WO2017122581A1 - オルガノポリシロキサン乳化組成物及び樹脂組成物 - Google Patents
オルガノポリシロキサン乳化組成物及び樹脂組成物 Download PDFInfo
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- WO2017122581A1 WO2017122581A1 PCT/JP2017/000213 JP2017000213W WO2017122581A1 WO 2017122581 A1 WO2017122581 A1 WO 2017122581A1 JP 2017000213 W JP2017000213 W JP 2017000213W WO 2017122581 A1 WO2017122581 A1 WO 2017122581A1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C08L101/00—Compositions of unspecified macromolecular compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the present invention relates to an organopolysiloxane emulsion composition containing a polyoxyalkylene-modified organopolysiloxane compound as an emulsifier or emulsification aid, and a resin composition containing the emulsion composition.
- Resin compositions such as urethane resins and acrylic resins can be divided into solvent-type ones that use organic solvents to improve film-forming properties and aqueous-type ones that do not contain organic solvents due to concerns about environmental pollution.
- Solvent-type resin compositions have a high boiling point such as N, N'-dimethylformamide (DMF) in many cases because the organic solvent volatilizes in the drying process and there is a concern that it may adversely affect the health of workers.
- An organic solvent is used.
- Artificial leather and synthetic leather internally or surface-treated with solvent-based and water-based resin compositions are used for automotive seats, furniture, clothing, etc., and require gloss, slipperiness and leveling. Has been.
- Polydimethylsiloxane with a high degree of polymerization is blended to meet the requirements of slipping and abrasion resistance, but in order to be able to blend polydimethylsiloxane into any solvent-type or aqueous-type resin composition It is necessary to emulsify the polydimethylsiloxane so that it can be dispersed in either DMF or water.
- an emulsified composition of polydimethylsiloxane emulsified with a nonionic surfactant, an anionic surfactant or a cationic surfactant is blended with a solvent-type resin composition such as DMF, it is not uniformly dispersed and is in an emulsified state.
- Patent Document 1 Japanese Patent No. 3023250 proposes a water-in-oil emulsified cosmetic containing a cyclic silicone, a surfactant, a highly polymerized side-chain polyoxyalkylene-modified silicone, ethanol, and titanium oxide.
- a polyoxyalkylene-modified silicone in which a short-chain polyoxyalkylene group is modified to a silicone side chain is used, and the structure is different from the polyoxyalkylene-modified organopolysiloxane compound contained in the emulsion composition of the present invention.
- Patent Document 2 Japanese Patent No. 3417567 proposes an emulsion of oil and lower alcohol using a side-chain polyoxyalkylene-modified silicone.
- a side-chain polyoxyalkylene-modified silicone as an emulsifier, the emulsion is stable even if it contains a high concentration of alcohol.
- This uses a polyoxyalkylene-modified silicone in which a short-chain polyoxyalkylene group is modified to a side chain of silicone, and the structure of the polyoxyalkylene-modified organopolysiloxane compound contained in the emulsion composition of the present invention is Different.
- the emulsified composition whose base oil is a liquid paraffin, a higher alcohol, silicone oil, etc. is illustrated, and is not aimed at emulsifying organopolysiloxane having a high degree of polymerization.
- Patent Document 3 Japanese Patent No. 3633820 proposes an emulsion containing polysiloxane, water-repellent treated powder, and ethanol using a both-end-modified polyoxyalkylene-modified silicone for cosmetic purposes. Since the emulsified composition of the present invention does not contain the treated powder, the blending components are different.
- the base oil is exemplified by an emulsified composition of cyclic siloxane or 6 cs low-viscosity polysiloxane, and is not intended to emulsify organopolysiloxane having a high degree of polymerization.
- Patent Document 4 Japanese Patent No. 5646355 proposes an emulsion containing polydimethylsiloxane, polyether-modified silicone and lower alcohol for cosmetics.
- the viscosity of polydimethylsiloxane is 20 to 10,000 mm 2 / s, which is different from the viscosity of the organopolysiloxane of the present invention.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2014-80713 proposes blending solid dimethyl silicone with urethane resin and using it as a surface treatment agent for synthetic resin.
- Non-emulsified dimethyl silicone is used, and it is considered that it cannot be blended in an aqueous resin composition. Therefore, it is not dispersed in the solvent-type and aqueous-type resin compositions, and is different from the emulsion composition of the present invention.
- Patent Document 6 Japanese Patent Application Laid-Open No. 2007-314919 proposes an aqueous resin composition containing a polyisocyanate crosslinking agent, a silicone compound, and a filler in a urethane resin.
- the silicone compound is a polyether-modified silicone and is different from the emulsified composition obtained by emulsifying the organopolysiloxane having a high polymerization degree according to the present invention.
- Patent Document 7 Japanese Patent No. 5186079 discloses a mixture of a one-end polyether-modified silicone and a nonionic surfactant, which can continuously impart a slightly hydrophilic property to the surface of a coating film, and protects against aquatic organisms.
- a coating additive for the purpose of exhibiting the soiling performance over a long period of time has been proposed.
- the present invention was developed for the purpose of imparting slipperiness and wear resistance to synthetic resins and artificial resins used in automobiles and bags, and the composition and application differ from those of the present invention.
- Japanese Patent No. 3023250 Japanese Patent No. 3417567 Japanese Patent No. 3633820
- the present invention has been made in view of the above circumstances, and an organopolysiloxane emulsion composition emulsified with a high polymerization degree organopolysiloxane dispersible in a solvent such as DMF or water, and the composition is blended.
- An object of the present invention is to provide a resin composition useful as a surface treatment agent or an internal treatment agent that imparts slipperiness and wear resistance to synthetic resins and artificial resins used in automobiles and bags.
- the present inventors have made it easy to use a polyoxyalkylene-modified organopolysiloxane compound having a specific structure as an emulsifier or an emulsifying aid, thereby easily producing a highly polymerized organopolysiloxane.
- Siloxane can be emulsified, and the resulting organopolysiloxane emulsion composition is excellent in solvent resistance to polar solvents such as DMF and is also dispersed in water. It was found that even when blended with a resin composition, it is possible to impart slipping property and wear resistance, and the present invention has been made.
- the present invention provides the following organopolysiloxane emulsion composition and resin composition.
- (A) Polyoxyalkylene-modified organopolysiloxane compound represented by the following general formula (1): 1 to 50 parts by mass, [Wherein L represents the following general formula (2) (In the formula, EO represents an oxyethylene group, and AO represents a linear or branched oxyalkylene group having 3 to 10 carbon atoms.
- R 1 is a linear or branched unsubstituted or 1 to 10 carbon atom or A substituted alkyl group, a hydrogen atom, a carboxy group, an acyl group having 2 to 10 carbon atoms, or a phenyl group, r is an integer of 0 to 10, s is an integer of 1 to 100, and t is an integer of 0 to 150.
- R may be the same or different, and a hydrogen atom, a hydroxy group, a linear or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, 6 to 6 carbon atoms A 20 aryl group, an aralkyl group having 7 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
- a is an integer of 2 to 4
- b is an integer of 0 to 2
- c is an integer of 50 to 1,000
- d is 0 or 1
- e is 0 or 1.
- N is an integer of 50 to 1,000.
- C The organopolysiloxane emulsion composition according to [1] or [2], wherein the viscosity of the organopolysiloxane at 25 ° C. is 500,000 mPa ⁇ s or more.
- organopolysiloxane emulsion composition according to any one of [1] to [4], wherein the organopolysiloxane is any one of dimethylpolysiloxane, phenyl-modified polysiloxane, hydroxy-modified polysiloxane, or a mixture thereof. .
- Urethane resin epoxy resin, phenol resin, melamine resin, urea resin, alkyd resin, polyimide resin, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, tetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile styrene resin, acrylic resin
- a resin composition comprising a resin selected from [1] to [5] and an organopolysiloxane emulsion composition according to any one of [1] to [5].
- the organopolysiloxane emulsion composition of the present invention can be dispersed in water or a polar solvent such as DMF.
- a polar solvent such as DMF.
- an organopolysiloxane emulsion composition is blended into a solvent-type or aqueous-type resin composition and used as a surface treatment agent or an internal treatment agent for synthetic leather or artificial leather, it exhibits slipperiness without impairing leveling properties and glossiness. It is possible to grant.
- the organopolysiloxane emulsion composition of the present invention is (A) Polyoxyalkylene-modified organopolysiloxane compound represented by the general formula (1) described later: 1 to 50 parts by mass, (B) Surfactant: 0 to 50 parts by mass, (C) Organopolysiloxane having a viscosity at 25 ° C. of 15,000 mPa ⁇ s or more: 100 parts by mass (D) Water: 0 to 10,000 parts by mass is contained.
- the polyoxyalkylene-modified organopolysiloxane compound as component (A) is represented by the following general formula (1).
- L represents the following general formula (2)
- EO represents an oxyethylene group
- AO represents a linear or branched oxyalkylene group having 3 to 10 carbon atoms.
- R 1 is a linear or branched unsubstituted or 1 to 10 carbon atom or A substituted alkyl group, a hydrogen atom, a carboxy group, an acyl group having 2 to 10 carbon atoms, or a phenyl group, r is an integer of 0 to 10, s is an integer of 1 to 100, and t is an integer of 0 to 150.
- R may be the same or different, and a hydrogen atom, a hydroxy group, a linear or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, 6 to 6 carbon atoms A 20 aryl group, an aralkyl group having 7 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
- a is an integer of 2 to 4
- b is an integer of 0 to 2
- c is an integer of 50 to 1,000
- d is 0 or 1
- e is 0 or 1.
- an organopolysiloxane having a high degree of polymerization can be easily emulsified.
- the particle size of can be reduced.
- (C) organopolysiloxane those having 20 million mPa ⁇ s or more are difficult to emulsify with (B) surfactant alone, and easy to contain (A) polyoxyalkylene-modified organopolysiloxane compound.
