applications Ser. No. 144,168 filed Oct. 10, 1961, and 149,964 filed Nov. 3, 1961.

Suprex®, an air floated kaolin clay with platelike particles of which 87-92% are minus 2 microns.

Aromex®, intermediate super abrasion furnace carbon blacks.

Essex®, semi-reinforcing furnace blacks.

Silene EF®, a precipitated hydrated calcium silicate of very fine particle size.

Hi-Sil®, a precipitated hydrated silica of very fine particle size.

Celite®, a diatomaceous earth which is principally a hydrated silica.

Alumina C®, a hydrated aluminum oxide of small particle size.

Kadox®, a zinc oxide filler.

Titanox®, a pigment grade commercial titanium dioxide.

Cab-O-Sil®, a very finely divided anhydrous silica.

Ludox®, a precipitated silica of very fine particle size.

The following examples illustrate typical methods by which various pigments are surface modified in accordance with this invention.

Example 1

8 grams of gamma aminopropyltriethoxysilane (A-1100) was dissolved in 3.3 liters of benzene in a 5-liter round bottom flask. 400 grams of carbon black (ISAF) was added and the resulting mixture was refluxed 2 hours. The resulting product contained 2% of the modifier based on the weight of the carbon black.

Example 2

"Suprex" was modified with 1.0% by weight with gamma aminopropyltriethoxysilane by adding the appropriate amount of the modifier using water as a solvent and then adding the clay and refluxing for 21/2 hours. The products were recovered and dried. The example was repeated with 2.0% and 3.0% gamma aminopropyltriethoxysilane.

Example 3

"Zeolex 23" was modified with 1% by weight with gamma aminopropyltriethoxysilane by adding the "Zeolex" to a benzene solution of the modifier and refluxing for 21/2 hours. The product was recovered and dried.

Example 4

"Suprex" was modified with 1.0% of "Z-6020" by adding 3.33 pounds "Z-6020" to 667 pounds of water while under agitation. 333 pounds of "Suprex" was slowly added to the solution while continuing the stirring until a homogeneous clay slip resulted. The clay slip was then spray dried in a 7-foot conical spray dryer operated at an inlet temperature of 600° F. and an outlet temperature of 250° F. A finely pulverized, chemically modified clay product was obtained. The example was repeated to produce 2.0% and 3.0% modifications of the "Suprex."

Example 5

Example 4 was repeated using "Y-2967" instead of "Z-6020."

Example 6

Example 4 was repeated using "A-1100" instead of "Z-6020."

Example 7

"Suprex" was modified with 1% of gamma aminopropyltriethoxysilane by adding 10 grams gamma aminopropyltriethoxysilane to 3.5 liters benzene, then adding 1 kilogram "Suprex" clay and refluxing for 3 hours. The modified clay was recovered and dried. This example was repeated using 2% and 3% instead of 1% gamma aminopropyltriethoxysilane.

Example 8

Example 7 was repeated using "Z-6020" in place of gamma aminopropyltriethoxysilane.

Example 9

Example 7 was repeated using "Y-2967" in place of gamma aminopropyltriethoxysilane.

The above examples illustrate the facility with which various inorganic pigments are modified with amino organosilanes.

The examples were repeated using each of the pigments named herein to produce modified pigments having properties similar to those discussed below.

While only three modifiers are exemplified, this is done for convenience since all those disclosed herein have been used for the purpose and come within the scope of this invention.

The physical properties of the various pigments disclosed herein are significantly altered by modification with the group of silanes disclosed herein. For example, when kaolin clay is so modified, a dramatic change in its properties is apparent. Where, before, the clay lacked significant affinity for direct dyes, it is modified by the process of this invention to be readily dyeable with direct dyes. The modified kaolin clays can be used as a filler for polyurethanes where, before modification, it was unusable since it prevented a cure of the polymer. This is illustrated in Table I in which the following formation was employed:

______________________________________          Parts______________________________________Vibrathane 50031            100Stearic acid     0.25Di-Cup 40C2 5Clay             60______________________________________ 1 A polyurethane produced by Naugatuck Chemical Division of U.S. Rubber Company. 2 A polymerizing crosslinking agent produced by Hercules Powder Company.

The compounds were mixed on a 6-inch by 12-inch laboratory mill and cured for 30 minutes at 307° F., except for the NBS abrasion test where the cure was for 60 minutes at 307° F.

