EP0255205A2 - Composition de traitement contenant des organes polysiloxanes ayant des radicaux polyoxyalkyléniques et alkoxysilylalkyliques - Google Patents

Composition de traitement contenant des organes polysiloxanes ayant des radicaux polyoxyalkyléniques et alkoxysilylalkyliques Download PDF

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Publication number
EP0255205A2
EP0255205A2 EP87304333A EP87304333A EP0255205A2 EP 0255205 A2 EP0255205 A2 EP 0255205A2 EP 87304333 A EP87304333 A EP 87304333A EP 87304333 A EP87304333 A EP 87304333A EP 0255205 A2 EP0255205 A2 EP 0255205A2
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EP
European Patent Office
Prior art keywords
radical
value
organopolysiloxane
denotes
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87304333A
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German (de)
English (en)
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EP0255205A3 (fr
Inventor
Isao Ona
Masaru Ozaki
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DuPont Toray Specialty Materials KK
Original Assignee
Toray Silicone Co Ltd
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Publication date
Application filed by Toray Silicone Co Ltd filed Critical Toray Silicone Co Ltd
Publication of EP0255205A2 publication Critical patent/EP0255205A2/fr
Publication of EP0255205A3 publication Critical patent/EP0255205A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences

Definitions

  • the present invention relates to an agent for treating solids. More specifically, the present inven­tion relates to a treatment agent which imparts a durable hydrophilicity and antistaticity to solid materials.
  • organopolysiloxane-polyoxyalkylene copolymer such as that disclosed in Japanese Patent Publication Number 44-6069 (6,069/69)
  • organosilyl-­terminated polyoxyalkylene-modified and alkoxysilylalkyl-­modified organopolysiloxane such as that disclosed in Japanese Patent Application Laid Open Number 57-139123 (139,123/82)
  • silicone-type agents for the treatment of solids are known as silicone-type agents for the treatment of solids.
  • treatment methods which employ organic surfactant and the treatment method using the organo­polysiloxane-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 lost upon exposure to water or organic solvent.
  • 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 is organo­polysiloxane having at least 1 polyoxyalkylene group as a side chain or molecular terminal and having the alkoxysilylalkyl group at least at one molecular terminal, is unknown.
  • the object of the present invention is to eliminate the problems described above by providing a novel agent for treating solids which can impart a durable hydro­philicity and antistaticity to solids. It is a particular object of this invention to provide a method for confer­ring durable hydrophilicity and antistaticity properties to fibers and fiber-containing materials.
  • the method of this invention 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.
  • 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.
  • both of the siloxane chain-terminating siloxane units bear alkoxy­silylalkyl radical.
  • the present invention relates to a composition for treating solids, said composition comprising an organo­polysiloxane compound which has the formula A(R2SiO) x (RQSiO) y (RGSiO) z SiR2A, wherein Q denotes a radical having the formula -R1SiX a R (3-a) , G denotes a radical having the formula -R1O(C2H4O) b (C3H6O) c R2, A denotes a radical selected from the group consist­ing 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, X denotes an alkoxy 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,
  • 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 is a group having the formula -R1SiX a R (3-a) and it functions to impart durability by tightly bonding the present organopolysiloxane to solids.
  • R1 is to be an alkylene group having 2 to 5 carbon atoms, and is exemplified by -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, -(CH2)4-, and -(CH2)5-.
  • the groups R1 within the mole­cule may be identical or different.
  • X is an alkoxy group having 1 to 4 carbon atoms, and it is exemplified by methoxy, ethoxy, propoxy, and methoxyethoxy.
  • the value of a is to be 2 or 3.
  • G is a group having the formula -R1O(C2H4O) b (C3H6O) c R2, and it functions to impart antistaticity and hydrophilicity to the solid.
  • R2 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.
  • b and c are both integers having values of 0 to 50 wherein the sum b + c is to have a value of 2 to 100.
  • x is an integer having a value of 5 to 500
  • y is an integer having a value of 0 to 100
  • z is an integer having a value of 0 to 100, with the condition that when A consists entirely of Q, z is then to be an integer having a value of 1 to 100.
  • 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.
  • the above-described organopolysiloxane can be used as is, or it may be dissolved in water as is, or it may be auto-emulsified in water.
  • it may be emulsified using a suitable emulsifying agent such as, for example, the salts of sulfate esters of higher alcohols, alkylbenzene­sulfonate salts, higher alcohol-polyoxyalkylene adducts, alkylphenol-polyoxyalkylene adducts, higher fatty acid sorbitan esters, etc.
  • the solid treatment agent of the present invention may be used by dissolving the above-­described organopolysiloxane in an organic solvent such as, for example, toluene, xylene, benzene, n-hexane, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, mineral terpene, perchloroethylene, trichloroethylene, etc.
  • an organic solvent such as, for example, toluene, xylene, benzene, n-hexane, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, mineral terpene, perchloroethylene, trichloroethylene, etc.
  • Solids 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 solid, for example, upon standing at room temperature, or upon blowing on hot air, or upon a heat treatment.
  • 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, organohydrogenpolysiloxanes, silanol-containing organo­polysiloxanes; etc.