- the organopolysiloxane emulsion composition of the present invention exhibits the effects of solvent resistance and salt resistance by including (A) a polyoxyalkylene-modified organopolysiloxane compound.
- R may be the same or different, and are a hydrogen atom, a hydroxy group, a linear or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , An aralkyl group having 7 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
- Examples of the linear or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and neopentyl group Alkyl groups such as hexyl group and octyl group, halogen-substituted alkyl groups such as chloromethyl group, chloropropyl group, bromoethyl group and trifluoropropyl group, and the aryl group having 6 to 20 carbon atoms includes phenyl group , A tolyl group, a xylyl group, a naphthyl group and the like.
- Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group and a phenylpropyl group.
- Examples of the alkoxy group having 1 to 20 carbon atoms include Methoxy group, ethoxy group, propoxy group and the like.
- R is preferably a linear or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and more preferably a methyl group or a phenyl group from the viewpoint of versatility. It is.
- a is an integer of 2 to 4
- b is an integer of 0 to 2
- c is an integer of 50 to 1,000, preferably an integer of 100 to 800, more preferably an integer of 200 to 600
- d is 0 or 1
- L is a polyoxyalkylene group represented by the above formula (2).
- R 1 is a linear or branched unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a carboxy group, an acyl group having 2 to 10 carbon atoms, or a phenyl group.
- the linear or branched unsubstituted or substituted alkyl group having 1 to 10 carbon atoms includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and neopentyl.
- R 1 is preferably a linear or branched unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and more preferably a hydrogen atom from the viewpoint of ease of synthesis.
- EO is an oxyethylene group
- AO is a linear or branched oxyalkylene group having 3 to 10 carbon atoms.
- Examples of AO include an oxypropylene group, an oxybutylene group, and an oxytetramethylene group.
- s is an integer of 1 to 80
- t is an integer of 0 to 100
- s is an integer of 3 to 50
- t is an integer of 3 to 50.
- the viscosity of the (A) polyoxyalkylene-modified organopolysiloxane compound becomes too high and becomes difficult to handle.
- the sum total of s + t in the average structural formula in one molecule is 15 or more, and preferably 25 or more.
- the solvent resistance of the organopolysiloxane emulsion composition containing (A) the polyoxyalkylene-modified organopolysiloxane compound is lowered, and the organopolysiloxane emulsion composition is dispersed in a polar solvent such as alcohol or ketone. In this case, the organopolysiloxane emulsion composition is destroyed and the silicone component is deposited.
- EO and AO may be block or random.
- Examples of the polyoxyalkylene group of the formula (2) include, but are not limited to, those represented by the following general formula. (In the formula, EO represents ethylene oxide, PO represents propylene oxide, and BO represents butylene oxide.)
- component (A) among the polyoxyalkylene-modified organopolysiloxane compounds represented by the above formula (1), a linear chain having polyoxyalkylene groups represented by the following general formula (3) at both ends A polyoxyalkylene-modified organopolysiloxane compound is preferred.
- L and R are the same as above.
- N is an integer of 50 to 1,000.
- n is an integer of 50 to 1,000, preferably an integer of 100 to 800, and more preferably an integer of 200 to 600.
- n is less than 50, the solvent resistance of the organopolysiloxane emulsion composition containing (A) the polyoxyalkylene-modified organopolysiloxane compound is lowered, and the film of the resin composition containing the organopolysiloxane emulsion composition of the present invention The gloss of the is reduced.
- the viscosity of the (A) polyoxyalkylene-modified organopolysiloxane compound becomes high and difficult to handle, and the emulsifying power of the (A) polyoxyalkylene-modified organopolysiloxane compound decreases, The average particle size of the emulsion in the organopolysiloxane emulsion composition does not become fine. Even when two or more types of (A) polyoxyalkylene-modified organopolysiloxane compounds are mixed, the average structural formula only needs to satisfy the range defined above.
- polyoxyalkylene-modified organopolysiloxane compound of component (A) examples include, but are not limited to, those represented by the following formula.
- Ph represents a phenyl group.
- EO represents ethylene oxide and PO represents propylene oxide.
- EO and PO may be random or block.
- the molecular weight of the polyoxyalkylene-modified organopolysiloxane compound (A) is preferably 8,500 to 100,000, more preferably 10,000 to 90,000, and further preferably 15,000 to 90,000. It is. When the molecular weight is less than 8,500, the solvent resistance of the organopolysiloxane emulsion composition containing the polyoxyalkylene-modified organopolysiloxane compound (A) may be lowered. It can be difficult.
- the molecular weight is a value of weight average molecular weight in terms of polystyrene of GPC (manufactured by TOSOH, HLC8220, tetrahydrofuran (THF) solvent) (hereinafter the same).
- the viscosity of the polyoxyalkylene-modified organopolysiloxane compound is preferably 5,000 mPa ⁇ s or more, more preferably 9,000 mPa ⁇ s or more, and further preferably 15,000 mPa ⁇ s or more.
- the viscosity is less than 5,000 mPa ⁇ s, the solvent resistance of the organopolysiloxane emulsion composition containing the polyoxyalkylene-modified organopolysiloxane compound (A) is lowered, and the resin containing the organopolysiloxane emulsion composition of the present invention is used. There is a possibility that the gloss of the film of the composition may be lowered.
- the viscosity is a value at 25 ° C. measured with a BM type or BH type rotational viscometer (hereinafter the same).
- the present invention includes [RSiO 3/2 ] units and [SiO 4/2 ] units in the molecule of the (A) polyoxyalkylene-modified organopolysiloxane compound.
- the hydrosilylation reaction catalyst is obtained by adding an unsaturated hydrocarbon group-containing polyoxyalkylene compound represented by the following general formula (5) to the terminal silicon atom-bonded hydrogen atom-containing organopolysiloxane compound represented by the following general formula (4).
- a polyoxyalkylene-modified organopolysiloxane compound is synthesized by a hydrosilylation reaction in the presence of a solvent or in a non-solvent.
- the resin composition containing the organopolysiloxane emulsion composition of the present invention can be used.
- the wear resistance of the film may be improved.
- organopolysiloxane compounds containing a terminal silicon atom-bonded hydrogen atom represented by the above formula (4) a linear organopolysiloxane containing silicon atom-bonded hydrogen atoms at both ends represented by the following general formula (6)
- a siloxane compound is preferred. (In the formula, R and n are the same as above.)
- Examples of the terminal silicon atom-bonded hydrogen atom-containing organopolysiloxane compound of formula (4) include, but are not limited to, those represented by the following formula. (In the formula, Ph is a phenyl group and Rf is a trifluoropropyl group. P and q are each an integer of 0 or more, and p + q is 50 to 1,000.)
- the unsaturated hydrocarbon group-containing polyoxyalkylene compound it is also possible to use a mixture of two or more unsaturated hydrocarbon group-containing polyoxyalkylene compounds satisfying the general formula (5).
- the average structural formula of the mixed oil it is only necessary that the average structural formula of the mixed oil satisfies the range of the general formula (5) described above.
- Examples of the unsaturated hydrocarbon group-containing polyoxyalkylene compound of formula (5) include, but are not limited to, those represented by the following formula. (In the formula, EO represents ethylene oxide, PO represents propylene oxide, and BO represents butylene oxide. EO, PO, and BO may be random or block.)
- the number of moles of unsaturated hydrocarbon groups in the unsaturated hydrocarbon group-containing polyoxyalkylene compound of formula (5) is the moles of silicon atom-bonded hydrogen atoms of the terminal silicon atom-bonded hydrogen atom-containing organopolysiloxane compound of formula (4).
- the number is preferably 0.7 equivalents or more and less than 2.0 equivalents, more preferably 1.0 equivalents or more and less than 2.0 equivalents. If it is less than 0.7 equivalent, the hydrophilicity of the polyoxyalkylene-modified organopolysiloxane compound (A) may be reduced, and it may not function as an emulsifier or emulsification aid.
- the hydrosilylation reaction catalyst used in the hydrosilylation reaction is a catalyst for promoting the hydrosilylation reaction, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferable.
- the platinum-based catalyst includes chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complex, platinum ketone complex, platinum vinylsiloxane complex, platinum tetrachloride, platinum fine powder, solid platinum on alumina or silica carrier , Platinum black, platinum olefin complexes, platinum alkenylsiloxane complexes, and platinum carbonyl complexes are exemplified, but chloroplatinic acid or platinum vinylsiloxane complexes are preferred from the standpoint of stability and versatility.
- the catalyst content is not particularly limited as long as it is an effective amount, but the catalyst metal is in mass relative to the total mass of the terminal silicon atom-bonded hydrogen atom-containing organopolysiloxane compound and the unsaturated hydrocarbon group-containing polyoxyalkylene compound.
- the amount is preferably within the range of 0.1 to 1,000 ppm, and particularly preferably within the range of 0.5 to 100 ppm.
- Examples of the solvent used for the hydrosilylation reaction include aromatic hydrocarbon solvents such as toluene and xylene, hydrocarbon solvents such as hexane and octane, ether solvents such as dibutyl ether, dioxane, and tetrahydrofuran (THF), ethyl acetate, and the like.
- aromatic hydrocarbon solvents such as toluene and xylene
- hydrocarbon solvents such as hexane and octane
- ether solvents such as dibutyl ether, dioxane, and tetrahydrofuran (THF), ethyl acetate, and the like.
- ester solvents such as butyl acetate
- ketone solvents such as methyl ethyl ketone (MEK)
- alcohol solvents such as ethanol, isopropanol and 1-butanol
- organic solvents such as chlorinated hydrocarbon solvents
- the content of the solvent is 0 to 1,000 parts by mass when the total of the terminal silicon atom-bonded hydrogen atom-containing organopolysiloxane compound and the unsaturated hydrocarbon group-containing polyoxyalkylene compound is 100 parts by mass. When used, it is preferably 50 parts by mass or more. If the content of the solvent is small, the progress of the hydrosilylation reaction may be slow. On the other hand, if the content of the solvent is large, there is a problem that waste of the solvent increases and causes environmental pollution.
