CA1293976C - Treating agent comprising organopolysiloxane containing polyoxyalkylene and alkoxysilylalkyl radicals - Google Patents
Treating agent comprising organopolysiloxane containing polyoxyalkylene and alkoxysilylalkyl radicalsInfo
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- CA1293976C CA1293976C CA000537247A CA537247A CA1293976C CA 1293976 C CA1293976 C CA 1293976C CA 000537247 A CA000537247 A CA 000537247A CA 537247 A CA537247 A CA 537247A CA 1293976 C CA1293976 C CA 1293976C
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
TREATING AGENT COMPRISING ORGANOPOLYSILOXANE CONTAINING
POLYOXYALKYLENE AND ALKOXYSILYLALKYL RADICALS
ABSTRACT OF THE DISCLOSURE
A composition for treating a solid material to give it durable hydrophilic and/or antistatic properties comprises a siloxane compound which has at least one G radical and one or more polyoxyalkylene groups, wherein G is a group having the formula -R1O(C2H4O)b(C3H6O)cR2 wherein R1 is an alkylene radical having from 2 to 5 carbon atoms, R2 is a hydrogen atom or a monovalent organic radical having from 1 to 5 carbon atoms, b is an integer having a value of from 0 to 50, c has a value of from 0 to 50, and plus c has a value of from 20 to 100. In a preferred embodiment the composition is useful to treat fibers and fiber containing materials. The composition can further contain a curing agent for the silicone.
POLYOXYALKYLENE AND ALKOXYSILYLALKYL RADICALS
ABSTRACT OF THE DISCLOSURE
A composition for treating a solid material to give it durable hydrophilic and/or antistatic properties comprises a siloxane compound which has at least one G radical and one or more polyoxyalkylene groups, wherein G is a group having the formula -R1O(C2H4O)b(C3H6O)cR2 wherein R1 is an alkylene radical having from 2 to 5 carbon atoms, R2 is a hydrogen atom or a monovalent organic radical having from 1 to 5 carbon atoms, b is an integer having a value of from 0 to 50, c has a value of from 0 to 50, and plus c has a value of from 20 to 100. In a preferred embodiment the composition is useful to treat fibers and fiber containing materials. The composition can further contain a curing agent for the silicone.
Description
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TREATING AGENT COMPRISING ORGANOPOLYSILOXANE CONTAINING
POLYOXYALKYLENE AND ALKOXYSILYLAI,KYL RADICALS
The present invention relates to an agent for treating solids. More specifically, the present inven-tion relates to a treatment agent which imparts a durable hydrophilicity and antistaticity to solid materials.
In order to impart hydrophilicity and antistaticity to solids such as, for example, moldings, sheet-form materials, foams, fibers, and powders, treatments have heretofore been carried out using various organic surfactants, for example, cationic types, anionic types, and nonionic types, etc.
Eurthermore, organopolysiloxane-polyoxyalkylene copolymer, such as that disclosed in Japanese Patent Publication Number 44-6069 (6,069/69~, and organosilyl-terminated polyoxyalkylene-modified and alkoxysilylalkyl-modified organopolysiloxane, such as that disclosed in Japanese Patent hpplication Laid Open Number 57-139123 (139,123/82), are known as silicone-type agents for the treatment of solids.
However, treatment methods which employ organic surfactant and the treatment method using the organo-polysiloxane-polyoxyalkylene copolymer as described in Japanese Patent Publication Number 44-6069 suffer from the problem of providing only a temporary hydrophilicity and antistaticity, and these effects are readily lo~t upon exposure to water or organic solvent.
While the silicone-type surfactant described in Japanese Patent Application Laid Open Number 57-139123 has the alkoxysilyl alkyl group as a side chain, an agent for treating solids whose principal agent i~ organo-poly~iloxane having at least 1 polyoxyalkylene group as a ~ide chain or molecular ~erminal and having the alkoxysilylalkyl group at least at one molecular terminal, is unknown.
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TREATING AGENT COMPRISING ORGANOPOLYSILOXANE CONTAINING
POLYOXYALKYLENE AND ALKOXYSILYLAI,KYL RADICALS
The present invention relates to an agent for treating solids. More specifically, the present inven-tion relates to a treatment agent which imparts a durable hydrophilicity and antistaticity to solid materials.
In order to impart hydrophilicity and antistaticity to solids such as, for example, moldings, sheet-form materials, foams, fibers, and powders, treatments have heretofore been carried out using various organic surfactants, for example, cationic types, anionic types, and nonionic types, etc.
Eurthermore, organopolysiloxane-polyoxyalkylene copolymer, such as that disclosed in Japanese Patent Publication Number 44-6069 (6,069/69~, and organosilyl-terminated polyoxyalkylene-modified and alkoxysilylalkyl-modified organopolysiloxane, such as that disclosed in Japanese Patent hpplication Laid Open Number 57-139123 (139,123/82), are known as silicone-type agents for the treatment of solids.
However, treatment methods which employ organic surfactant and the treatment method using the organo-polysiloxane-polyoxyalkylene copolymer as described in Japanese Patent Publication Number 44-6069 suffer from the problem of providing only a temporary hydrophilicity and antistaticity, and these effects are readily lo~t upon exposure to water or organic solvent.
While the silicone-type surfactant described in Japanese Patent Application Laid Open Number 57-139123 has the alkoxysilyl alkyl group as a side chain, an agent for treating solids whose principal agent i~ organo-poly~iloxane having at least 1 polyoxyalkylene group as a ~ide chain or molecular ~erminal and having the alkoxysilylalkyl group at least at one molecular terminal, is unknown.
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The object of the present invention is to eliminate the problems described above by providing a novel agent for trea~ing solids which can impart a durable hydro-philicity and antistaticity to solids. It is a particular object of this invention to provide a method for confer-ring durable hydrophilicity and antistaticity properties to fibers and fiber-containing materials.
These objects, and others which will become apparent upon consideration of the following disclosure an.d appended claims, are obtained by the method of this invention which, briefly stated, comprises treating a solid material with a composition which comprises, as its principal component, an organopolysiloxane compound which contains at least one siloxane chain-terminating siloxane unit bearing an alkoxysilylalkyl radical and at least one siloxane unit bearing a polyoxyalkylene radical. In a preferred embodiment of this invention both of the siloxane chain-terminating siloxane units bear alkoxy-silylalkyl radical.
The present invention relates to a composition for treating solids, said composition comprising an organo-polysiloxane compound which has the Eormula A(R2SiO)X(RQSiO)y(RGSiO)zSiR2A, wherein Q denotes a radical having the formula -R SiXaR(3-a)~
G denotes a radical having the formula _Rlo(c2~I4o)b(c3H6o)cR ~
A denote~ a radical ~elected from the group consist-ing oE Q and G radicals, at least one A radical ~ being a Q radical, x has a value of from 5 to 500, y has a ~alue of from O to 100, z has a value of from O to 100, with the proviso that when A
. aonsists entirely of Q, then z is an integer with a value of fram 1 to 100, X denotes an alkoxy or alkoxyalkoxy radical having from 1 to 4 carbon atoms, ; !
The object of the present invention is to eliminate the problems described above by providing a novel agent for trea~ing solids which can impart a durable hydro-philicity and antistaticity to solids. It is a particular object of this invention to provide a method for confer-ring durable hydrophilicity and antistaticity properties to fibers and fiber-containing materials.