                                  TABLE I__________________________________________________________________________                      Example 2                      Suprex                           Suprex                                Suprex                      plus 1%                           plus 2%                                plus 3%            Control                 Suprex                      Modifier                           Modifier                                Modifier__________________________________________________________________________Parts filler/100 parts polymer            None 60    60   60   60Tensile, p.s.i   5,240                 No cure                      3,680                           3,770                                3,840Stress, 300%, p.s.i            830  No cure                      2,070                           3,190                                --Elongation, percent            500  No cure                      470  425  265Shore A Hardness g            56   No cure                       71   71   75NBS Abrasion, percent of standard            129  No cure                      122  172  202__________________________________________________________________________

The results illustrate the improved properties of modified kaolin clay filled polyurethane over both the compound filled with unmodified kaolin and the unfilled compound. Note, for example, the increase in abrasion resistance with increased modification of kaolin. It is also apparent from the data that unmodified kaolin is unsatisfactory as a filler for polyurethanes since the polymer did not cure. The use of modified kaolin clay not only improves the properties of the polyurethane but also decreases the raw material cost since the filler is much less expensive than the polymer.

                                  TABLE II__________________________________________________________________________MODIFIED SUPREX CLAYS IN VIBRATHANE 5003                              Example 2               Minutes   Suprex                              1%   2%   Example 4                                              Example                                                    Example 9               Cured at                    Unfilled                         Filled                              Modifier                                   Modifier                                        1% Z-6020                                              1% Z-6020                                                    1% Y-2967Physical Properties 305° F.                    Control                         Control                              Water                                   Water                                        Water Benzene                                                    Benzene__________________________________________________________________________200% Modulus        30   430  1,270                              1,340                                   2,900                                        --    2,900 1,710               60   500  1,310                              1,530                                   2,990                                        2,890 1,710 --               75   510  1,330                              1,480                                   2,820                                        --    2,860 1,840300% Modulus        30   830  1,570                              2,070                                   3,190                                        --    3,270 2,060               60   1,050                         1,640                              2,220                                   3,340                                        3,330 3,270 2,090               75   1,040                         1,630                              2,520                                   3,200                                        --    3,240 2,170Tensile Strength    30   5,240                         4,340                              3,680                                   3,770                                        2,960 3,470 4,040               60   4,890                         3,850                              3,920                                   3,490                                        3,620 3,290 3,610               75   5,320                         3,640                              3,560                                   3,510                                        --    3,240 3,950Elongation          30   500  570  470  425  190   365   560               60   440  525  450  335  360   315   500               75   450  505  440  370  --    300   510Hardness, Shore A   30   56   72   71   71   75    75    70               60   59   74   73   73   76    76    71               75   59   74   73   73   13    76    71Crescent Tear       30   65   285  280  238  225   235   303               60   68   270  230  243  205   193   220               75   73   243  231  225  --    193   225NBS Abrasion Index, Percent               60   74.8 63.6 77.2 109.5                                        143.5 131.4 68.2               75   80.3 62.2 87.4 137.0                                        105.5 152.1 81.5Hardness, Shore A, NBS Specimens               60   55   71   72   75   76    76    71               75   56   73   73   75   76    76    72NBS Abrasion (Gum=100%)               60   100  85   103  147  192   176   91               75   107  83   117  183  141   204   109Compression Set "B" 22 hrs./158° F.               60   5.5  34.0 17.5 11.3 10.1  12.0  25.0               75   5.1  36.7 16.5 12.0 9.5   11.0  23.9Mooney Viscosity, ML 4'/212° F.               --   44   60   65   65   83    65    64Mooney Scorch, MS/265° F.               --   23   26   20   16   12.5  18    23__________________________________________________________________________

Table II demonstrates dramatic improvements in properties of polyurethane filled with amino organosilane modified clays.

When modified carbon black is used as the filler in a rubber recipe, good results compared to unmodified black are achieved with a 2% by weight modification using gamma aminopropyltriethoxysilane. The results listed in Table III are based upon tests in the following recipe.

______________________________________         Parts/100 RHC______________________________________Smoked sheet    100.0ISAF carbon black           45.0Zinc oxide      3.0Stearic acid    3.0Pine tar        3.0Age rite HP1           1.0NOBS special2           0.35Sulfur          2.75Total           158.10______________________________________ 1 An antioxidant containing phenylbeta-naphthylamine and N,Ndiphenyl-para-phenylenediamine. 2 Accelerator containing Noxydiethylene benzothlazol2-sulfenamide.

The batches were mixed on a Banbury using speed #1, ram pressure of 30 p.s.i., and a starting temperature of 125° F.; the final batch mix was on a 6-inch by 12-inch mill and the inlet water temperature was 158° F. The compound was cured for 70 minutes at 275° F., then tested. The results are listed in Table III.