- a pH adjuster such as potassium acetate (Japanese Patent Publication No. 62-34039) in order to prevent or suppress the dehydrogenation reaction.
- the reaction temperature of the hydrosilylation reaction is preferably in the range of 50 to 150 ° C. When the reaction temperature is lower than 50 ° C., the reaction rate may decrease. When the reaction temperature is higher than 150 ° C., the unsaturated hydrocarbon may undergo internal transfer and the hydrosilylation reaction may not proceed.
- the reaction time is preferably 2 to 15 hours.
- the alkyl ether moiety may be oxidized.
- no bromination may be performed by removing an allyl ether group with an acidic substance or alkylating by a hydrogenation reaction.
- you may add tocopherol and BHT (dibutylhydroxytoluene) as antioxidant to the obtained (A) polyoxyalkylene modified organopolysiloxane compound.
- the polyoxyalkylene-modified organopolysiloxane compound may be paste, gel, or solid depending on the structure and may not have fluidity. Usually, when the (A) polyoxyalkylene-modified organopolysiloxane compound having no fluidity is produced, it is better to produce it in an organic solvent because the hydrosilylation reaction proceeds efficiently.
- the (A) polyoxyalkylene-modified organopolysiloxane compound is a paste, gel, or solid that does not have fluidity, it is not effectively dispersed when emulsified, and (C) emulsification of organopolysiloxane May not be possible.
- the organic solvent solution of the (A) polyoxyalkylene-modified organopolysiloxane compound may be an organic solvent that dissolves the component (A), and the organic solvent used in the production of the component (A) can be used as it is.
- the (B) nonionic surfactant solution (dissolved product) of (A) polyoxyalkylene-modified organopolysiloxane compound is an organic solvent solution (dissolved product) of the above-mentioned (A) polyoxyalkylene-modified organopolysiloxane compound. Further, (B-1) a nonionic surfactant described later can be blended, and heated and reduced in pressure.
- a nonionic surfactant (B-1) described later is added to an organic solvent solution of a polyoxyalkylene-modified organopolysiloxane compound, and the pressure is reduced to 3 to 50 mmHg and heated to room temperature (20 ° C.) to 120 ° C.
- the organic solvent is distilled off by (B-1) nonionic surfactant.
- the heating temperature at that time is preferably less than 120 ° C. If the temperature is higher than 120 ° C, the alkyl ether moiety may be oxidized.
- an antifoaming agent can be added.
- surfactant examples include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
- Nonionic surfactants include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Nonionic surfactants such as esters and glycerin fatty acid esters can be mentioned.
- polyoxyethylene octyl ether examples thereof include polyoxyethylene octyl ether, polyoxyethylene polyoxypropylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, Examples thereof include oxyethylene polyoxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene polyoxypropylene tridecyl ether, and polyoxyethylene cetyl ether. It is also possible to use a reactive surfactant having a functional group.
- Anionic surfactants include alkyl sulfates such as lauryl sulfate, alkylbenzene sulfonic acids and salts thereof, sulfate esters of monoalkyl polyoxyethylene ethers, acetate salts of monoalkyl polyoxyethylene ethers, alkyl naphthyl sulfonic acids And salts thereof, alkali metal sulforesinates, alkali metal sulfosuccinates, alkyl phosphoric acids and salts thereof, monoalkyl polyoxyethylene ether phosphate esters, fatty acid sulfonated glyceryl esters, alkyl sulfate alkali metal salts and sulfate esters Is mentioned.
- alkyl sulfates such as lauryl sulfate, alkylbenzene sulfonic acids and salts thereof, sulfate esters of monoalkyl polyoxyethylene ethers, a
- lauryl sulfate examples thereof include lauryl sulfate, sodium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether acetate, sodium dodecylbenzenesulfonate, polyoxyethylenesulfosuccinic acid.
- examples thereof include disodium lauryl, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl ether phosphate, sodium alkylnaphthalene sulfonate, and the like. It is also possible to use a reactive surfactant having a functional group.
- Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, sulfonium salts, phosphonium salts, and acetates. Specific examples thereof include stearylamine acetate, lauryltrimethylammonium chloride, cetyltrimethylammonium, stearyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride.
- amphoteric surfactants include alkyl betaines and alkyl imidazolines. Specific examples thereof include lauryldimethylaminoacetic acid betaine, lauryldimethylamine oxide, and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.
- Anionic surfactants, cationic surfactants, and amphoteric surfactants have charges in their molecules, so their use is limited, or atoms such as sulfur and nitrogen contained in surfactants act as catalyst poisons to inhibit reactions. There is a case.
- the nonionic surfactant is preferably a polyoxyalkylene alkyl ether or a polyoxyethylene sorbitan fatty acid ester from the viewpoint of emulsifying properties.
- the nonionic surfactant is a nonionic surfactant that is liquid at 25 ° C., and can dissolve the (A) polyoxyalkylene-modified organopolysiloxane compound.
- Polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester
- Such nonionic surfactants can be mentioned.
- polyoxyethylene octyl ether examples thereof include polyoxyethylene octyl ether, polyoxyethylene polyoxypropylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, Examples thereof include oxyethylene polyoxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene polyoxypropylene tridecyl ether, and polyoxyethylene cetyl ether.
- nonionic surfactants polyoxyalkylene alkyl ethers or polyoxyethylene sorbitan fatty acid esters are preferable from the viewpoint of emulsifying properties, and more preferably, the number of moles of ethylene oxide added is 2 to 14, and HLB Is from 7.5 to 15. HLB is according to the Griffin equation. Two or more kinds of nonionic surfactants may be mixed and used as long as the HLB of the mixed surfactant satisfies the above value.
- the organopolysiloxane of component (C) has a viscosity at 25 ° C. of 15,000 mPa ⁇ s or more.
- Specific examples of the organopolysiloxane include cyclic siloxane, methyl hydrogen polysiloxane, dimethyl polysiloxane, alkyl-modified polysiloxane, aralkyl-modified polysiloxane, vinyl-modified polysiloxane, amino-modified polysiloxane, amino acid-modified polysiloxane, and fluorine-modified.
- Examples include polysiloxane, epoxy-modified polysiloxane, (meth) acryl-modified polysiloxane, hydroxy-modified polysiloxane, and phenyl-modified polysiloxane. From the viewpoint of versatility, dimethylpolysiloxane, hydroxy-modified polysiloxane, and phenyl-modified polysiloxane are preferable.
- the viscosity of the organopolysiloxane at 25 ° C. is 15,000 mPa ⁇ s or more, preferably 500,000 to 100,000,000 mPa ⁇ s, more preferably 750,000 to 100,000,000 mPa ⁇ s. is there. If the viscosity is lower than 15,000 mPa ⁇ s, the slipperiness and the like may be lowered, and the gloss of the film of the resin composition containing the organopolysiloxane emulsion composition of the present invention may be lowered. 100,000,000 mPa ⁇ s If the viscosity is higher than s, there is a possibility that a large load is applied to the apparatus during emulsification. (C) component may mix 2 or more types of organopolysiloxane, and the viscosity of the mixed organopolysiloxane should just satisfy said range.
- the content of the (A) polyoxyalkylene-modified organopolysiloxane compound is 1 to 50 parts by mass when the content of (C) the organopolysiloxane is 100 parts by mass. Yes, preferably 1 to 40 parts by mass, more preferably 3 to 35 parts by mass. If the content of the (A) polyoxyalkylene-modified organopolysiloxane compound is less than 1 part by mass, the (C) organopolysiloxane may not be emulsified due to a decrease in emulsification.
- the solvent resistance and salt resistance of the organopolysiloxane emulsion composition may be lowered.
- the amount of (A) polyoxyalkylene-modified organopolysiloxane compound is more than 50 parts by mass, the transparency of the film of the resin composition containing the organopolysiloxane emulsion composition may be lowered.
- component (C) is emulsified by dispersing in component (A) and component (B).
- component (C) is dispersed and emulsified only in component (D) and / or component (A) and / or component (B).
- the content of the surfactant (B) is 0 to 50 parts by mass, preferably 3 to 3 parts per 100 parts by mass of the (C) organopolysiloxane.
- the amount is 40 parts by mass, more preferably 5 to 35 parts by mass.
- B) When there are more surfactant than 50 mass parts, there exists a possibility of inhibiting the abrasion resistance of the film
- the mass ratio of (A) polyoxyalkylene-modified organopolysiloxane compound and (B) surfactant is not specified, but the mass ratio ((A) polyoxyalkylene-modified organopolysiloxane Compound / (B) surfactant) is preferably 0.1 or more, particularly 0.2 to 10.0, and particularly preferably 0.5 to 5.0.
- the ratio is less than 0.1.
- the total amount of (A) polyoxyalkylene-modified organopolysiloxane compound and (B) surfactant is not particularly specified, but 5 to 100 parts by mass when the content of (C) organopolysiloxane is 100 parts by mass. It is preferably 10 to 75 parts by mass, and more preferably 25 to 75 parts by mass.
- (D) water may be blended as necessary from the viewpoint of the required product form such as self-emulsification type or emulsion type or emulsification properties. Accordingly, the content of (D) water is 0 to 10,000 parts by mass, preferably 0 to 5,000 parts by mass, when the content of (C) organopolysiloxane is 100 parts by mass. The amount is preferably 0 to 1,000 parts by mass. When the amount is more than 10,000 parts by mass, the stability is lowered and there is a risk of separation. If the water content in (D) is within the above range, the particle size will not change over time.