These objects, and others which will become apparent upon consideration of the following disclosure an.d appended claims, are obtained by the method of this invention which, briefly stated, comprises treating a solid material with a composition which comprises, as its principal component, an organopolysiloxane compound which contains at least one siloxane chain-terminating siloxane unit bearing an alkoxysilylalkyl radical and at least one siloxane unit bearing a polyoxyalkylene radical. In a preferred embodiment of this invention both of the siloxane chain-terminating siloxane units bear alkoxy-silylalkyl radical.
The present invention relates to a composition for treating solids, said composition comprising an organo-polysiloxane compound which has the Eormula A(R2SiO)X(RQSiO)y(RGSiO)zSiR2A, wherein Q denotes a radical having the formula -R SiXaR(3-a)~
G denotes a radical having the formula _Rlo(c2~I4o)b(c3H6o)cR ~
A denote~ a radical ~elected from the group consist-ing oE Q and G radicals, at least one A radical ~ being a Q radical, x has a value of from 5 to 500, y has a ~alue of from O to 100, z has a value of from O to 100, with the proviso that when A
. aonsists entirely of Q, then z is an integer with a value of fram 1 to 100, X denotes an alkoxy or alkoxyalkoxy radical having from 1 to 4 carbon atoms, ; !
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R de~otes a monovalent hydrocarbon or halogenated hydrocarbon radical having from 1 to 10 carbon atoms, Rl denotes an alkylene radical having from 2 to 5 carbon atoms, R2 denotes a hydrogen atom or a monovalent organic radical having from 1 to 5 carbon atoms, a has a value of 2 or 3, b has a value of from 0 to 50, c has a value of from 0 to 50, and b plus c has a value of from 2 to 100;
there being present in said organopolysiloxane at least one G radical.
By way of explanation of the preceding, R in the above formulas is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and it is exemplified by alkyl groups such as methyl, ethyl, propyl, and octyl; by substituted alkyl groups such as 3,3,3-trifluoropropyl, 2-phenylethyl and 2-phenylpropyl; by aryl groups such as phenyl and tolyl; and by substituted aryl groups. Alkyl groups, most preferably methyl, are preferred here. The groups R
in a single molecule may be identical or different.
A can be a Q or G group, delineated below, with -the proviso that at least one A is a Q group. Preferably all A groups are Q groups.
Q i~ a group having the formula -RlSiXaR(3 a) and it functions to impart durability by tightly bonding -the present organopolysiloxane to solid3. Rl is to be an al}cylene group having 2 to 5 carbon atom~, and is exemplified by -CH2CH2-~ -CH2cH2cH2 '1 l 3 2 -(CH2)4-, and -(CE12)5-. The groups R within the mole-cule may be identical or different. X i9 an alkoxy group having 1 to 4 carbon atoms, and it is exemplified by methoxy, ethoxy, propoxy, and methoxy~thoxy.
The value of a i~ to be 2 or 3.
G is a group having the formula -R10(C~H40)btC3H60)CR2, and it unctions to impart antistaticity and hydrophilicity to the solid. R is to be the hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and said monovalent hydrocarbon groups are exemplified by alkyl groups such as methyl, ethyl, and propyl, and by acyl groups such as acetyl and propionyl. In each G group b and c are both integers having values of O to 50 wherein the sum b + c is to have a value of 2 to 100.
In the organopolysiloxane x is an integer having a value of 5 to 500, y is an integer having a value of O to 100, and z is an integer having a value of O to 100, with the condition that when A consists entirely of Q, z is then to be an inteqer having a value of 1 to 100. When x is 50, lubricity will also be imparted to the solid.
The organopolysiloxane to be used in the present invention can be synthesized, for example, by addition reacting diorganohydrogensilyl-terminated diorganosiloxane-organohydrogensiloxane copolymer with alkoxysilyl group-containing alkene and alkenyl-substituted polyoxyalkylene compound, the latter two being used in the appropriate ratio, under the catalytic activity of a platinum-type catalyst such as chloroplatinic acid. Further synthesis details are disclosed in the examples below.
With regard to the use of the present invention's agent for treating solids, the claimed composition can be used as is, or it may be dissolved in water as is, or it may be auto-emulsified in water. Alternatively, it may be emulsified using a suitable emulsifying agent such as, for example, the salt~ of sulfate esters of higher alcohols, alkylbenzene-sulfonate salts, higher alcohol-polyoxyalkylene adducts, alkylphenol-polyoxyalkylene adducts, higher fatty acid sorbitan e~ters, etc.
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Alternatively, the ~olid treatment agent of the present invention may be used by dis~olving the above-described organopolysiloxane in an organic solvent ~uch as, for example, toluene, xylene, benzene, n-hexane, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketona, ethyl acetate, butyl acekate, mineral terpene, perchloroethylene, trichloroethylene, etc.
Solid~ may be treated with the treatment agent of the present invention by methods such as spraying, roll coating, brush coating, immersion, etc. While the quantity of adhesion will vary with the type of solid and so cannot be strictly specified, it will generally be 0.01 to 10.0 wt % based on the solid. After application, a durable hydrophilicity and antistaticity will be imparted to the ~olid, for example, upon standing at room temperature, or upon blowing on hot air, or upon a heat treatment.
Furthermore, treatment may be conducted using the treatment agent of the present invention in combination with the metal salts of organic acids, for example, their zinc, tin, zirconium, etc., salts such as zinc stearate, zinc oleate, dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, zirconium stearate; and/or amino-containing alkoxysilanes, epoxy-containing alkoxysilanes, organohydrogenpolysiloxanés, ~ilanol-containing orqano-poly~iloxane~; etc.
Solid~ which may be treated with the treatment agent of the pre3ent invention are exemplified by various fibers and their fabrics; sheet-form materials such a~
paper, natural and ~ynthetic leathers, Cellophane * and plastic films; foams ~uch a~ synthetic resin foams;
synthetic resin moldings; natural and synthetic rubber moldings; metal moldings; glas~ moldings; and powder~
such a~ inorganic powders and synthetic resin powders.
The afore~aid fibers are exemplified in terms of ~pecies by natural fibers ~uch as hair, wool, silk, flax, * trade mark ~., ~L2q~3~
cotton and asbestos; by regenerated ~ibers such as rayon and acetate; by synthetic fibers such as polyester, polyamide, "Vinylon"* polyacryl nitrile, polyethylane, polypropylen~ and spandex and by glass fibers; carbon fibers; and silicon carbide fibers. They are exemplified in terms of form by the staple, filament, tow, and yarn.
Their fabrics are exemplified by knits, nonwovens, resin-finished fabrics, and sewn articles thereof.
The invention will be explained in the ~ollowing using illustrative examples. I~ the examples and refer-ence examples, parts = weight parts and % = weight %, and the viscosity is the value measured at 25C.
Reference ExamPle 1 Vinyltrimethoxysilane, 148.2 g, is placed in a three-neck 500 ml flask equipped with a reflux condenser, the internal temperature i~ raised to 60C by heating, 0.15 g 2% isopropanolic chloroplatinic acid solution is added, and 51.8 g tetramethyldisiloxane is dripped in.