  • 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 alkoxysilane
  • Solids which may be treated with the treatment agent of the present invention are exemplified by various fibers and their fabrics; sheet-form materials such as paper, natural and synthetic leathers, cellophane and plastic films; foams such as synthetic resin foams; synthetic resin moldings; natural and synthetic rubber moldings; metal moldings; glass moldings; and powders such as inorganic powders and synthetic resin powders.
  • the aforesaid fibers are exemplified in terms of species by natural fibers such as hair, wool, silk, flax, cotton and asbestos; by regenerated fibers such as rayon and acetate; by synthetic fibers such as polyester, polyamide, vinylon, polyacryl nitrile, polyethylene, polypropylene 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.
  • viscosity is the value measured at 25°C.
  • Siloxane II, 89.1 g, having the formula H(Me2SiO)41(MeHSiO)6SiMe2H, 7.5 g vinyltrimethoxysilane, and 60 g toluene are placed in a 500 ml three-neck flask equipped with a reflux condenser, the internal temperature is raised to 80°C by heating, 0.1 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction is conducted at 110°C for 30 minutes.
  • a siloxane, 69.3 g, having the formula H(Me2SiO)20(MeHSiO)4SiMe2H, 11.0 g methylvinyldimethoxysilane and 60 g toluene are placed in a 500 ml three-neck flask equipped with a reflux condenser, the internal temperature is raised to 80°C by heating, 0.1 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction is carried out for 30 minutes at 105°C.
  • 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 flask equipped with a reflux condenser, the internal tempera­ture is raised to 80°C by heating, 0.25 g 2% isopropanolic chloroplatinic acid solution is added, and a reaction is conducted at 125°C for 1 hour. After the reaction, the volatiles are stripped in vacuo at 140°C/5 mmHg.
  • the organopolysiloxane-­finished fabric (before and after washing) is laid out horizontally on spread out filter paper, a drop of water is delivered from a syringe, and the time required for its soaking in is then measured.
  • the % residual organopolysiloxane after washing is analyzed using an X-ray fluorescent analyzer from Rigaku Corp. based on the difference in silicon atom counts before and after washing the treated fabric. The results are reported in Table 1.
  • Example 1 Treatment is conducted exactly as in Example 1, with the exception that 1 part Organopolysiloxane (i) having a viscosity of 1,200 cS and the formula is used in place of Organopolysiloxane A. Testing is conducted as in Example 1, and these results are also reported in Table 1.
  • Organopolysiloxane B synthesized according to Reference Example 2 and having the formula N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, 0.5 part, dibutyltin diacetate, 0.2 part and 99.5 parts toluene are mixed to homogeneity to prepare a treatment bath.
  • 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.
  • the obtained organopolysiloxane-finished fabric is then cut in half, and one sample of organopoly­siloxane-finished fabric is washed once under the wash conditions of Example 1 and rinsed twice. Test samples are thus prepared of organopolysiloxane-finished fabric before and after washing.
  • An antistaticity test is carried out as follows.
  • the treated fabrics (before and after washing) are allowed to stand at 20°C/RH 65% for 1 week. Their 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 as 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 soap and 10 steel balls are placed in a 450 ml glass bottle. Washed and unwashed samples of organopoly­siloxane-finished fabric and untreated fabric are respec­tively placed in the bottle, treated at 60°C for 30 minutes, and then gently rinsed with water and dried.
  • 10% aqueous solutions are prepared using, respectively, Organopolysiloxane (ii) (used in Comparison Example 3) or nonionic surfactant (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 for 6 hours. After this, the upper surface of a thermostatted water bath (set at 60°C ⁇ 2°C) is covered and sealed with each film, wherein the treated surface is down. The status of the films is inspected after 3 hours.
  • the film treated with Organopolysiloxane A, a treatment agent of the present invention is hydro­philic, presents uniform wetting of the lower film surface, and is transparent. However, the lower surfaces of the other 2 films are not hydrophilic, and are adhered with water droplets and are opaque.
  • carbon black powder is similarly treated with Organopolysiloxane (ii) to afford a carbon black powder having a 1% add-on of Organopoly­siloxane (ii).
  • each carbon black powder is separately placed in 1 l of water, followed by stirring for 3 hours, filtration and drying. 5 Parts of each of the obtained carbon black powders is then separately dispersed to homogeneity in an aqueous acrylic emulsion paint to produce a paint.
  • the paint containing the Organopoly­siloxane D-treated carbon black powder presented a uniform dispersion, and did not suffer from sedimentation.
  • the Organopolysiloxane (ii)-treated carbon black powder underwent rapid sedimentation, and the dispersion was inhomogeneous.
  • the present invention's agent for treating solids has as its principal agent an organopolysiloxane which has the alkoxysilylalkyl group at least at one molecular terminal and which also has at least 1 polyoxy­alkylene group as a pendant group or at the molecular terminals, it can impart a durable hydrophilicity and antistaticity to solid materials. As a consequence, it is very useful industrially.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Silicon Polymers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP87304333A 1986-05-16 1987-05-15 Composition de traitement contenant des organes polysiloxanes ayant des radicaux polyoxyalkyléniques et alkoxysilylalkyliques Withdrawn EP0255205A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP112391/86 1986-05-16
JP11239186A JPS62267359A (ja) 1986-05-16 1986-05-16 固体材料処理剤