- organopolysiloxane can be emulsified with (A) polyoxyalkylene-modified organopolysiloxane compound and (B) surfactant
- (D) it is not necessary to add water.
- an organopolysiloxane emulsion composition is blended with a solvent-type resin composition, if the organopolysiloxane emulsion composition contains water, it may be separated from water depending on the solvent and may not be uniform. In such a case, it is better to use an organopolysiloxane emulsion composition that does not contain water.
- the specific emulsification method of the organopolysiloxane emulsion composition of the present invention is mainly as follows.
- the first is a method in which (A) water is added after emulsifying a mixture of (A) a polyoxyalkylene-modified organopolysiloxane compound, (B) a surfactant and (C) an organopolysiloxane.
- the second is a method of emulsifying a mixture of (A) a polyoxyalkylene-modified organopolysiloxane compound, (B) a surfactant, (C) an organopolysiloxane and (D) water.
- the third is a method of blending (A) a polyoxyalkylene-modified organopolysiloxane compound after emulsifying a mixture of (B) a surfactant, (C) an organopolysiloxane and (D) water.
- the fourth is a method of blending (B) a surfactant after emulsifying a mixture of (A) a polyoxyalkylene-modified organopolysiloxane compound, (C) an organopolysiloxane and (D) water.
- the fifth is a method of emulsifying a mixture of (A) a polyoxyalkylene-modified organopolysiloxane compound and (C) an organopolysiloxane, and then blending (B) a surfactant and (D) water.
- the emulsification method of the present invention is described in detail below.
- a mixture of (A) a polyoxyalkylene-modified organopolysiloxane compound, (B) a surfactant, and (C) an organopolysiloxane is stirred by revolving motion and rotational motion of two or three blades. It emulsifies with a planetary mixer.
- the organopolysiloxane emulsion composition is prepared by diluting with a disper as a stirrer by rotation of a tooth-shaped blade or a homomixer as a stirrer by rotation of a rotor in a stator.
- the second emulsification method is as follows. A mixture of (A) polyoxyalkylene-modified organopolysiloxane compound, (B) surfactant, (C) organopolysiloxane, and (D) water is emulsified with a planetary mixer. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, (A) a polyoxyalkylene-modified organopolysiloxane compound, (B) a surfactant or (D) water is added as necessary to add a planetary mixer, Dilute with a disper or homomixer to prepare an organopolysiloxane emulsion composition.
- the third emulsification method is as follows.
- (B) A surfactant, (C) an organopolysiloxane, and (D) a mixture of water are emulsified with a planetary mixer or a disper. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, (A) a polyoxyalkylene-modified organopolysiloxane compound and, if necessary, (B) a surfactant or (D) water are blended, and a planetary mixer Then, the mixture is stirred with a disper or a homomixer to prepare an organopolysiloxane emulsion composition.
- the fourth emulsification method is as follows. A mixture of (A) polyoxyalkylene-modified organopolysiloxane compound, (C) organopolysiloxane, and (D) water is emulsified with a planetary mixer or disper. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, (A) polyoxyalkylene-modified organopolysiloxane compound, (B) surfactant or (D) water is further added as necessary, and a planetary mixer is added. Then, it is diluted with a disper or a homomixer to prepare an organopolysiloxane emulsion composition.
- the fifth emulsification method is as follows. A mixture of (A) polyoxyalkylene-modified organopolysiloxane compound and (C) organopolysiloxane is emulsified with a planetary mixer or a disper. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, (A) polyoxyalkylene-modified organopolysiloxane compound, (B) surfactant or (D) water is further added as necessary, and a planetary mixer is added. Then, it is diluted with a disper or a homomixer to prepare an organopolysiloxane emulsion composition.
- the concentration of (C) organopolysiloxane in the organopolysiloxane emulsion composition of the present invention is preferably in the range of 1 to 90% by mass. If it is less than 1% by mass, there is a problem in the stability of the emulsion composition. If it is more than 90% by mass, the emulsion has a high viscosity and is difficult to handle. Moreover, depending on the composition of the organopolysiloxane emulsion composition, it may be separated over time. In that case, separation may be suppressed by reducing the amount of water contained in the organopolysiloxane emulsion composition.
- the temperature during emulsification is preferably 0 to 80 ° C., more preferably 0 to 40 ° C.
- the emulsion may not be emulsified or the produced emulsion may be unstable.
- the pressure may be not only normal pressure but also reduced pressure or increased pressure.
- foam may be difficult to mix and may be effectively emulsified.
- the pressure when reducing the pressure is higher than the vapor pressure of the raw material, and care is taken so that the raw material does not volatilize.
- emulsifier that can stir the raw material and the emulsified composition for emulsification.
- a planetary mixer that is a stirrer by the revolution and rotation of two or three blades
- a gate mixer Inoue Seisakusho
- Hibismix Priormics
- two blades of revolution, rotation, and tooth profile By using Hibis Dispermix 3D-5 type (Primics Co., Ltd.) which is a stirrer with high-speed rotation of blades, emulsification can be effectively carried out.
- colloid mill IKA, PUC, Nippon Seiki Seisakusho, Iwaki
- stirrer composed of a rotor and a stator
- high shear mixer silica, Primics
- Homodisper (Primics), Ajihomomixer (Primics), Combimix (Primics), which is a triaxial dispersion kneader combining a homomixer, homodisper and anchor mixer, in-direction screw or in-direction screw It is also possible to use HAAKE Mini LabII (Thermo Scientific), MC15, MC5 (Leo Laboratories), etc., which are 2-axis mixers having In the case of using a triaxial dispersion kneader combination mix (Primics) or Hibis Dispersix (Primics), it is possible to emulsify only with an anchor mixer.
- the organopolysiloxane emulsion composition of the present invention includes polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl pyrrolidone, alginates, xanthan gum, heavy acrylic acid as a protective colloid agent or thickener. You may mix
- antibacterial agents or antiseptics such as oxazoline compounds and aromatic carboxylates, fragrances, antioxidants, rust inhibitors, dyes, fillers, curing catalysts, organic powders, inorganic powders and the like may be blended. .
- the average particle size of the emulsion of the organopolysiloxane emulsion composition of the present invention is not specified, but it is 20 ⁇ m or less, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less. If the average particle size is larger than 20 ⁇ m, separation may occur immediately when the organopolysiloxane emulsion composition is dispersed in a solvent such as water or dimethylformamide. In the organopolysiloxane emulsion composition of the present invention, when the average particle size of the emulsion is 1.5 ⁇ m or more, it can be measured by Multisizer 3 manufactured by Beckman Coulter, Inc.
- the average particle size of the emulsion is less than 1.5 ⁇ m Can be measured by LA920 or LA960 manufactured by Horiba, Ltd., or N4 PLUS manufactured by Beckman Coulter, Inc.
- the lower limit of the average particle diameter is not particularly limited, but is usually 0.1 ⁇ m or more, particularly 0.5 ⁇ m or more.
- the organopolysiloxane emulsion composition of the present invention can be used as a surface treatment agent or an internal treatment agent for synthetic leather or artificial leather. Good slipperiness can be imparted by blending the organopolysiloxane emulsion composition with a resin composition mainly composed of a resin such as an acrylic resin or a urethane resin.
- the resin used in the resin composition is a thermosetting resin such as urethane resin, epoxy resin, phenol resin, melamine resin, urea resin, alkyd resin, polyimide resin, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyacetic acid.
- thermoplastic resins such as vinyl, tetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile styrene resin, and acrylic resin. From the viewpoint of versatility, a urethane resin or an acrylic resin is preferable.
- the organopolysiloxane emulsion composition When the organopolysiloxane emulsion composition is blended with the resin composition, the organopolysiloxane emulsion composition may be blended into the resin composition as it is and dispersed uniformly, or once dispersed in a solvent such as water, DMF, or MEK. Then, it may be blended in the resin composition.
- a known stirrer such as a homomixer, Satake stirrer, static mixer, Ross mixer, Hobart mixer, Henschel mixer, paddle mixer, ribbon mixer, etc. is used. do it.
- the blending amount of the organopolysiloxane emulsion composition with respect to the resin composition is 0.01 to 30% by mass with respect to the solid content of the resin.
- the content is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass.
- slipperiness may not be obtained, and when it exceeds 30% by mass, glossiness and leveling property may be deteriorated.
- Examples of the method for forming a film by applying the resin composition of the present invention on the surface of artificial leather or synthetic leather as a surface treatment agent include the following methods. Direct spraying methods such as direct spraying and direct coating methods such as a gravure coater, knife coater, comma coater, and air knife coater can be mentioned. From the viewpoint of versatility and stability of the resin composition, the direct coating method using a gravure coater is most preferable.
- the coating amount is preferably in the range of 3 to 100 g / m 2 , more preferably in the range of 5 to 30 g / m 2 after drying.
- the drying conditions after the application of the resin composition of the present invention are not particularly limited as long as the water or solvent in the resin composition evaporates and a crosslinking reaction of the resin occurs as necessary. For about 10 seconds to 5 minutes, more preferably at 80 to 130 ° C. for about 30 seconds to 2 minutes.
- Examples of methods for producing artificial leather by blending the resin composition of the present invention as an internal treatment agent include the following methods.
- the artificial leather is produced by applying the resin composition of the present invention and various polymer compounds to a non-woven sheet-like material mainly composed of ultrafine fibers, which are raw materials for artificial leather, and heat drying.
- the applying method to the non-woven sheet can be performed by any method such as an impregnation method, a spray method, and a coating method.
- Examples of the heat drying method include hot air drying, infrared heating, high frequency heating, and the like. Considering the amount of capital investment and the ease of maintenance, a hot air dryer is generally used.
- the drying temperature is 20 to 150 ° C. When heated at a temperature higher than 150 ° C., there is a possibility that the heat resistance of the resin is lowered and the fiber is deteriorated.