Organosiloxane I having the following formula is obtained by a reaction at 100C for 2 hours and distillation i vacuo at 140C/5 mmHg.
(CH30)3sicH2cH2si(cH3)2osi(cH3)2cH2cH2(ocH3)3 Organosiloxane I, 61.4 g, methylhydrogensiloxane cyclic tetramer, 59.8 g, cyclic dimethylsiloxane tetramer, 368.9 g, and 15 g thoroughly dried activated clay as polymerization catalyst are placed in a three-neck 500 ml flask equipped with a reflux condenser, and polymerized at 75C for 10 hours. ~fter cooling, filtration is conducted using an assistant.
Exactly 136.9 g of thi~ organopolysiloxane product, 13.4 g vinyltrimethoxysilane, 149.7 g allyl-containing polyether having the following formula CH2=CHCH20(CH2CH20)12CH3 and 90 g toluene are placed in a 500 ml three-neck fla~k equipped with a reflux condenser, the internal temperature is raised to 60C by heating, 0.38 g 2% isopropanolic chloroplatinic acid ~olution iB
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added, and a reaction i9 then carried out at 120C for 2 hours. After the completion o the reaction, the volatiles ar~ st~ipped in vacuo. The product is identi-fied by infrared absorption spectral analysis and nuclear magnetic resonance analysis as an organopolysiloxane ~Organopolysiloxane A, viscosity = 305 cS~ having the following formula:
eo)3sicH2cH2(Me2sio~3l(Mesio)2~Melio)4siMe2cH2cH~si(oMe)3 (MeO)3SiCH2CH2 (cH2)3o(cH2cH2o)l2 3 Reference Example 2 Siloxane II, 89.1 y, having the ormula El(Me2sio)4l(MeHsio)6siMe2H~
7.5 g vinyltr.imethoxysilane, and 60 g toluene are placed in a 500 ml three-neck flask equipped with a r~flux condenser, the internal temperature is raised to 80C by heating, 0.1 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction is conducted at 110C
for 30 minutes. After cooling to 80C, 103.4 g allyl-containing polyether I having the formula CH2=cHcH2o~cH2cH2o)l2H is added, the temperature is raised to 90C, 0.15 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction is conducted a-t 120C for 1 hour. After the end o~ the reaction, the volatiles are stripped in vacuo at 140C/5 mmHg. Infra-red absorption spectral analy~i3 and nuclear magnetic resonance analysis conirm the product to be an organopoly-siloxane (Organopolysiloxane B, vi~cosity ~ 1,100 cS) having the following formula:
(Meo)3sic~2cH2(Me2sio)4l(Mesllo)6siM~2cH2 2 ( 3 (CH2)30(CH2CH20)12H
Reerence ~ ple 3 A siloxane, 69.3 g, having -ths formula H(M~2sio)2o(Me~Isio)4siMe2H~
11.0 g methylvinyldimethoxysilane and 60 g toluene are r~,3~p 7ç~
placed in a 500 ml three-neck flask equipped ~ith a ~eflux condensar, the internal temperature i~ raised to 80C by hea-ting, 0.1 g 2% isopropar~oli~ chloroplatinic acid solution is added, and a reaction is carried out for 30 minutes at 105C. ~ftar cooling to 80C~ 119.7 g allyl-containing polyether having the formula CH2=CHCH20(C2H40)8(C3H60)4H is added, the temperature is raised to 90C, 0.15 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction i5 conducted at 120C for 1 hour. After the end of the reaction, the volatiles are stripped in vacuo at 140C/5 mmHg. Infra-red absorption spectral analysis and nuclear magnetic resonance analysis confirm the product to be an organo-polysiloxane (Organopolysiloxane C, viscosity = 500 cS) having the following formula:
Me(MeO)2SiC2H4(Me2SiO)20(Me I io)4siMe2c2H4si(oMe)2Me C3H60(C2H40)8(c3H6o)4 Reference Example 4 Siloxane II, as used in Reference Example 2, 89.1 g, vinyltrimethoxysilane, 7.5 g, allyl group-containing polyether I as used in Reference Example 2, 103.4 g, and 60 g toluene are placed in a three-neck 500 ml flaak equipped with a reflux condenser, the internal tempera-ture is raised to 80C by heating, 0.25 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction ia conducted at 125C for 1 hour. After the reaction, -the volatiles are s-tripped in vacuo at 140C/5 mmHg.
Infrared abaorption analyaia and nuclear magnetic resonance analy~is confirm thi~ material to be an organo-polysiloxane (Organopolyslloxane D, viscoaity = SOO cS) having the followlng structure:
~3 2CH2(Me2SiO)41(~e7iO)1(MeSiO)5SiMe2CH~
(MeO)3SiCH2CH2 (CH2)30(CH2cH20)l2H
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Example 1 One part of the Organopoly~iloxane A synthesized according to Reference Example 1 and having the formula O)3SiCH2CH2(Me2SiO~31(MeSiO)2~MeSiO~SiMe2CH2CH2Si(oMe~3 ~MeO)3Sic~2c~2 (CH~)30(CH2CH2O)12CH3 8 parts glyoxal-type re~in (Sumitex Resin NS-2*from Sumitomo Chemical Co., Ltd.), 2 part amine catalyst P'sumitex Accelator X-80"*rom Sumitomo Chemical Co., Ltd.), 0.5 part of a tin cataly~t (50% emulsion of dibutyltin dilaurate), and 88.9 part~ water are mixed to homogeneity to prepare a treatment bath. Two sheets of twilled fabric (40 cm x 20 cm~ 65% polyester/35% cotton) are immersed in thi 9 treatment bath or 30 seconds, adjusted to a 100% expression ratio on a mangle, dried at room temperature for 10 hours, and then heated in an oven at 150C for 5 minutes. The resulting organopolysiloxane-finished fabrics are then each cut in half. One sheet of the re~ulting four fabric sheets is washed once, one sheet i~ wa~hed 5 time3, and one ~heet i~ washed 10 times (wash condition~ a~ below). Following tnis, these are rinsed twice with water (under the wash conditions, but with no detergent) to afford wa~hed fabric~. Bath ratio = 1/50: Time = 10 minutes: Temperatur~ = 40C.
Detergent = 0.5% aqueou~ ~olution of'~ew White"* ~from Lion Corp.) In the water ab~orptivity teYt, the organopolysiloxane-finished fabric (before and ater wa~hlng) i~ laid out horizontally on ~pread out filter paper, a drop of water i~ dalivered from a ~yringe, and the time required for its ~oalting in i~ then mea~ur~d.
To measure the residual organopolysiloxane, the %
residual organopolysiloxane after washlng 1~ analyzed u~ing an X-ray fluore3c2nt analyzer from Rigaku Corp.
ba~ed on tho difference in ~illcon atom count~ before and `' * trade mark i,' ~3~
after washing the treated fabric. The re~ult~ are reported in Table 1.
Comparison ExamPle 1 Treatment is conducted exactly as in Example 1, with the exception that 1 part Organopoly~iloxane (i) having a viscosity of 1,200 cS and the formula Me(Me2sio)55(Melio)2(Melio)5SiMe3 (Meo)3sicH2cH2 (CH2)30(CH2~H~0)12CH3 is used in place of Organopolysiloxane A. Testing is conducted a~ in Example 1, and these results are al50 reported in Table 1.