              TABLE III______________________________________                                 Abrasion,        Percent  Modulus, Tensile,                                 Huber-Pigment      Modifier p.s.i.   p.s.i. Williams______________________________________ISAF Carbon Black        None     1,780    4,590  100.0 Control.ISAF Carbon Black        1   1,970    4,720  107.9______________________________________ 1 2.0% gamma aminopropyltriethoxysilane.

This data indicates that when carbon black is modified with controlled amounts of modifier, the properties which it imparts to rubber are improved in respect to modulus, tensile, and abrasion resistance.

When modified Zeolex is used as a filler for rubber compounds, it imparts to the rubber improved properties of modulus, tensile strength, tear resistance and abrasion resistance when compared to these same properties in rubber filled with unmodified Zeolex. The results in Table IV are based upon the following recipe:

______________________________________        Parts/100 RHC______________________________________GRS 15021 100.0Pliolite S6B2          20.0Zinc oxide     3.0Stearic acid   2.0Cumar MH 21/23          7.5Zeolex 23      66.5Santocure4          2.0DOTG5     1.0Sulfur         2.5Total          204.5______________________________________ 1 Emulsion copolymer of 23.5% styrene and 76.5% butadiene. 2 A styrenebutadiene copolymer of high styrene content. 3 Paracumarene-indene resin. 4 nCyclohexyl-2-benzothiazole sulfenamide accelerator. 5 Diortho-tolylguanidine.

The recipe was mixed on a Banbury mixer at speed #1, ram pressure of 30 p.s.i., and at a starting temperature of 125° F. The final batch was mixed on a 6-inch by 12-inch mill with a water inlet temperature of 158° F. The compound was cured at 292° F., then tested. The results are shown in Table IV.

              TABLE IV______________________________________Cure    200%     300%     400%Minutes Modulus  Modulus  Modulus                            Tensile                                  Elongation______________________________________PIGMENT-ZEOLEX 23 UNMODIFIED-CONTROL5        80      --       --     80    28010       80      --       --     80    28015      470      650      860    1,300 60520      720      1,000    1,350  1,640 46030      750      1,060    1,450  1,560 420______________________________________PIGMENT-ZEOLEX 23 MODIFIED WITH 10% GAMMAAMINO-PROPYLTRIETHOXYSILANE5       690      1,010    1,340  1,970 58010      910      1,300    1,710  2,480 55015      1,010    1,400    1,820  2,360 51020      1,070    1,480    1,920  2,280 47030      1,090    1,480    1,940  2,360 480______________________________________        Abrasion Index1                   Shore HardnessPigment        10'    15'    20'  10'  15'  20'______________________________________Zeolex 23 Control          2 41.5   47.5 60   72   77Modified Zeolex 23          61.7   63.0   62.3 76   76   77______________________________________        Tear Resistance, Avg.Pigment        5'       10'      15'   20'______________________________________Zeolex 23 Control          37.5     38.5     174   160Modified Zeolex 23          216.5    193.5    195   187.5______________________________________ 1 Percent of NBS Standard sample. 2 Not cured.

The results indicate that Zeolex 23 modified with gamma aminopropyltriethoxysilane, when compared with unmodified Zeolex 23 used as a filler for rubber, is faster curing, has increased modulus, increased tensile strength, and improved tear resistance and abrasion resistance.

It should also be noted that physical and "wet" electrical properties of filled resin systems can be significantly improved by treating the fillers in accordance with this invention.

I have found that in addition to the concepts disclosed above, the properties of the modified pigments are affected by the solvent used in their preparation.

The properties of carbon blacks, clays and silicates modified in aqueous systems, such as disclosed in Example 2, vary markedly from the properties of these same pigments modified in nonaqueous systems as disclosed in Examples 1 and 3.

In order to demonstrate these differences, regular Suprex clay, Suprex clay of Example 2, and Suprex clay modified in nonaqueous solvent according to the teachings of Example 7 were used in producing rubber compounds using the following recipe.

______________________________________              Parts by weight______________________________________Smoked sheet1   100Clay (as specified in Table V)                104Zinc oxide           5Sulfur               3Captax               1Stearic acid         4______________________________________ 1 Natural rubber.

The compounds were mixed on a 6-inch by 12-inch laboratory mill and then cured at 260° F. to produce 30-, 45-, and 60-minute cures of each.

Table V below compares the abrasion index and the 200% modulus level of each of the test materials.