- an organopolysiloxane having a high degree of polymerization can be emulsified. It can be blended in any of the solvent-type and aqueous-type resin compositions, and gives good slipperiness. Therefore, the resin composition of the present invention is useful as a surface treatment agent or an internal treatment agent for synthetic leather and artificial leather such as automobile seats and bags.
- the viscosity is a value at 25 ° C. measured with a BM type or BH type rotational viscometer.
- a weight average molecular weight is the value of the weight average molecular weight by polystyrene conversion of the THF solvent measured by GPC (product made from TOSOH, HLC8220).
- Example 1 Under nitrogen atmosphere, the following general formula (6a) A silicon atom-bonded hydrogen atom-containing organopolysiloxane represented by the formula (viscosity 2,800 mm 2 / s, amount of hydrogen atom bonded to silicon atom 0.006 mol / 100 g) 85 parts by mass (85 g), and the following general formula (5a) After adding 15 parts by mass (15 g) of an unsaturated group-containing polyoxyalkylene compound represented by the formula and 250 parts by mass (250 g) of isopropyl alcohol, the mixture was heated to an internal temperature of 75 ° C.
- Example 2 The following general formula (9) (K indicates the number of the following viscosity) Surfactant-dissolving compound A of the polyoxyalkylene-modified organopolysiloxane compound obtained in Example 1 above and 35 parts by mass (35 g) of both ends hydroxydimethylpolysiloxane (viscosity 30 million mPa ⁇ s) represented by -1 15 parts by mass (15 g) was stirred at 20-30 rpm for 120 minutes with Hibismix (manufactured by Primex) to obtain an emulsified composition B. When the average particle diameter was measured with LA920 manufactured by Horiba, Ltd., it was 0.9 ⁇ m.
- Example 3 To 350 parts by mass (350 g) of polyoxyalkylene-modified organopolysiloxane compound A (29 mass% isopropanol solution) (weight average molecular weight 50,000 by GPC) represented by the above general formula (7) obtained in Example 1, Nonionic surfactant Sannonic SS120 (Sanyo Chemical Industries, polyoxyethylene alkyl ether, HLB14.5) 50 parts by mass (50 g) was added, and isopropyl alcohol was distilled off under reduced pressure under conditions of 10 to 15 mmHg and 35 to 40 ° C. As a result, a surfactant-dissolving compound A-2 of a polyoxyalkylene-modified organopolysiloxane compound was obtained.
- Nonionic surfactant Sannonic SS120 Sanyo Chemical Industries, polyoxyethylene alkyl ether, HLB14.5
- isopropyl alcohol was distilled off under reduced pressure under conditions of 10 to 15 mmHg and 35 to 40 ° C
- polyoxyalkylene-modified organopolysiloxane compound B represented by the following general formula (10) (Weight average molecular weight 14,000) was synthesized at a reaction rate of 90% or more (the polyoxyalkylene-modified organopolysiloxane compound B is a 29% by mass isopropanol solution).
- Example 5 84 parts by mass of a silicon atom-bonded hydrogen atom-containing organopolysiloxane represented by the above general formula (6a) (viscosity: 2,800 mm 2 / s, amount of hydrogen atom bonded to silicon atom: 0.006 mol / 100 g) under a nitrogen atmosphere ( 84g) and the following general formula (5b) After adding 16 parts by mass (16 g) of an unsaturated group-containing polyoxyalkylene compound represented by the formula and 250 parts by mass (250 g) of isopropyl alcohol, the mixture was heated to an internal temperature of 75 ° C.
- (6a) viscosity: 2,800 mm 2 / s, amount of hydrogen atom bonded to silicon atom: 0.006 mol / 100 g
- 5b After adding 16 parts by mass (16 g) of an unsaturated group-containing polyoxyalkylene compound represented by the formula and 250 parts by mass (250 g) of isopropyl alcohol, the mixture was heated to an internal
- nonionic surfactant TERGITOL-TMN6 manufactured by Dow Chemical Co., Ltd., 90% by mass polyoxyethylene alkyl ether aqueous solution, HLB13.1 ) 60 parts by mass (60 g) was added, and water contained in isopropyl alcohol and nonionic surfactant TERGITOL-TMN6 was distilled off under reduced pressure under the conditions of 10 to 15 mmHg and 35 to 40 ° C.
- Example 6 35 parts by mass (35 g) of both ends hydroxydimethylpolysiloxane (viscosity 30 million mPa ⁇ s) represented by the above general formula (9) and the polyoxyalkylene-modified organopolysiloxane compound obtained in Example 5 above
- Surfactant-dissolving compound C 15 parts by mass (15 g) and water 5 parts by mass (5 g) were stirred with Hibismix (manufactured by Primics) at 20-30 rpm for 90 minutes to obtain emulsion composition F.
- the average particle diameter was measured with a Multisizer 3 manufactured by Beckman Coulter, Inc. and found to be 5.2 ⁇ m.
- Example 7 35 parts by mass (35 g) of both ends hydroxydimethylpolysiloxane (viscosity 30 million mPa ⁇ s) represented by the above general formula (9) and the polyoxyalkylene-modified organopolysiloxane compound obtained in Example 5 above
- Surfactant-dissolving compound C 15 parts by mass (15 g) was stirred for 90 minutes at 20-30 rpm with Hibismix (manufactured by Primics), 5 parts by mass of water (5 g) was added, and homodisper (manufactured by Primics) at 500 rpm. The mixture was stirred for 3 minutes to obtain an emulsified composition G.
- the average particle size was 5.7 ⁇ m as measured by Multisizer 3 manufactured by Beckman Coulter.
- Example 8 Under nitrogen atmosphere, silicon atom-bonded hydrogen atom-containing organopolysiloxane represented by the above general formula (6b) (viscosity 75 mm 2 / s, amount of hydrogen atom bonded to silicon atom 0.05 mol / 100 g) 54 parts by mass (54 g) And the following general formula (5c) After adding 46 parts by mass (46 g) of an unsaturated group-containing polyoxyalkylene compound and 100 parts by mass (100 g) of isopropyl alcohol, the mixture was heated to an internal temperature of 75 ° C.
- polyoxyalkylene-modified organopolysiloxane compound D represented by the following general formula (12) (Weight average molecular weight 10,000) was synthesized at a reaction rate of 90% or more (the polyoxyalkylene-modified organopolysiloxane compound D is a 50% by mass isopropanol solution).
- Isopropyl alcohol was distilled off under reduced pressure under conditions of 10 to 15 mmHg and 35 to 40 ° C. to obtain a polyoxyalkylene-modified organopolysiloxane compound D-1.
- the viscosity of the polyoxyalkylene-modified organopolysiloxane compound D-1 was 80,000 mPa ⁇ s.
- Example 9 87 parts by mass (87 g) of silicon atom-bonded hydrogen atom-containing organopolysiloxane represented by the above general formula (6a) (viscosity 2,800 mm 2 / s, amount of hydrogen atom bonded to silicon atom 0.006 mol / 100 g); The following general formula (5d) After adding 13 parts by mass (13 g) of an unsaturated group-containing polyoxyalkylene compound represented by the formula and 250 parts by mass (250 g) of isopropyl alcohol, the mixture was heated to an internal temperature of 75 ° C.
- nonionic surfactant TERGITOL-TMN6 manufactured by Dow Chemical Co., Ltd., 90% by mass polyoxyethylene alkyl ether aqueous solution, HLB13.1 ) 60 parts by mass (60 g) was added, and water contained in isopropyl alcohol and nonionic surfactant TERGITOL-TMN6 was distilled off under reduced pressure under the conditions of 10 to 15 mmHg and 35 to 40 ° C.
- a surfactant-dissolving compound E-1 was obtained.
- 35 parts by mass (35 g) of both ends hydroxydimethylpolysiloxane (viscosity 7 million mPa ⁇ s) represented by the above general formula (8), and a surfactant-dissolving compound of the polyoxyalkylene-modified organopolysiloxane compound obtained above Emulsion composition I was obtained by stirring 15 parts by mass (15 g) of E-1 for about 120 minutes at 20 to 30 rpm with Hibismix (Primix). When the average particle diameter was measured with LA920 manufactured by Horiba, Ltd., it was 0.9 ⁇ m.
- the polyoxyalkylene-modified organopolysiloxane compound F is a 50% by mass isopropanol solution.
- the pressure was reduced at 110 to 120 ° C.
- polyoxyalkylene-modified organopolysiloxane compound F-1 weight average molecular weight by GPC 8,000.
- the viscosity of the polyoxyalkylene-modified organopolysiloxane compound F-1 was 1,800 mPa ⁇ s.
- the polyoxyalkylene-modified organopolysiloxane compound G is a 29% by mass isopropanol solution.
- Nonionic surfactant TERGITOL-TMN6 manufactured by Dow Chemical Co., polyoxyethylene alkyl ether 90% by mass aqueous solution, HLB 13.1) 5.5 parts by mass (5.5 g) and both ends represented by the above general formula (8) Hydroxydimethylpolysiloxane (viscosity: 7 million mPa ⁇ s) 35 parts by mass (35 g) and ion-exchanged water 5 parts by mass (5 g) were stirred with Hibismix (Primics) at 30-40 rpm for about 60 minutes to emulsify composition Product K was obtained. When the average particle diameter was measured with Multisizer 3 manufactured by Beckman Coulter, it was 13.5 ⁇ m.
- Nonionic surfactant TERGITOL-TMN6 manufactured by Dow Chemical Co., polyoxyethylene alkyl ether 90% by mass aqueous solution, HLB 13.1) 5.5 parts by mass (5.5 g) and both ends represented by the above general formula (9) Hydroxydimethylpolysiloxane (viscosity 30 million mPa ⁇ s) 35 parts by mass (35 g) and ion-exchanged water 5 parts by mass (5 g) were stirred for about 60 minutes at 30 to 40 rpm with Hibismix (manufactured by Primics). Not emulsified.