Table 1 Water Absorptivity % Residual (second~) Organopolysiloxane Number of Washes . O 1 5 10 0 1 5 10 Example 16.3 4.4 2.3 2.0100.0 94.5 87.0 85.0 Comparison Example 1 17.5 12.2 9.3 6.6 100.0 81.8 72.2 66.0 ExamDle 2 Five parts of Organopolysiloxane B, ~ynthesized according to Reference Example 2 and having the ormula (MeO)3SiCH2CE12(Me2SiO)~,~l(M~SiO)6SiMe2CH2CH2Si(OMe)3 (C~I2)3o(cH2cH2o)l2oH
N-(b0ta-aminoethyl)-gamma~aminopropyltrimethoxysilane, 0.5 part, dibutyltin dlacetate, 0.2 part and ~9.5 part~
toluene are mixed to homogeneity to prepare a treatment bath. 65% polyester/35% cotton broadcloth (40 cm x 20 cm), which ha~ been coated wit~ a 3~ add-on of the glyoxal-type resin a~ used in the treatment ba~h in Example 1, i~ immarsed ln thi~ treatment bath for 30 ~econd~ adjuated to an expre~lon ratio of 100% ucing a 3~7~
mangle, dried at room temperature by standing for 10 hours, and then heated in an oven at 150C for 5 minutes.
The obtained organopolysiloxane-finished fabric is cut in half, and one sample i.s washed once under the wash conditions of Example 1 and rinsed twice with water to afford a washed sampla.
Both before and after washing, the organopolysiloxane-finished fabric is subjected to the water absorptivity test and testing of the % residual organopolysiloxane as described in Example 1. These results are reported in Table 2.
Comparison Example 2 Treatmsnt and testing are conducted by the methods described in Example 2, with the exception that Organo-polysiloxane ~i), as used in Comparison Example 1, is used instead of Organopolysiloxane.B. These results are also reported in Table 2.
Example 3 Treatment and testing are conducted by the methods of Example 2, with the exception that 5 parts Organopoly-siloxane C (viscosity = 500 cS), synthesized as in Reference Example 3 and having the following formula Me(MeO)2SiC2H4(Me2SiO)20(MeIio)4siMe2c2H4si(oMe)2Me C3H60(C2H40)8(c3H6o)4 is used in place of organopolysiloxane B. These results are reported in Table 2.
Comparison ExamPle_ Treatment and testing are conducted as described in Example 2, with the exception that 5 part~ Organopoly-siloxane (ii) having a viscosity of 1,000 cS and the formula Me(Me2sio)4l(Mesio38siMe2oMe (CH2)3O(CH2CH20)25H
3~
is used in place of Organopoly~iloxane B. These result~
are raported in Table 2.
Table 2 Water Ab~orptivity % R2sidual (seconds~ rgano~oly~iloxane Before Wash After Wash After Wash Example 2 4.5 5.~ 60 Example 3 4.3 5.5 45 Comparison Example 2 5.0 5.5 55 Comparison Example 3 3.1 10.5 11 Example 4 Organopoly~iloxane A as used in Example 1, 5 parts, i~ dissolved to homogeneity in 995 parts toluene. A 65%
polyester/35% cotton broadcloth (40 x 20 cm), coaked with a 3% add-on of the glyoxal-type re~in, i8 the~ immersed in thi~ solution for 30 second3, adjusted to an expres-sion ratio of 100% on a mangle, dried by standing at room temperature for 10 hour~, and then heated in an oven for 5 minutea at 150C. The obtained organopolysiloxane-fini~hed fabric iB then cut in half, and one sample of organopoly-siloxane-finished fabric i~ washed once under the wa~h conditions o~ Example 1 and rinsed twice. Test samples are thus prepared o organopolysiloxane-finished fabric before and after wa~hlny.
An antistaticity test i~ carried out a~ follows.
The treated fabric~ (before and after wa~hing) are allowed to stand at 20~C/RH 65% or 1 week. Their ' ~ ': '!. '' .
3~76 triboelectrification voltages are then measured using a Kyodai Kaken"rotary static tester (800 rpm for 60 seconds).
Cotton fabric (unbleached muslin #3) is used as the friction fabric.
A soiling resistance test is conducted a~ follows.
An artificial soilant is prepared by thoroughly mixing and pulverizing 300 g ASTM No. 1 oil, 3 g coal tar, 5 g dried clay powder, 5 g portland cement and 5 g sodium dodecylbenzenesulfonate in a mortar. 5 ml of this artificial soilant, 100 ml of a 0.5% aqueous solution of "Marseilles ~ ~ and 10 steel balls are placed in a 450 ml glass bottle. Washed and unwashed samples of organopoly-siloxane-finished fabric and untreated fabric are respec-tively placed in the bottle, treated at 60C for 30 minutes, and then gently rinsed with water and dried.
These are then washed for 10 minutes on high in an automatic reversing rotary washing machine using a 0.5%
agueous solution of"Marseilles Soap"*. After then washing in water and drying, the reflectance of the test fabrics i3 measured at a wavelength of 550 millimicrons using a reflectometer. These test results are reported in Table 3.
Comparison ExamPle 4 Treatment and testing are cond~cted by the methods of Example 4, but using 5 parts of the Organopolysiloxane (ii) used in Comparison Example 3 in place of Organopoly-siloxane A. These results are also reported in Table 3.
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Table 3 Triboel0ctrification ~ Reflectance at Voltaqe (V) 550 millimicrons Before After Wa~h Wash Example 4 880 1030 71 Comparison Example ~ 900 1530 53 Untreated Fabric 1650 1610 53 Example 5 Organopolysiloxane A as synthesized in Reference Example 1, 10 partR, and 1 part zinc stearate are dis-solved to homo~eneity in 89 parts water to prepare a treatment solution. This is then applied at an organo-polysiloxane add-on of 0.2 g/m2 by spraying on one side of a plasma-processed polyethylene terephthalate film.
After coating, the film is dried at room temperature overnight and then heated in an oven at 130C for 10 minute 3 .
In the compari~on example~, 10% a~ueous solutions ar~ prepared using, respectively, Organopolysiloxane (ii) (u~ed in Comparison Exampla 3) or nonionic ~urfactant (NS-210 from Nippon Oils and Fats Co., Ltd.), and each is then sprayed on one side of the plasma-processed polyethylene terephthalate film at an add-on of 0.2 g/m2, followed by drying and heating.
The obtained three treated films are immersed in running water ~or 6 hours. After thi~, the upper surface of a thermostatted water bath (set at 60C t 2C) is covered and sealed with each film, wherein the treated J surface i3 down. The status of the films i~ inspected .. . ....
*trade mark after 3 hour~. The film treated with Organopoly~iloxane A, a treatmen-t agent of the present invention, is hydro-philic, presents uniorm wetting of ths lower film surface, and i~ transparent. However, the lower surfaces of the other 2 films are not hydrophilic, and are adhered with water droplets and ar~ opaque.
Example 6 A 0.5% aqueous solution of Organopolysiloxane D, 100 g, (synthesized in Reference Example 4~ is prepared, 50 g carbon black powder is added, and this mixture i5 allowed to dry by standing. Heating at 100C for 5 minutes then affords a carbon black powder having a 1% add-on of Organopolysiloxane D.