Publications (2)

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EP0255205A2 true EP0255205A2 (fr) 1988-02-03
EP0255205A3 EP0255205A3 (fr) 1990-01-10

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EP (1) EP0255205A3 (fr)
JP (1) JPS62267359A (fr)
CA (1) CA1293976C (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0510631A1 (fr) * 1991-04-24 1992-10-28 Dow Corning Toray Silicone Company, Limited Polyester modifié par du siloxane pour le traitement de fibres
WO1994028229A3 (fr) * 1993-05-27 1995-01-26 Comfort Tech Inc Polymeres presentant des proprietes d'hydrophilie et de remouillabilite durables accrues et procede pour les produire
US6733840B2 (en) 2002-06-05 2004-05-11 General Electric Company Silicone compositions for textile applications
US6863762B2 (en) * 2000-11-09 2005-03-08 Canon Kabushiki Kaisha Method for manufacturing fiber aggregate, fiber aggregate, and liquid container using such fiber aggregate
EP2151420B1 (fr) * 2008-08-05 2019-01-23 Evonik Degussa GmbH Imperméabilisation d'éléments de construction en fibres minérales
CN114031780A (zh) * 2021-11-05 2022-02-11 广州集泰化工股份有限公司 一种抗静电硅胶化合物及其制备方法与应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2327034C (fr) 1999-12-01 2007-07-17 Canon Kabushiki Kaisha Methode pour refaire la surface d'un element, element a la surface refaite, methode de production d'elements a la surface refaite, liquide de traitement de surface pour obtenir une surface refaite et methode de production du liquide de traitement de surfaces
CA2327067A1 (fr) * 1999-12-06 2001-06-06 Canon Kabushiki Kaisha Corps de fibres a surface reformee, reservoir utilisant un absorbeur a fibres, et methode de fabrication d'absorbeur a fibres pour l'ejection de liquide
JP7575190B2 (ja) * 2017-06-26 2024-10-29 ダウ シリコーンズ コーポレーション シリコーンポリエーテルコポリマー組成物、その調製方法、およびシーラント

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE618428A (fr) * 1961-06-01
JPS55123648A (en) * 1979-03-16 1980-09-24 Shin Etsu Chem Co Ltd Cold-setting composition
JPS61148284A (ja) * 1984-12-21 1986-07-05 Toray Silicone Co Ltd 固体材料処理剤

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0510631A1 (fr) * 1991-04-24 1992-10-28 Dow Corning Toray Silicone Company, Limited Polyester modifié par du siloxane pour le traitement de fibres
WO1994028229A3 (fr) * 1993-05-27 1995-01-26 Comfort Tech Inc Polymeres presentant des proprietes d'hydrophilie et de remouillabilite durables accrues et procede pour les produire
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
US6863762B2 (en) * 2000-11-09 2005-03-08 Canon Kabushiki Kaisha Method for manufacturing fiber aggregate, fiber aggregate, and liquid container using such fiber aggregate
US6733840B2 (en) 2002-06-05 2004-05-11 General Electric Company Silicone compositions for textile applications
EP2151420B1 (fr) * 2008-08-05 2019-01-23 Evonik Degussa GmbH Imperméabilisation d'éléments de construction en fibres minérales
CN114031780A (zh) * 2021-11-05 2022-02-11 广州集泰化工股份有限公司 一种抗静电硅胶化合物及其制备方法与应用

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Publication number Publication date
JPS62267359A (ja) 1987-11-20
CA1293976C (fr) 1992-01-07
EP0255205A3 (fr) 1990-01-10

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