- Emulsification Whether or not emulsification of the hydroxydimethylpolysiloxane at both ends according to Examples 1 to 9 and Comparative Examples 1 to 5 was carried out by shaking 0.5 g of a sample and 9.5 g of ion-exchanged water in a glass bottle, and observing the appearance. Evaluated by criteria. ⁇ : Sample can be dispersed in water ⁇ : Sample cannot be dispersed in water
- Solvent resistance A solvent resistance test was conducted on the organopolysiloxane emulsion compositions A to K. Emulsified compositions A to K (0.5 g) and DMF (dimethylformamide) (9.5 g) were placed in a glass bottle and shaken. The state of the solution was observed and evaluated according to the following criteria. ⁇ : The organopolysiloxane is hardly precipitated and the emulsion composition is dispersed in DMF. ⁇ : The organopolysiloxane is partially deposited and a part of the emulsion composition is dispersed in DMF. A state in which an object is destroyed and organopolysiloxane is deposited
- Slip property 1 A test of slipperiness 1 was performed on the organopolysiloxane emulsion compositions A to K. Emulsified compositions A to K are diluted with water so as to be a 20% by mass aqueous solution. Next, 10 g of an aqueous acrylic resin (40-418EF (manufactured by DIC)) and 0.25 g of a 20% by mass aqueous solution of the emulsified compositions AK are placed in a glass bottle and shaken to mix uniformly. Wire bar No.
- the aqueous acrylic resin blended with the emulsified composition in 3 is applied to paperboard PA2831 (manufactured by BYK) and then dried at room temperature (25 ° C.) for 1 hour. The coated surface of the paperboard was rubbed with a finger to confirm the slipperiness and evaluated according to the following criteria.
- Slip property 2 A test of slipperiness 2 was performed on the organopolysiloxane emulsion compositions A to K. Emulsified compositions A to K are diluted with DMF so as to be a 20% by mass DMF solution. When the emulsion compositions A to K are diluted in DMF, the emulsion composition is broken and a large amount of silicone is deposited, the slip 2 test is not performed.
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Abstract
Description
溶剤型及び水性型の樹脂組成物により内添処理もしくは表面処理した人工皮革や合成皮革は、自動車のシートや家具、衣料品等の用途に使用されており、光沢、すべり性、レベリング性が要求されている。すべり性や耐摩耗性の要求を満たすために高重合度のポリジメチルシロキサンが配合されるが、溶剤型や水性型のいずれの樹脂組成物にもポリジメチルシロキサンを配合できるようにするためには、ポリジメチルシロキサンがDMFや水のいずれにも分散できるように乳化等をする必要がある。しかし、ノニオン界面活性剤、アニオン界面活性剤又はカチオン界面活性剤で乳化したポリジメチルシロキサンの乳化組成物をDMF等の溶剤型の樹脂組成物に配合すると、均一には分散せず、乳化の状態を維持できなくなり、ポリジメチルシロキサンが析出する。従って、DMF等の溶剤にも水にも分散可能な高重合度のポリジメチルシロキサン乳化組成物の開発が求められていた。
〔1〕
(A)下記一般式(1)で表されるポリオキシアルキレン変性オルガノポリシロキサン化合物:1~50質量部、
で表されるポリオキシアルキレン基であり、Rは同一もしくは異なってもよく、水素原子、ヒドロキシ基、炭素数1~20の直鎖もしくは分岐鎖の非置換又は置換のアルキル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、又は炭素数1~20のアルコキシ基である。aは2~4の整数、bは0~2の整数、cは50~1,000の整数、dは0又は1、eは0又は1である。]
(B)界面活性剤:0~50質量部、
(C)25℃における粘度が15,000mPa・s以上であるオルガノポリシロキサン:100質量部、
(D)水:0~10,000質量部
を含有することを特徴とするオルガノポリシロキサン乳化組成物。
〔2〕
(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物が、下記一般式(3)で表されるポリオキシアルキレン基を両末端に有するポリオキシアルキレン変性オルガノポリシロキサン化合物である〔1〕に記載のオルガノポリシロキサン乳化組成物。
〔3〕
(C)オルガノポリシロキサンの25℃における粘度が500,000mPa・s以上である〔1〕又は〔2〕に記載のオルガノポリシロキサン乳化組成物。
〔4〕
乳化物の平均粒径が20μm以下である〔1〕~〔3〕のいずれかに記載のオルガノポリシロキサン乳化組成物。
〔5〕
(C)オルガノポリシロキサンが、ジメチルポリシロキサン、フェニル変性ポリシロキサン、ヒドロキシ変性ポリシロキサンのいずれか、もしくはそれらの混合物である〔1〕~〔4〕のいずれかに記載のオルガノポリシロキサン乳化組成物。
〔6〕
ウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、アルキド樹脂、ポリイミド樹脂、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリ酢酸ビニル、テトラフルオロエチレン、アクリロニトリルブタジエンスチレン樹脂、アクリロニトリルスチレン樹脂、アクリル樹脂から選択される樹脂と、〔1〕~〔5〕のいずれかに記載のオルガノポリシロキサン乳化組成物を配合する樹脂組成物。
[オルガノポリシロキサン乳化組成物]
本発明のオルガノポリシロキサン乳化組成物は、
(A)後述する一般式(1)で表されるポリオキシアルキレン変性オルガノポリシロキサン化合物:1~50質量部、
(B)界面活性剤:0~50質量部、
(C)25℃における粘度が15,000mPa・s以上であるオルガノポリシロキサン:100質量部、
(D)水:0~10,000質量部
を含有することを特徴とする。
(A)成分であるポリオキシアルキレン変性オルガノポリシロキサン化合物は、下記一般式(1)で表されるものである。
で表されるポリオキシアルキレン基であり、Rは同一もしくは異なってもよく、水素原子、ヒドロキシ基、炭素数1~20の直鎖もしくは分岐鎖の非置換又は置換のアルキル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、又は炭素数1~20のアルコキシ基である。aは2~4の整数、bは0~2の整数、cは50~1,000の整数、dは0又は1、eは0又は1である。]
上記式(2)において、R1は炭素数1~10の直鎖もしくは分岐鎖の非置換又は置換のアルキル基、水素原子、カルボキシ基、炭素数2~10のアシル基、又はフェニル基であり、炭素数1~10の直鎖もしくは分岐鎖の非置換又は置換のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基等のアルキル基、クロロメチル基、クロロプロピル基、ブロモエチル基、トリフルオロプロピル基等のハロゲン置換アルキル基が挙げられ、炭素数2~10のアシル基としては、例えば、アセチル基、オクタノイル基等が挙げられる。R1として、好ましくは炭素数1~10の直鎖もしくは分岐鎖の非置換又は置換のアルキル基、又は水素原子であり、合成の容易性からより好ましくは水素原子である。
EO、AOはブロックでもランダムでもよい。rは上記の値を満たせばよいが、汎用性の観点からr=1が最も好ましい。
なお、2種類以上の(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物を混合した場合でも、平均構造式が上記に規定した範囲を満たせばよい。
例えば、下記一般式(4)で表される末端ケイ素原子結合水素原子含有オルガノポリシロキサン化合物に、下記一般式(5)で表される不飽和炭化水素基含有ポリオキシアルキレン化合物をヒドロシリル化反応触媒存在下、溶媒中もしくは非溶媒中、ヒドロシリル化反応によりポリオキシアルキレン変性オルガノポリシロキサン化合物を合成する。
なお、式(4)の末端ケイ素原子結合水素原子含有オルガノポリシロキサン化合物の分子内には、[R2SiO2/2]単位だけでなく、[RSiO3/2]単位や[SiO4/2]単位を含むことも可能である。[RSiO3/2]単位や[SiO4/2]単位を(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物の分子内に含むことで、本発明のオルガノポリシロキサン乳化組成物を含む樹脂組成物の皮膜の耐摩耗性が向上する可能性がある。
触媒の含有量は、有効量であれば特に限定されないが、末端ケイ素原子結合水素原子含有オルガノポリシロキサン化合物と不飽和炭化水素基含有ポリオキシアルキレン化合物との合計質量に対して触媒金属が質量で0.1~1,000ppmの範囲以内となるような量であることが好ましく、特に0.5~100ppmの範囲以内となる量であることが好ましい。
溶媒の含有量は、末端ケイ素原子結合水素原子含有オルガノポリシロキサン化合物と不飽和炭化水素基含有ポリオキシアルキレン化合物との合計を100質量部としたとき、0~1,000質量部である。用いる場合は50質量部以上であることが好ましい。溶媒の含有量が少ないとヒドロシリル化反応の進行が遅くなる場合があり、一方で溶媒の含有量が多いと溶媒の廃棄物が増え環境汚染の原因となる問題がある。