In the comparison example, carbon black powder is similarly treated with Organopolysiloxane (iij to afford a carbon black powder having a 1% add-on o Organopoly-siloxane (ii).
50 g of each carbon black powder is separately placed in 1 1 of water, followed by ~kirring for 3 hours, filtration and drying. 5 Parts o~ each o the obtained carbon black powders is then separately dispersed to homogeneity in an a~ueous acrylic emulsion pain-t to produce a paint. The paint containing the Organopoly-siloxane D-treated carbon black powder presented a uniform dispersion, and did not suffer from sedimentation.
However, the Organopolysiloxane (ii)-treated carbon black powder underwent rapicl sedimentation, and the dispersion was inhomogeneous. These observation~ indicate that the pre~ent inVention' 8 agent for treating ~olids ha~ the capacity to lmpart a durable hydrophilicity.
Because the pressnt invention'~ agent for treating ~olid~ ha~ a~ it~ principal agent an organopoly~iloxane which ha~ the alkoxysilylalkyl group at least at one molecular terminal and which al~o ha~ at lea~t 1 polyoxy-alkylene group a~ a pendant group or at the molecular terminal~, it can impart a durable hydrophilicity and .~
antistaticity to solid materials. As a consequence, it is very us~ful industrially.
R de~otes a monovalent hydrocarbon or halogenated hydrocarbon radical having from 1 to 10 carbon atoms, Rl denotes an alkylene radical having from 2 to 5 carbon atoms, R2 denotes a hydrogen atom or a monovalent organic radical having from 1 to 5 carbon atoms, a has a value of 2 or 3, b has a value of from 0 to 50, c has a value of from 0 to 50, and b plus c has a value of from 2 to 100;
there being present in said organopolysiloxane at least one G radical.
By way of explanation of the preceding, R in the above formulas is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and it is exemplified by alkyl groups such as methyl, ethyl, propyl, and octyl; by substituted alkyl groups such as 3,3,3-trifluoropropyl, 2-phenylethyl and 2-phenylpropyl; by aryl groups such as phenyl and tolyl; and by substituted aryl groups. Alkyl groups, most preferably methyl, are preferred here. The groups R
in a single molecule may be identical or different.
A can be a Q or G group, delineated below, with -the proviso that at least one A is a Q group. Preferably all A groups are Q groups.
Q i~ a group having the formula -RlSiXaR(3 a) and it functions to impart durability by tightly bonding -the present organopolysiloxane to solid3. Rl is to be an al}cylene group having 2 to 5 carbon atom~, and is exemplified by -CH2CH2-~ -CH2cH2cH2 '1 l 3 2 -(CH2)4-, and -(CE12)5-. The groups R within the mole-cule may be identical or different. X i9 an alkoxy group having 1 to 4 carbon atoms, and it is exemplified by methoxy, ethoxy, propoxy, and methoxy~thoxy.
The value of a i~ to be 2 or 3.
G is a group having the formula -R10(C~H40)btC3H60)CR2, and it unctions to impart antistaticity and hydrophilicity to the solid. R is to be the hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and said monovalent hydrocarbon groups are exemplified by alkyl groups such as methyl, ethyl, and propyl, and by acyl groups such as acetyl and propionyl. In each G group b and c are both integers having values of O to 50 wherein the sum b + c is to have a value of 2 to 100.
In the organopolysiloxane x is an integer having a value of 5 to 500, y is an integer having a value of O to 100, and z is an integer having a value of O to 100, with the condition that when A consists entirely of Q, z is then to be an inteqer having a value of 1 to 100. When x is 50, lubricity will also be imparted to the solid.
The organopolysiloxane to be used in the present invention can be synthesized, for example, by addition reacting diorganohydrogensilyl-terminated diorganosiloxane-organohydrogensiloxane copolymer with alkoxysilyl group-containing alkene and alkenyl-substituted polyoxyalkylene compound, the latter two being used in the appropriate ratio, under the catalytic activity of a platinum-type catalyst such as chloroplatinic acid. Further synthesis details are disclosed in the examples below.
With regard to the use of the present invention's agent for treating solids, the claimed composition can be used as is, or it may be dissolved in water as is, or it may be auto-emulsified in water. Alternatively, it may be emulsified using a suitable emulsifying agent such as, for example, the salt~ of sulfate esters of higher alcohols, alkylbenzene-sulfonate salts, higher alcohol-polyoxyalkylene adducts, alkylphenol-polyoxyalkylene adducts, higher fatty acid sorbitan e~ters, etc.
~:.
~ ~, 5 ~ 3~7~
Alternatively, the ~olid treatment agent of the present invention may be used by dis~olving the above-described organopolysiloxane in an organic solvent ~uch as, for example, toluene, xylene, benzene, n-hexane, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketona, ethyl acetate, butyl acekate, mineral terpene, perchloroethylene, trichloroethylene, etc.
Solid~ may be treated with the treatment agent of the present invention by methods such as spraying, roll coating, brush coating, immersion, etc. While the quantity of adhesion will vary with the type of solid and so cannot be strictly specified, it will generally be 0.01 to 10.0 wt % based on the solid. After application, a durable hydrophilicity and antistaticity will be imparted to the ~olid, for example, upon standing at room temperature, or upon blowing on hot air, or upon a heat treatment.
Furthermore, treatment may be conducted using the treatment agent of the present invention in combination with the metal salts of organic acids, for example, their zinc, tin, zirconium, etc., salts such as zinc stearate, zinc oleate, dibutyltin diacetate, dibutyltin dioleate, dibutyltin dilaurate, zirconium stearate; and/or amino-containing alkoxysilanes, epoxy-containing alkoxysilanes, organohydrogenpolysiloxanés, ~ilanol-containing orqano-poly~iloxane~; etc.
Solid~ which may be treated with the treatment agent of the pre3ent invention are exemplified by various fibers and their fabrics; sheet-form materials such a~
paper, natural and ~ynthetic leathers, Cellophane * and plastic films; foams ~uch a~ synthetic resin foams;
synthetic resin moldings; natural and synthetic rubber moldings; metal moldings; glas~ moldings; and powder~
such a~ inorganic powders and synthetic resin powders.
The afore~aid fibers are exemplified in terms of ~pecies by natural fibers ~uch as hair, wool, silk, flax, * trade mark ~., ~L2q~3~
cotton and asbestos; by regenerated ~ibers such as rayon and acetate; by synthetic fibers such as polyester, polyamide, "Vinylon"* polyacryl nitrile, polyethylane, polypropylen~ and spandex and by glass fibers; carbon fibers; and silicon carbide fibers. They are exemplified in terms of form by the staple, filament, tow, and yarn.
Their fabrics are exemplified by knits, nonwovens, resin-finished fabrics, and sewn articles thereof.
The invention will be explained in the ~ollowing using illustrative examples. I~ the examples and refer-ence examples, parts = weight parts and % = weight %, and the viscosity is the value measured at 25C.
Reference ExamPle 1 Vinyltrimethoxysilane, 148.2 g, is placed in a three-neck 500 ml flask equipped with a reflux condenser, the internal temperature i~ raised to 60C by heating, 0.15 g 2% isopropanolic chloroplatinic acid solution is added, and 51.8 g tetramethyldisiloxane is dripped in.