              TABLE V______________________________________        Abrasion Index,                   200% Modulus        Percent    p.s.i.Clay           30'    45'    60'  30'  45'  60'______________________________________Suprex Control 55.0   55.9   53.7 760  960  990Suprex 3% Modifier          72.8   68.6   65.2 2,000                                  2,070                                       2,170(Benzene)Suprex 3% Modifier          84.6   85.5   70.7 1,740                                  1,970                                       1,990(Water)______________________________________

The results as set forth in Table V clearly indicate that clays modified in accordance with the invention impart superior properties to rubber compounds when used as a filler therein. These results also demonstrate that the clays modified in an aqueous system give a higher abrasion resistance and a lower modulus than clays modified in a nonaqueous system.

While natural rubber was used in the recipes tested in Table V, these tests were also conducted with similar results from recipes using SBR, polyurethanes and polybutadiene.

The foregoing is illustrative only and additional modifications may be made without departing from the substance of the invention as defined in the appended claims.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2742378 *Aug 2, 1952Apr 17, 1956Gen Tire & Rubber CoFillers having vinyl siloxane groups bonded to the surface thereof and copolymers thereof with ethylenically unsaturated polymerizable monomers
US2832754 *Jan 21, 1955Apr 29, 1958Union Carbide CorpAlkoxysilylpropylamines
US3015569 *Nov 26, 1958Jan 2, 1962Interchem CorpTreatment of pigments
US3029209 *Aug 12, 1959Apr 10, 1962Minerals & Chem Philipp CorpPolyurethane foams filled with organophilic kaolin clay and method for making same
US3150109 *Aug 1, 1961Sep 22, 1964Minerals & Chem Philipp CorpFilled polyurethane foams and method for making same
US3158519 *Jun 30, 1960Nov 24, 1964Owens Corning Fiberglass CorpContinuous process for producing molding compounds
US3168389 *Dec 28, 1960Feb 2, 1965Pittsburgh Plate Glass CoSilane forming size and glass fiber strands threated therewith for resin reinforcement
GB863412A * Title not available
Non-Patent Citations
Reference
1 *Jellinek et al., Silane Finishes for Fibrous Glass, Presented Before the Society of Plastic Industries, Chicago, Ill., Feb. 5-7, 1957.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5356471 *Aug 17, 1993Oct 18, 1994Merck Patent Gesellschaft Mit Beschrankter HaftungPigments of dark surface color
US5707437 *Aug 30, 1996Jan 13, 1998E. I. Du Pont De Nemours And CompanySilanized titanium dioxide pigments resistant to discoloration when incorporated in polymers
US5889090 *May 15, 1997Mar 30, 1999E. I. Dupont Denemours & CompanyWhite pigment treated with organosilicon compound
US6790904Jun 3, 2002Sep 14, 2004Ppg Industries Ohio, Inc.Resin containing particles have been chemically modified to have a surface tension lower than that of the film-forming resin as cured without particles; improved mar and scratch resistance
US6808808Jan 14, 2003Oct 26, 2004Freeman Gary MCoating composition containing surface treated clay mixture, the surface treated clay mixture used therefor, and methods of their use
US6861115May 18, 2001Mar 1, 2005Cabot CorporationInk jet recording medium comprising amine-treated silica
US6916368Feb 6, 2003Jul 12, 2005Ppg Industries Ohio, Inc.Containing submicron-sized particles and multi-component composite coating compositions comprising a pigmented or colored base coat and a transparent or clear topcoat
US6964992May 16, 2002Nov 15, 2005Cabot CorporationProduct formed from the contact between fumed silica particles and at least one aminoorganosiloxane.
US7141618Jun 3, 2002Nov 28, 2006Ppg Industries Ohio, Inc.Powder coating; wear resistance; reducing surface tension
US8043715Jun 6, 2006Oct 25, 2011E. I. Du Pont De Nemours And CompanyPaper and paper laminates containing modified titanium dioxide
EP0232745A1 *Jan 16, 1987Aug 19, 1987Hewlett-Packard CompanyProcess for increasing the dispersibility of carbon black
EP0468140A2 *Apr 16, 1991Jan 29, 1992Degussa AktiengesellschaftWith organosilicium-compound chemically modified carbon blacks, method for their preparation and their use
EP0816420A1 *Jun 17, 1997Jan 7, 1998THE GOODYEAR TIRE & RUBBER COMPANYAminosilane compounds in silica-filled rubber compositions
WO2006002085A1Jun 15, 2005Jan 5, 2006Grace W R & CoChemically assisted milling of silicas
WO2013181021A1 *May 21, 2013Dec 5, 2013Kamin LlcMethods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom
Classifications
U.S. Classification106/475, 106/465, 106/490, 106/486, 106/420
International ClassificationC09C3/12, C08K9/06
Cooperative ClassificationC09C3/12, C08K9/06
European ClassificationC08K9/06, C09C3/12