さらに、加熱及び減圧をすることにより、イソプロピルアルコール溶媒を留去することができる。その際、120℃より温度が高いとアルキルエーテル部位が酸化するおそれがあるため、120℃未満で行うことが望ましい。
さらに、上記の方法では、ヒドロシリル化反応後に酸性物質によるアリルエーテル基の除去あるいは水素添加反応によるアルキル化によって無臭化を行ってもよい。また、得られた(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物に酸化防止剤としてトコフェロールやBHT(ジブチルヒドロキシトルエン)を添加してもよい。
(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物の(B-1)ノニオン界面活性剤溶液(溶解品)の製造方法は以下の通りである。(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物の有機溶剤溶液に、後述する(B-1)ノニオン界面活性剤を加え、3~50mmHgに減圧し、室温(20℃)~120℃に加熱することにより有機溶剤を留去し、(B-1)ノニオン界面活性剤に置換する。その際の加熱温度は120℃未満が好ましい。120℃より温度が高いとアルキルエーテル部位が酸化するおそれがある。溶剤を留去する際に泡立ちが発生するような場合は消泡剤を添加することも可能である。
(B)成分である界面活性剤としては、ノニオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤が挙げられる。
ノニオン界面活性剤について詳述する。本発明に好適に用いられるノニオン界面活性剤は、25℃で液状のノニオン界面活性剤であり、(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物を溶解できるものである。ポリオキシエチレンアルキルエーテル等のポリオキシアルキレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、グリセリン脂肪酸エステルのようなノニオン界面活性剤等を挙げることができる。これらの具体例としては、ポリオキシエチレンオクチルエーテル、ポリオキシエチレンポリオキシプロピレンオクチルエーテル、ポリオキシエチレンノニルエーテル、ポリオキシエチレンデシルエーテル、ポリオキシエチレンポリオキシプロピレンデシルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンポリオキシプロピレンラウリルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンポリオキシプロピレントリデシルエーテル、ポリオキシエチレンセチルエーテルなどが挙げられる。上記のノニオン界面活性剤のうち、乳化性の観点から好ましくはポリオキシアルキレンアルキルエーテルもしくはポリオキシエチレンソルビタン脂肪酸エステルであり、その中でもより好ましくはエチレンオキサイドの付加モル数が2~14であり、HLBが7.5~15のものである。HLBはグリフィンの式による。2種類以上のノニオン界面活性剤を混合して使用してもよく、混合した界面活性剤のHLBが上記の値を満たしていればよい。
(C)成分のオルガノポリシロキサンとしては、25℃における粘度が15,000mPa・s以上のものである。
オルガノポリシロキサンとして、具体的には、環状シロキサン、メチルハイドロジェンポリシロキサン、ジメチルポリシロキサン、アルキル変性ポリシロキサン、アラルキル変性ポリシロキサン、ビニル変性ポリシロキサン、アミノ変性ポリシロキサン、アミノ酸変性ポリシロキサン、フッ素変性ポリシロキサン、エポキシ変性ポリシロキサン、(メタ)アクリル変性ポリシロキサン、ヒドロキシ変性ポリシロキサン、フェニル変性ポリシロキサンが例示される。汎用性の観点から、好ましくはジメチルポリシロキサン、ヒドロキシ変性ポリシロキサン、フェニル変性ポリシロキサンが挙げられる。
(C)成分は、2種類以上のオルガノポリシロキサンを混合してもよく、混合したオルガノポリシロキサンの粘度が上記の範囲を満たせばよい。
本発明のオルガノポリシロキサン乳化組成物において、(D)成分である水を含まない場合、(C)成分は(A)成分及び(B)成分に分散して乳化するものである。また、(D)成分である水を含む場合、(C)成分は(D)成分及び/又は(A)成分及び/又は(B)成分にのみ分散して乳化するものである。
(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物と(B)界面活性剤の合計量に特に指定はないが、(C)オルガノポリシロキサンの含有量を100質量部としたとき、5~100質量部であり、好ましくは10~75質量部であり、より好ましくは25~75質量部である。(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物と(B)界面活性剤の合計量が(C)オルガノポリシロキサンの含有量を100質量部としたとき、5質量部未満だと(C)オルガノポリシロキサンの乳化ができないもしくは乳化物が安定でない場合があり、一方で100質量部を超えると得られる樹脂組成物の皮膜の耐摩耗性を阻害する可能性がある。
本発明のオルガノポリシロキサン乳化組成物において、(D)水は自己乳化型やエマルジョン型等の要求される製品の形態もしくは乳化性等の観点から必要に応じて配合すればよい。従って、(D)水の含有量は(C)オルガノポリシロキサンの含有量を100質量部としたとき、0~10,000質量部であり、好ましくは0~5,000質量部であり、より好ましくは0~1,000質量部である。10,000質量部より多いと安定性が低下し、大きく分離するおそれがある。(D)の水の含有量が上記の範囲内であれば、粒径は経時で変化しない。(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物及び(B)界面活性剤により(C)オルガノポリシロキサンの乳化が可能な時は(D)水を配合する必要はない。特に溶剤型の樹脂組成物にオルガノポリシロキサン乳化組成物を配合する際、オルガノポリシロキサン乳化組成物に水が含まれていると溶剤によっては水と分離し均一にならない場合がある。そのような場合は、水を含まないオルガノポリシロキサン乳化組成物を使用したほうがよい。
本発明のオルガノポリシロキサン乳化組成物の具体的な乳化方法は主に以下に示す通りである。第一は(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物、(B)界面活性剤及び(C)オルガノポリシロキサンの混合物を乳化した後に(D)水を配合する方法である。第二は(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物、(B)界面活性剤、(C)オルガノポリシロキサン及び(D)水の混合物を乳化する方法である。第三は(B)界面活性剤、(C)オルガノポリシロキサン及び(D)水の混合物を乳化した後に(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物を配合する方法である。第四は(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物、(C)オルガノポリシロキサン及び(D)水の混合物を乳化した後に(B)界面活性剤を配合する方法である。第五は(A)ポリオキシアルキレン変性オルガノポリシロキサン化合物及び(C)オルガノポリシロキサンの混合物を乳化した後に(B)界面活性剤及び(D)水を配合する方法である。本発明の乳化方法について以下に詳述する。
本発明のオルガノポリシロキサン乳化組成物は、合成皮革や人工皮革の表面処理剤もしくは内添処理剤として使用することが可能である。アクリル樹脂やウレタン樹脂といった樹脂を主成分とする樹脂組成物にオルガノポリシロキサン乳化組成物を配合することで、良好なすべり性を付与することができる。
本発明の樹脂組成物の塗工後の乾燥条件は、樹脂組成物中の水もしくは溶剤が蒸発し、必要に応じて樹脂の架橋反応が起きれば特に制限はないが、通常は20~150℃で10秒~5分間程度の加熱、より好ましくは80~130℃で30秒~2分間程度の加熱である。
窒素雰囲気下、下記一般式(6a)
続いて、下記一般式(8)
で示される両末端ヒドロキシジメチルポリシロキサン(粘度700万mPa・s)35質量部(35g)、及び上記で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物A-1 15質量部(15g)をハイビスミックス(プライミクス社製)により20~30rpmで約120分撹拌して乳化組成物Aを得た。平均粒径を(株)堀場製作所製のLA920で測定したところ、0.7μmであった。
下記一般式(9)
で示される両末端ヒドロキシジメチルポリシロキサン(粘度3,000万mPa・s)35質量部(35g)と、上記実施例1で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物A-1 15質量部(15g)をハイビスミックス(プライミクス社製)により20~30rpmで120分撹拌して乳化組成物Bを得た。平均粒径を(株)堀場製作所製のLA920で測定したところ、0.9μmであった。
実施例1で得られた上記一般式(7)で示されるポリオキシアルキレン変性オルガノポリシロキサン化合物A(29質量%イソプロパノール溶液)(GPCによる重量平均分子量50,000)350質量部(350g)に、ノニオン界面活性剤サンノニックSS120(三洋化成工業社製、ポリオキシエチレンアルキルエーテル、HLB14.5)50質量部(50g)を添加し、10~15mmHg、35~40℃の条件でイソプロピルアルコールを減圧留去し、ポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物A-2を得た。
続いて、上記一般式(9)で示される両末端ヒドロキシジメチルポリシロキサン(粘度3,000万mPa・s)35質量部(35g)と、上記で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物A-2 15質量部(15g)をハイビスミックス(プライミクス社製)により20rpmで60分撹拌して乳化組成物Cを得た。平均粒径をベックマンコールター社製Multisizer3で測定したところ、4.9μmであった。
窒素雰囲気下、下記一般式(6b)
続いて、上記一般式(8)で示される両末端ヒドロキシジメチルポリシロキサン(粘度700万mPa・s)35質量部(35g)、及び上記で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物B 15質量部(15g)をハイビスミックス(プライミクス社製)により20~30rpmで約120分撹拌して乳化組成物Dを得た。平均粒径を(株)堀場製作所製のLA920で測定したところ、0.7μmであった。
窒素雰囲気下、上記一般式(6a)で示されるケイ素原子結合水素原子含有オルガノポリシロキサン(粘度2,800mm2/s、ケイ素原子に結合した水素原子の量0.006mol/100g)84質量部(84g)と、下記一般式(5b)
続いて、上記一般式(9)で示される両末端ヒドロキシジメチルポリシロキサン(粘度3,000万mPa・s)35質量部(35g)、及び上記で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物C 15質量部(15g)をハイビスミックス(プライミクス社製)により20~30rpmで90分撹拌して乳化組成物Eを得た。平均粒径をベックマンコールター社製Multisizer3で測定したところ、5.6μmであった。
上記一般式(9)で示される両末端ヒドロキシジメチルポリシロキサン(粘度3,000万mPa・s)35質量部(35g)と、上記実施例5で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物C 15質量部(15g)と、水5質量部(5g)をハイビスミックス(プライミクス社製)により20~30rpmで90分撹拌して乳化組成物Fを得た。平均粒径をベックマンコールター社製Multisizer3で測定したところ、5.2μmであった。
上記一般式(9)で示される両末端ヒドロキシジメチルポリシロキサン(粘度3,000万mPa・s)35質量部(35g)と、上記実施例5で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物C 15質量部(15g)をハイビスミックス(プライミクス社製)により20~30rpmで90分撹拌し、さらに水5質量部(5g)を加え、ホモディスパー(プライミクス社製)500rpmで3分撹拌して乳化組成物Gを得た。平均粒径をベックマンコールター社製Multisizer3で測定したところ、5.7μmであった。
窒素雰囲気下、上記一般式(6b)で示されるケイ素原子結合水素原子含有オルガノポリシロキサン(粘度75mm2/s、ケイ素原子に結合した水素原子の量0.05mol/100g)54質量部(54g)と、下記一般式(5c)
10~15mmHg、35~40℃の条件でイソプロピルアルコールを減圧留去し、ポリオキシアルキレン変性オルガノポリシロキサン化合物D-1を得た。ポリオキシアルキレン変性オルガノポリシロキサン化合物D-1の粘度は80,000mPa・sであった。
上記一般式(6a)で示されるケイ素原子結合水素原子含有オルガノポリシロキサン(粘度2,800mm2/s、ケイ素原子に結合した水素原子の量0.006mol/100g)87質量部(87g)と、下記一般式(5d)
ポリオキシアルキレン変性オルガノポリシロキサン化合物E(29質量%イソプロパノール溶液)350質量部(350g)に、ノニオン界面活性剤TERGITOL-TMN6(ダウケミカル社製、ポリオキシエチレンアルキルエーテル90質量%水溶液、HLB13.1)60質量部(60g)を添加し、10~15mmHg、35~40℃の条件でイソプロピルアルコール及びノニオン界面活性剤TERGITOL-TMN6に含まれる水を減圧留去し、ポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物E-1を得た。
上記一般式(8)で示される両末端ヒドロキシジメチルポリシロキサン(粘度700万mPa・s)35質量部(35g)、及び上記で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物E-1 15質量部(15g)をハイビスミックス(プライミクス社製)により20~30rpmで約120分撹拌して乳化組成物Iを得た。平均粒径を(株)堀場製作所製のLA920で測定したところ、0.9μmであった。
窒素雰囲気下、上記一般式(6b)で示されるケイ素原子結合水素原子含有オルガノポリシロキサン(粘度75mm2/s、ケイ素原子に結合した水素原子の量0.05mol/100g)55質量部(55g)と、下記一般式(5e)
窒素バブリングをしながら110~120℃、30mmHg以下で減圧をして、イソプロパノールを留去し、ポリオキシアルキレン変性オルガノポリシロキサン化合物F-1(GPCによる重量平均分子量8,000)を得た。ポリオキシアルキレン変性オルガノポリシロキサン化合物F-1の粘度は1,800mPa・sであった。
窒素雰囲気下、下記一般式(6c)
上記で得られたポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶解化合物G-1 15質量部(15g)、及び上記一般式(8)で示される両末端ヒドロキシジメチルポリシロキサン(粘度700万mPa・s)35質量部(35g)を配合し、ハイビスミックス(プライミクス社製)により40~50rpmで60分撹拌したが、両末端ヒドロキシジメチルポリシロキサンは乳化しなかった。
比較例1で得られた上記一般式(14)で示されるポリオキシアルキレン変性オルガノポリシロキサン化合物F-1 10質量部(10g)と、ノニオン界面活性剤TERGITOL-TMN6(ダウケミカル社製、ポリオキシエチレンアルキルエーテル90質量%水溶液、HLB13.1)5.5質量部(5.5g)と、上記一般式(8)で示される両末端ヒドロキシジメチルポリシロキサン(粘度700万mPa・s)35質量部(35g)と、イオン交換水5質量部(5g)をハイビスミックス(プライミクス社製)により30~40rpmで約60分撹拌して乳化組成物Jを得た。平均粒径をベックマンコールター社製Multisizer3で測定したところ、1.7μmであった。
ノニオン界面活性剤TERGITOL-TMN6(ダウケミカル社製、ポリオキシエチレンアルキルエーテル90質量%水溶液、HLB13.1)5.5質量部(5.5g)と、上記一般式(8)で示される両末端ヒドロキシジメチルポリシロキサン(粘度700万mPa・s)35質量部(35g)と、イオン交換水5質量部(5g)をハイビスミックス(プライミクス社製)により30~40rpmで約60分撹拌して乳化組成物Kを得た。平均粒径をベックマンコールター社製のMultisizer3で測定したところ、13.5μmであった。
ノニオン界面活性剤TERGITOL-TMN6(ダウケミカル社製、ポリオキシエチレンアルキルエーテル90質量%水溶液、HLB13.1)5.5質量部(5.5g)と、上記一般式(9)で示される両末端ヒドロキシジメチルポリシロキサン(粘度3,000万mPa・s)35質量部(35g)と、イオン交換水5質量部(5g)をハイビスミックス(プライミクス社製)により30~40rpmで約60分撹拌したが、乳化しなかった。
実施例1~9、比較例1~5による両末端ヒドロキシジメチルポリシロキサンの乳化の可否を、サンプル0.5gとイオン交換水9.5gをガラス瓶に入れて振とうし、外観を観察し、下記基準で評価した。
○:水にサンプルの分散が可能
×:水にサンプルの分散が不可
オルガノポリシロキサン乳化組成物A~Kに対して耐溶剤性試験を行った。
乳化組成物A~K0.5gとDMF(ジメチルホルムアミド)9.5gをガラス瓶に入れて振とうし、溶液の状態を観察し、下記基準で評価した。
○:オルガノポリシロキサンの析出がほとんどなく、乳化組成物がDMFに分散した状態
△:オルガノポリシロキサンの一部が析出し、乳化組成物の一部がDMFに分散した状態
×:DMFにより乳化組成物が破壊され、オルガノポリシロキサンが析出した状態
オルガノポリシロキサン乳化組成物A~Kに対してすべり性1の試験を行った。
乳化組成物A~Kを20質量%水溶液になるように水で希釈する。次に水性アクリル樹脂(40-418EF(DIC社製))10g及び乳化組成物A~Kの20質量%水溶液0.25gをガラス瓶に入れて振とうし、均一混合させる。ワイヤーバーNo.3で乳化組成物を配合した水性アクリル樹脂を板紙PA2831(BYK社製)に塗布した後、室温(25℃)で1時間乾燥させる。指で板紙の塗布表面をこすり、すべり性を確認し、下記基準で評価した。
すべり性2:
オルガノポリシロキサン乳化組成物A~Kに対してすべり性2の試験を行った。
乳化組成物A~Kを20質量%DMF溶液になるようにDMFで希釈する。乳化組成物A~KをDMFに希釈した際、乳化組成物が破壊されシリコーンの析出が多く見られたものについてはすべり性2の試験をしないものとする。DMF溶剤系ポリウレタン樹脂(サンプレンLQ-258(三洋化成工業社製))10g及び乳化組成物A~K0.25gをガラス瓶に入れて振とうし、均一混合させる。ワイヤーバーNo.3で乳化組成物を配合した溶剤系ポリウレタン樹脂を板紙PA2831(BYK社製)に塗布した後、室温(25℃)で1時間乾燥させる。指で板紙の塗布表面をこすり、すべり性を確認し、下記基準で評価した。
○:乳化組成物A~Kを配合しなかった場合より、すべり性良好
△:乳化組成物A~Kを配合しなかった場合とすべり性同等
×:乳化組成物A~Kを配合しなかった場合よりすべり性悪いもしくは樹脂中でオルガノポリシロキサンが析出する
Claims (6)
- (A)下記一般式(1)で表されるポリオキシアルキレン変性オルガノポリシロキサン化合物:1~50質量部、
で表されるポリオキシアルキレン基であり、Rは同一もしくは異なってもよく、水素原子、ヒドロキシ基、炭素数1~20の直鎖もしくは分岐鎖の非置換又は置換のアルキル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、又は炭素数1~20のアルコキシ基である。aは2~4の整数、bは0~2の整数、cは50~1,000の整数、dは0又は1、eは0又は1である。]
(B)界面活性剤:0~50質量部、
(C)25℃における粘度が15,000mPa・s以上であるオルガノポリシロキサン:100質量部、
(D)水:0~10,000質量部
を含有することを特徴とするオルガノポリシロキサン乳化組成物。 - (C)オルガノポリシロキサンの25℃における粘度が500,000mPa・s以上である請求項1又は2に記載のオルガノポリシロキサン乳化組成物。
- 乳化物の平均粒径が20μm以下である請求項1~3のいずれか1項に記載のオルガノポリシロキサン乳化組成物。
- (C)オルガノポリシロキサンが、ジメチルポリシロキサン、フェニル変性ポリシロキサン、ヒドロキシ変性ポリシロキサンのいずれか、もしくはそれらの混合物である請求項1~4のいずれか1項に記載のオルガノポリシロキサン乳化組成物。
- ウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、アルキド樹脂、ポリイミド樹脂、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリ酢酸ビニル、テトラフルオロエチレン、アクリロニトリルブタジエンスチレン樹脂、アクリロニトリルスチレン樹脂、アクリル樹脂から選択される樹脂と、請求項1~5のいずれか1項に記載のオルガノポリシロキサン乳化組成物を配合する樹脂組成物。
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WO2016111225A1 (ja) * | 2015-01-09 | 2016-07-14 | 信越化学工業株式会社 | ポリオキシアルキレン変性ジオルガノポリシロキサン化合物及びその製造方法並びにオルガノポリシロキサン乳化組成物 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018029966A1 (ja) * | 2016-08-10 | 2018-02-15 | 信越化学工業株式会社 | オルガノポリシロキサン乳化組成物及び樹脂組成物 |
US11242458B2 (en) | 2016-08-10 | 2022-02-08 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane emulsion composition and resin composition |
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JP2017125139A (ja) | 2017-07-20 |
EP3404068B1 (en) | 2023-07-26 |
EP3404068A1 (en) | 2018-11-21 |
TWI713673B (zh) | 2020-12-21 |
KR102691899B1 (ko) | 2024-08-06 |
US20190023850A1 (en) | 2019-01-24 |
KR20180102109A (ko) | 2018-09-14 |
TW201734137A (zh) | 2017-10-01 |
US10703908B2 (en) | 2020-07-07 |
CN108473771A (zh) | 2018-08-31 |
JP6601229B2 (ja) | 2019-11-06 |
EP3404068A4 (en) | 2019-08-14 |
CN108473771B (zh) | 2021-07-23 |
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