Organosiloxane I having the following formula is obtained by a reaction at 100C for 2 hours and distillation i vacuo at 140C/5 mmHg.
(CH30)3sicH2cH2si(cH3)2osi(cH3)2cH2cH2(ocH3)3 Organosiloxane I, 61.4 g, methylhydrogensiloxane cyclic tetramer, 59.8 g, cyclic dimethylsiloxane tetramer, 368.9 g, and 15 g thoroughly dried activated clay as polymerization catalyst are placed in a three-neck 500 ml flask equipped with a reflux condenser, and polymerized at 75C for 10 hours. ~fter cooling, filtration is conducted using an assistant.
Exactly 136.9 g of thi~ organopolysiloxane product, 13.4 g vinyltrimethoxysilane, 149.7 g allyl-containing polyether having the following formula CH2=CHCH20(CH2CH20)12CH3 and 90 g toluene are placed in a 500 ml three-neck fla~k equipped with a reflux condenser, the internal temperature is raised to 60C by heating, 0.38 g 2% isopropanolic chloroplatinic acid ~olution iB
,.. . -i * trade mark .A
?3~
added, and a reaction i9 then carried out at 120C for 2 hours. After the completion o the reaction, the volatiles ar~ st~ipped in vacuo. The product is identi-fied by infrared absorption spectral analysis and nuclear magnetic resonance analysis as an organopolysiloxane ~Organopolysiloxane A, viscosity = 305 cS~ having the following formula:
eo)3sicH2cH2(Me2sio~3l(Mesio)2~Melio)4siMe2cH2cH~si(oMe)3 (MeO)3SiCH2CH2 (cH2)3o(cH2cH2o)l2 3 Reference Example 2 Siloxane II, 89.1 y, having the ormula El(Me2sio)4l(MeHsio)6siMe2H~
7.5 g vinyltr.imethoxysilane, and 60 g toluene are placed in a 500 ml three-neck flask equipped with a r~flux condenser, the internal temperature is raised to 80C by heating, 0.1 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction is conducted at 110C
for 30 minutes. After cooling to 80C, 103.4 g allyl-containing polyether I having the formula CH2=cHcH2o~cH2cH2o)l2H is added, the temperature is raised to 90C, 0.15 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction is conducted a-t 120C for 1 hour. After the end o~ the reaction, the volatiles are stripped in vacuo at 140C/5 mmHg. Infra-red absorption spectral analy~i3 and nuclear magnetic resonance analysis conirm the product to be an organopoly-siloxane (Organopolysiloxane B, vi~cosity ~ 1,100 cS) having the following formula:
(Meo)3sic~2cH2(Me2sio)4l(Mesllo)6siM~2cH2 2 ( 3 (CH2)30(CH2CH20)12H
Reerence ~ ple 3 A siloxane, 69.3 g, having -ths formula H(M~2sio)2o(Me~Isio)4siMe2H~
11.0 g methylvinyldimethoxysilane and 60 g toluene are r~,3~p 7ç~
placed in a 500 ml three-neck flask equipped ~ith a ~eflux condensar, the internal temperature i~ raised to 80C by hea-ting, 0.1 g 2% isopropar~oli~ chloroplatinic acid solution is added, and a reaction is carried out for 30 minutes at 105C. ~ftar cooling to 80C~ 119.7 g allyl-containing polyether having the formula CH2=CHCH20(C2H40)8(C3H60)4H is added, the temperature is raised to 90C, 0.15 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction i5 conducted at 120C for 1 hour. After the end of the reaction, the volatiles are stripped in vacuo at 140C/5 mmHg. Infra-red absorption spectral analysis and nuclear magnetic resonance analysis confirm the product to be an organo-polysiloxane (Organopolysiloxane C, viscosity = 500 cS) having the following formula:
Me(MeO)2SiC2H4(Me2SiO)20(Me I io)4siMe2c2H4si(oMe)2Me C3H60(C2H40)8(c3H6o)4 Reference Example 4 Siloxane II, as used in Reference Example 2, 89.1 g, vinyltrimethoxysilane, 7.5 g, allyl group-containing polyether I as used in Reference Example 2, 103.4 g, and 60 g toluene are placed in a three-neck 500 ml flaak equipped with a reflux condenser, the internal tempera-ture is raised to 80C by heating, 0.25 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction ia conducted at 125C for 1 hour. After the reaction, -the volatiles are s-tripped in vacuo at 140C/5 mmHg.
Infrared abaorption analyaia and nuclear magnetic resonance analy~is confirm thi~ material to be an organo-polysiloxane (Organopolyslloxane D, viscoaity = SOO cS) having the followlng structure:
~3 2CH2(Me2SiO)41(~e7iO)1(MeSiO)5SiMe2CH~
(MeO)3SiCH2CH2 (CH2)30(CH2cH20)l2H
~33~3~
Example 1 One part of the Organopoly~iloxane A synthesized according to Reference Example 1 and having the formula O)3SiCH2CH2(Me2SiO~31(MeSiO)2~MeSiO~SiMe2CH2CH2Si(oMe~3 ~MeO)3Sic~2c~2 (CH~)30(CH2CH2O)12CH3 8 parts glyoxal-type re~in (Sumitex Resin NS-2*from Sumitomo Chemical Co., Ltd.), 2 part amine catalyst P'sumitex Accelator X-80"*rom Sumitomo Chemical Co., Ltd.), 0.5 part of a tin cataly~t (50% emulsion of dibutyltin dilaurate), and 88.9 part~ water are mixed to homogeneity to prepare a treatment bath. Two sheets of twilled fabric (40 cm x 20 cm~ 65% polyester/35% cotton) are immersed in thi 9 treatment bath or 30 seconds, adjusted to a 100% expression ratio on a mangle, dried at room temperature for 10 hours, and then heated in an oven at 150C for 5 minutes. The resulting organopolysiloxane-finished fabrics are then each cut in half. One sheet of the re~ulting four fabric sheets is washed once, one sheet i~ wa~hed 5 time3, and one ~heet i~ washed 10 times (wash condition~ a~ below). Following tnis, these are rinsed twice with water (under the wash conditions, but with no detergent) to afford wa~hed fabric~. Bath ratio = 1/50: Time = 10 minutes: Temperatur~ = 40C.
Detergent = 0.5% aqueou~ ~olution of'~ew White"* ~from Lion Corp.) In the water ab~orptivity teYt, the organopolysiloxane-finished fabric (before and ater wa~hlng) i~ laid out horizontally on ~pread out filter paper, a drop of water i~ dalivered from a ~yringe, and the time required for its ~oalting in i~ then mea~ur~d.
To measure the residual organopolysiloxane, the %
residual organopolysiloxane after washlng 1~ analyzed u~ing an X-ray fluore3c2nt analyzer from Rigaku Corp.
ba~ed on tho difference in ~illcon atom count~ before and `' * trade mark i,' ~3~
after washing the treated fabric. The re~ult~ are reported in Table 1.
Comparison ExamPle 1 Treatment is conducted exactly as in Example 1, with the exception that 1 part Organopoly~iloxane (i) having a viscosity of 1,200 cS and the formula Me(Me2sio)55(Melio)2(Melio)5SiMe3 (Meo)3sicH2cH2 (CH2)30(CH2~H~0)12CH3 is used in place of Organopolysiloxane A. Testing is conducted a~ in Example 1, and these results are al50 reported in Table 1.
Table 1 Water Absorptivity % Residual (second~) Organopolysiloxane Number of Washes . O 1 5 10 0 1 5 10 Example 16.3 4.4 2.3 2.0100.0 94.5 87.0 85.0 Comparison Example 1 17.5 12.2 9.3 6.6 100.0 81.8 72.2 66.0 ExamDle 2 Five parts of Organopolysiloxane B, ~ynthesized according to Reference Example 2 and having the ormula (MeO)3SiCH2CE12(Me2SiO)~,~l(M~SiO)6SiMe2CH2CH2Si(OMe)3 (C~I2)3o(cH2cH2o)l2oH
N-(b0ta-aminoethyl)-gamma~aminopropyltrimethoxysilane, 0.5 part, dibutyltin dlacetate, 0.2 part and ~9.5 part~
toluene are mixed to homogeneity to prepare a treatment bath. 65% polyester/35% cotton broadcloth (40 cm x 20 cm), which ha~ been coated wit~ a 3~ add-on of the glyoxal-type resin a~ used in the treatment ba~h in Example 1, i~ immarsed ln thi~ treatment bath for 30 ~econd~ adjuated to an expre~lon ratio of 100% ucing a 3~7~
mangle, dried at room temperature by standing for 10 hours, and then heated in an oven at 150C for 5 minutes.
The obtained organopolysiloxane-finished fabric is cut in half, and one sample i.s washed once under the wash conditions of Example 1 and rinsed twice with water to afford a washed sampla.
Both before and after washing, the organopolysiloxane-finished fabric is subjected to the water absorptivity test and testing of the % residual organopolysiloxane as described in Example 1. These results are reported in Table 2.
Comparison Example 2 Treatmsnt and testing are conducted by the methods described in Example 2, with the exception that Organo-polysiloxane ~i), as used in Comparison Example 1, is used instead of Organopolysiloxane.B. These results are also reported in Table 2.
Example 3 Treatment and testing are conducted by the methods of Example 2, with the exception that 5 parts Organopoly-siloxane C (viscosity = 500 cS), synthesized as in Reference Example 3 and having the following formula Me(MeO)2SiC2H4(Me2SiO)20(MeIio)4siMe2c2H4si(oMe)2Me C3H60(C2H40)8(c3H6o)4 is used in place of organopolysiloxane B. These results are reported in Table 2.
Comparison ExamPle_ Treatment and testing are conducted as described in Example 2, with the exception that 5 part~ Organopoly-siloxane (ii) having a viscosity of 1,000 cS and the formula Me(Me2sio)4l(Mesio38siMe2oMe (CH2)3O(CH2CH20)25H
3~
is used in place of Organopoly~iloxane B. These result~
are raported in Table 2.
Table 2 Water Ab~orptivity % R2sidual (seconds~ rgano~oly~iloxane Before Wash After Wash After Wash Example 2 4.5 5.~ 60 Example 3 4.3 5.5 45 Comparison Example 2 5.0 5.5 55 Comparison Example 3 3.1 10.5 11 Example 4 Organopoly~iloxane A as used in Example 1, 5 parts, i~ dissolved to homogeneity in 995 parts toluene. A 65%
polyester/35% cotton broadcloth (40 x 20 cm), coaked with a 3% add-on of the glyoxal-type re~in, i8 the~ immersed in thi~ solution for 30 second3, adjusted to an expres-sion ratio of 100% on a mangle, dried by standing at room temperature for 10 hour~, and then heated in an oven for 5 minutea at 150C. The obtained organopolysiloxane-fini~hed fabric iB then cut in half, and one sample of organopoly-siloxane-finished fabric i~ washed once under the wa~h conditions o~ Example 1 and rinsed twice. Test samples are thus prepared o organopolysiloxane-finished fabric before and after wa~hlny.
An antistaticity test i~ carried out a~ follows.
The treated fabric~ (before and after wa~hing) are allowed to stand at 20~C/RH 65% or 1 week. Their ' ~ ': '!. '' .
3~76 triboelectrification voltages are then measured using a Kyodai Kaken"rotary static tester (800 rpm for 60 seconds).
Cotton fabric (unbleached muslin #3) is used as the friction fabric.
A soiling resistance test is conducted a~ follows.
An artificial soilant is prepared by thoroughly mixing and pulverizing 300 g ASTM No. 1 oil, 3 g coal tar, 5 g dried clay powder, 5 g portland cement and 5 g sodium dodecylbenzenesulfonate in a mortar. 5 ml of this artificial soilant, 100 ml of a 0.5% aqueous solution of "Marseilles ~ ~ and 10 steel balls are placed in a 450 ml glass bottle. Washed and unwashed samples of organopoly-siloxane-finished fabric and untreated fabric are respec-tively placed in the bottle, treated at 60C for 30 minutes, and then gently rinsed with water and dried.
These are then washed for 10 minutes on high in an automatic reversing rotary washing machine using a 0.5%
agueous solution of"Marseilles Soap"*. After then washing in water and drying, the reflectance of the test fabrics i3 measured at a wavelength of 550 millimicrons using a reflectometer. These test results are reported in Table 3.
Comparison ExamPle 4 Treatment and testing are cond~cted by the methods of Example 4, but using 5 parts of the Organopolysiloxane (ii) used in Comparison Example 3 in place of Organopoly-siloxane A. These results are also reported in Table 3.
* trade mark **trade mark 3'7~
1~
Table 3 Triboel0ctrification ~ Reflectance at Voltaqe (V) 550 millimicrons Before After Wa~h Wash Example 4 880 1030 71 Comparison Example ~ 900 1530 53 Untreated Fabric 1650 1610 53 Example 5 Organopolysiloxane A as synthesized in Reference Example 1, 10 partR, and 1 part zinc stearate are dis-solved to homo~eneity in 89 parts water to prepare a treatment solution. This is then applied at an organo-polysiloxane add-on of 0.2 g/m2 by spraying on one side of a plasma-processed polyethylene terephthalate film.
After coating, the film is dried at room temperature overnight and then heated in an oven at 130C for 10 minute 3 .
In the compari~on example~, 10% a~ueous solutions ar~ prepared using, respectively, Organopolysiloxane (ii) (u~ed in Comparison Exampla 3) or nonionic ~urfactant (NS-210 from Nippon Oils and Fats Co., Ltd.), and each is then sprayed on one side of the plasma-processed polyethylene terephthalate film at an add-on of 0.2 g/m2, followed by drying and heating.
The obtained three treated films are immersed in running water ~or 6 hours. After thi~, the upper surface of a thermostatted water bath (set at 60C t 2C) is covered and sealed with each film, wherein the treated J surface i3 down. The status of the films i~ inspected .. . ....
*trade mark after 3 hour~. The film treated with Organopoly~iloxane A, a treatmen-t agent of the present invention, is hydro-philic, presents uniorm wetting of ths lower film surface, and i~ transparent. However, the lower surfaces of the other 2 films are not hydrophilic, and are adhered with water droplets and ar~ opaque.
Example 6 A 0.5% aqueous solution of Organopolysiloxane D, 100 g, (synthesized in Reference Example 4~ is prepared, 50 g carbon black powder is added, and this mixture i5 allowed to dry by standing. Heating at 100C for 5 minutes then affords a carbon black powder having a 1% add-on of Organopolysiloxane D.
In the comparison example, carbon black powder is similarly treated with Organopolysiloxane (iij to afford a carbon black powder having a 1% add-on o Organopoly-siloxane (ii).
50 g of each carbon black powder is separately placed in 1 1 of water, followed by ~kirring for 3 hours, filtration and drying. 5 Parts o~ each o the obtained carbon black powders is then separately dispersed to homogeneity in an a~ueous acrylic emulsion pain-t to produce a paint. The paint containing the Organopoly-siloxane D-treated carbon black powder presented a uniform dispersion, and did not suffer from sedimentation.
However, the Organopolysiloxane (ii)-treated carbon black powder underwent rapicl sedimentation, and the dispersion was inhomogeneous. These observation~ indicate that the pre~ent inVention' 8 agent for treating ~olids ha~ the capacity to lmpart a durable hydrophilicity.
Because the pressnt invention'~ agent for treating ~olid~ ha~ a~ it~ principal agent an organopoly~iloxane which ha~ the alkoxysilylalkyl group at least at one molecular terminal and which al~o ha~ at lea~t 1 polyoxy-alkylene group a~ a pendant group or at the molecular terminal~, it can impart a durable hydrophilicity and .~
antistaticity to solid materials. As a consequence, it is very us~ful industrially.
Claims (7)
1. A composition for treating solids, said composi-tion comprising an organopolysiloxane compound which has the formula A(R2SiO)x(RQSiO)y(RGSiO)2SiR2A, wherein Q denotes a radical having the formula -R1SiXaR(3-a), G denotes a radical having the formula -R1O(C2H4O)b(C3H6O)cR2, A denotes a radical selected from the group consist-ing of Q and G radicals, at least one A radical being a Q radical, x has a value of from 5 to 500, y has a value of from 0 to 100, z has a value of from 0 to 100, with the proviso that when A
consists entirely of Q, then z is an integer with a value of from 1 to 100, X denotes an aloxy or alkoxyalkoxy radical having from 1 to 4 carbon atoms, R denotes a monovalent hydrocarbon or halogenated hydrocarbon radical having from 1 to 10 carbon atoms, R1 denotes an alkylene radical having from 2 to 5 carbon atoms, R2 denotes a hydrogen atom or a monovalent organic radical having from 1 to 5 carbon atoms, a has a value of 2 or 3, b has a value of from 0 to 50, c has a value of from 0 to 50, and b plus c has a value of from 2 to 100;
there being present in said organopolysiloxane at least one G radical.
consists entirely of Q, then z is an integer with a value of from 1 to 100, X denotes an aloxy or alkoxyalkoxy radical having from 1 to 4 carbon atoms, R denotes a monovalent hydrocarbon or halogenated hydrocarbon radical having from 1 to 10 carbon atoms, R1 denotes an alkylene radical having from 2 to 5 carbon atoms, R2 denotes a hydrogen atom or a monovalent organic radical having from 1 to 5 carbon atoms, a has a value of 2 or 3, b has a value of from 0 to 50, c has a value of from 0 to 50, and b plus c has a value of from 2 to 100;
there being present in said organopolysiloxane at least one G radical.
2. A composition according to claim 1 further comprising a curing amount of a curing agent comprising a curing catalyst and/or a crosslinking compound for silanol groups.
3. A composition according to claim 1 further comprising a glyoxal resin.
4. A method for treating a solid, said method comprising applying the composition of claim 1 to the solid and heating the composition-containing solid to a temperature of from 50 to 150°C.
5. A method for improving the hydrophilicity of a fabric containing polyester fibers said method comprising applying the composition of claim 1 to the fabric and heating the composition-containing fabric to a tempera-ture of from 50 to 150°C.
6. A treated solid provided by the method of claim 4.
7. A treated fabric provided by the method of claim 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP112391/86 | 1986-05-16 | ||
| JP11239186A JPS62267359A (en) | 1986-05-16 | 1986-05-16 | Solid material-treating agent |
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| Publication Number | Publication Date |
|---|---|
| CA1293976C true CA1293976C (en) | 1992-01-07 |
Family
ID=14585495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000537247A Expired - Lifetime CA1293976C (en) | 1986-05-16 | 1987-05-15 | Treating agent comprising organopolysiloxane containing polyoxyalkylene and alkoxysilylalkyl radicals |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0255205A3 (en) |
| JP (1) | JPS62267359A (en) |
| CA (1) | CA1293976C (en) |
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| JP3007711B2 (en) * | 1991-04-24 | 2000-02-07 | 東レ・ダウコーニング・シリコーン株式会社 | Fiber treatment agent |
| US5408012A (en) * | 1993-05-27 | 1995-04-18 | Comfort Technologies, Inc. | Polymers having enhanced durable hydrophilicity and durable rewetting properties and process of producing the same |
| CA2327034C (en) | 1999-12-01 | 2007-07-17 | Canon Kabushiki Kaisha | Method of reforming element surface, element with reformed surface, method of manufacturing element with reformed surface, surface treatment liquid for forming reformed surface, and method of manufacturing surface treatment liquid |
| CA2327067A1 (en) * | 1999-12-06 | 2001-06-06 | Canon Kabushiki Kaisha | Surface reformed fiber body, liquid container using fiber absorber, and method of producing fiber absorber for use in liquid ejection |
| JP4521981B2 (en) * | 2000-11-09 | 2010-08-11 | キヤノン株式会社 | Manufacturing method of fiber assembly |
| US6733840B2 (en) | 2002-06-05 | 2004-05-11 | General Electric Company | Silicone compositions for textile applications |
| DE102008040986A1 (en) * | 2008-08-05 | 2010-02-11 | Evonik Goldschmidt Gmbh | Hydrophobization of mineral fiber components |
| JP7160850B2 (en) * | 2017-06-26 | 2022-10-25 | ダウ シリコーンズ コーポレーション | SILICONE POLYETHER COPOLYMERS, SEALANTS CONTAINING SAME, AND RELATED METHODS |
| CN114031780B (en) * | 2021-11-05 | 2023-06-13 | 广州集泰化工股份有限公司 | Antistatic silica gel compound and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL279187A (en) * | 1961-06-01 | |||
| JPS55123648A (en) * | 1979-03-16 | 1980-09-24 | Shin Etsu Chem Co Ltd | Cold-setting composition |
| JPS61148284A (en) * | 1984-12-21 | 1986-07-05 | Toray Silicone Co Ltd | Agent for treating solid material |
-
1986
- 1986-05-16 JP JP11239186A patent/JPS62267359A/en active Pending
-
1987
- 1987-05-15 EP EP87304333A patent/EP0255205A3/en not_active Withdrawn
- 1987-05-15 CA CA000537247A patent/CA1293976C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62267359A (en) | 1987-11-20 |
| EP0255205A3 (en) | 1990-01-10 |
| EP0255205A2 (en) | 1988-02-03 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |