WO2020255895A1 - 水中油型シリコーンエマルジョン組成物およびその用途 - Google Patents
水中油型シリコーンエマルジョン組成物およびその用途 Download PDFInfo
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Definitions
- the present invention relates to an oil-in-water silicone emulsion composition, and more particularly to an oil-in-water silicone emulsion composition containing a relatively large amount of colloidal silica and its use, and more particularly by removing water.
- the present invention relates to an oil-in-water silicone emulsion composition containing colloidal silica, which has rubber-like elasticity, has no adhesiveness on the surface, and can form a friction-reducing cured film.
- An oil-in-water silicone emulsion composition that forms a cured film with mold release, release, water repellency, stain resistance, and heat resistance by removing water is a paint, paper coating agent, mold release agent, release agent, etc. It is used in fiber treatment agents and cosmetics.
- a composition composed of a hydroxyl group-containing diorganosiloxane, a silicone resin, and an aminoxy group-terminated diorganosiloxane see, for example, Patent Document 1
- a hydroxyl group-containing diorganosiloxane or a side chain as a cross-linking agent.
- Proposed compositions in which a compound selected from linear siloxane having an aminoxy group, cyclic aminoxisiloxane, aminoxisilane, and a partial hydrolysis product thereof are mixed and then emulsified. ing.
- these compositions have a problem that the strength of the cured film and the adhesion of the cured film to the substrate are not sufficient, and the adhesiveness remains on the surface of the substrate.
- Patent Documents 3 to 6 and the like have been proposed, and the applicants of the present application have proposed in Patent Document 7.
- compositions still have room for improvement in the strength of the cured film and the adhesion of the cured film to the substrate, and the adhesiveness remains on the surface of the cured film, so that the surface is particularly smooth. / There remains a problem that it cannot be applied to a base material that requires a feel and a base material that requires a friction-reducing surface.
- An object of the present invention is to obtain a cured film which can be uniformly applied to a base material, has less surface adhesiveness (tack) by removing water, and has excellent adhesion to the base material and film strength. It is to provide an oil-in-water silicone emulsion composition which can be formed, its use and manufacturing method.
- the present inventors have (A) at least two hydroxyl groups or hydrolyzable groups bonded to a silicon atom in one molecule, and have a viscosity at 25 ° C. of 100.
- the oil-in-water silicone emulsion composition can form a cured film having excellent adhesion to a substrate and film strength by the above structure, and a relatively large amount of colloidal silica with respect to the component (A). Since it contains (in terms of solid content), the surface of the formed cured film is in a smooth and tack-free state without causing adhesiveness, and a smooth cured film having excellent friction-reducing properties can be formed on the surface of the base material.
- the oil-in-water silicone emulsion composition of the present invention can be uniformly applied to the surface of the base material and contains a relatively large amount of colloidal silica (in terms of solid content) with respect to the component (A). By removing water, a cured film having less surface adhesiveness (tack) and excellent adhesion to a substrate and film strength can be formed.
- the oil-in-water silicone emulsion composition is preferably used as a surface treatment agent because it has rubber-like elasticity by removing water, has no adhesiveness on the surface, and can form a friction-reducing cured film. It is possible to provide a base material having the cured film.
- the oil-in-water silicone emulsion composition of the present invention can be efficiently produced. Further, according to the surface treatment method of the present invention, it has sufficient strength on the surface of a wide variety of base materials, that is, rubber-like elasticity and sufficient adhesion to the base material, and has surface adhesiveness (tack). It is possible to efficiently form a cured film that is smooth and has excellent friction reduction properties on the surface of the base material.
- oil-in-water silicone emulsion composition of the present invention will be described in detail.
- the component (A) has at least two groups selected from the group consisting of a hydroxyl group bonded to a silicon atom, an alkoxy group and an alkoxyalkoxy group in one molecule, and has a viscosity at 25 ° C. of 100,000 to 20,000. It is a polyorganosiloxane in the range of 000 mPa ⁇ s, and is the main component of the oil-in-water silicone emulsion composition of the present invention.
- the molecular structure of the polyorganosiloxane component (A) may be linear, cyclic, branched, dendritic, or network-like, but it must be linear or linear with some branches. Is preferable.
- a group selected from the group consisting of a hydroxyl group, an alkoxy group and an alkoxyalkoxy group may be present at the end of the molecular chain, at the side chain of the molecular chain, or at both of them.
- Alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, decyloxy group and the like.
- the alkoxy group is preferably from 10 to 10, and the alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and a methoxypropoxy group.
- Examples of the organic group bonded to a silicon atom other than the group selected from the group consisting of a hydroxyl group, an alkoxy group and an alkoxyalkoxy group include an unsubstituted monovalent hydrocarbon group and a substituted monovalent hydrocarbon group.
- the unsubstituted monovalent hydrocarbon group preferably has 1 to 10 carbon atoms in terms of assisting emulsification, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 2 carbon atoms. It is preferably an alkenyl group of ⁇ 10, and more preferably a methyl group or a phenyl group.
- the substituted monovalent hydrocarbon group a part or all of the hydrogen atom of the above-mentioned unsubstituted monovalent hydrocarbon group, particularly an alkyl group having 1 to 10 carbon atoms or a phenyl group, is a halogen atom such as fluorine or chlorine;
- a substituent such as an epoxy functional group; a methacryl functional group; an acrylic functional group; an amino functional group; a sulfur-containing functional group; an alkoxy group; a hydroxycarbonyl group; an alkoxycarbonyl group.
- the strength of the cured film obtained by removing water from the oil-in-water silicone emulsion composition of the present invention, the adhesion to the substrate, and the reduction of the surface adhesiveness (tack) of the cured film containing the component (B) and the reduction of friction is in the range of 100,000 mPa ⁇ s to 20,000,000 mPa ⁇ s, and in the range of 300,000 mPa ⁇ s to 10,000,000 mPa ⁇ s.
- the viscosity of the component (A) is less than the above lower limit, the strength and group of the cured film obtained by removing water from the oil-in-water silicone emulsion composition even if the amount of the component (B) is in the range described later.
- the adhesion to the material may be insufficient, and the surface adhesiveness of the cured film may occur, so that a smooth surface may not be realized.
- the viscosity of the component (A) exceeds the above upper limit, there arises a problem that synthesis is difficult by emulsion polymerization and it is difficult to obtain a stable emulsion by a conventional method.
- Such component (A) is preferably a diorganopolysiloxane that blocks hydroxyl groups at both ends of the molecular chain. Such capped at both molecular terminals with hydroxyl groups diorganopolysiloxane of the general formula: HO polyorganosiloxane represented by (R 1 2 SiO) m H is exemplified.
- R 1 is the same as an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom other than the hydroxyl group or the hydrolyzable group, and among them, an alkyl group having 1 to 10 carbon atoms, An aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are preferable, and a methyl group or a phenyl group is particularly preferable.
- m is an integer of 2 or more, and the viscosity at 25 ° C. is preferably a number in the above viscosity range of 100,000 mPa ⁇ s to 20,000,000 mPa ⁇ s.
- a polyorganopolysiloxane having the above structure can be used, and the production method thereof is not particularly limited, and the polyorganopolysiloxane obtained by a known production method such as an equilibrium polymerization method is used. May be emulsified in water with an emulsifier such as the component (C1) described later, but the component (A) is considered from the viewpoint of handling workability during production and particle size and stability during emulsion dispersion.
- Organopolysiloxane obtained by emulsion polymerization using an organopolysiloxane having a lower degree of polymerization, which is a precursor of the above, can be preferably used.
- polyorganosiloxane having at least two hydroxyl groups or hydrolyzable groups bonded to a silicon atom (a), which is a precursor of the component (A), and aminoxy bonded to a silicon atom (b).
- a polyorganosiloxane obtained by emulsifying and polymerizing an aminoxi group-containing organic silicon compound having an average of two groups in one molecule in the presence of the component (C1) described later, more preferably the component (C2).
- (A) is preferably a chain-like polyorganosiloxane having a lower viscosity than the component (A) and having a hydroxyl group or a hydrolyzable group bonded to a silicon atom at both ends of the molecular chain. More specifically, the component (a) has a viscosity at 25 ° C.
- n H is (a) a viscosity above viscosity range of components at 25 ° C., preferably The number is preferably in the range of 50 to 50,000 mPa ⁇ s.
- R 1 is the same as an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom other than the above-mentioned hydroxyl group or hydrolyzable group, and is particularly preferably a methyl group or a phenyl group.
- An aminoxy group-containing organosilicon compound having an average of two aminoxy groups bonded to silicon atoms in one molecule has good surface hardness without stickiness by reacting and cross-linking the components (a). It is a component for promoting the formation of a cured film having rubber-like elasticity.
- the component (b) contains an aminoxy group bonded to two silicon atoms on average in one molecule, and two aminoxi groups may be present only in the side chain of the molecule chain on average, and both ends of the molecule chain. It may be present only at the end of the molecule chain and at the side chain of the molecule chain, one on average.
- (B) When the number of aminoxic groups in one molecule is 3 or more on average in one molecule, gelation of the mixture is likely to occur inside the emulsifying device or in the pre-mixing step before emulsification during emulsification, and gel is applied to the manufacturing device. Objects may adhere to it, and the obtained cured film may not stretch well.
- aminoxy group-containing organic silicon compounds include polydiorganosiloxanes that block both ends of the molecular chain, diorganosiloxane / organoaminoxisiloxane copolymers that block the aminoxy groups at one end of the molecular chain, and triorganosilyl groups that block both ends of the molecular chain.
- examples thereof include a closed diorganosiloxane / organoaminoxiloxane copolymer, a cyclic diorganosiloxane / organoaminoxisiloxane copolymer, and a diaminoxidiorganosilane.
- the blending amount of the component (b) is 0.1 to 100 parts by mass, preferably 0.5 to 50 parts by mass, and 1 to 20 parts by mass with respect to 100 parts by mass of the component (a). Is more preferable.
- the component (b) is preferably of the general formula: R 2 R 1 2 SiO (R 1 R 3 SiO) n (R 1 2 SiO) p SiR 1 2 R 2 Indicated by.
- R 1 is the same as described above, and is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. Is preferably a methyl group or a phenyl group.
- R 3 is an aminoxy group.
- R 2 is an aminoxic group; when n is 1, one of R 2 is an aminoxic group, and the remaining R 2 is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, carbon. It is a group selected from the group consisting of a halogen-substituted monovalent hydrocarbon group having 1 to 10 atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and an alkoxyalkoxy group having 2 to 10 carbon atoms; when n is 2, R 2 Is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and an alkoxyalkoxy group having 2 to 10 carbon atoms. It is a group selected from the group consisting of.
- Examples of the unsubstituted monovalent hydrocarbon include the same groups as described above, and among them, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms are preferable. In particular, it is preferably a methyl group or a phenyl group.
- the halogen-substituted monovalent hydrocarbon group is a group in which a part or all of the hydrogen atoms of the above-mentioned unsubstituted monovalent hydrocarbon group is substituted with a halogen atom, and is a chloromethyl group, 3,3,3-trifluoro.
- halogen-substituted alkyl group such as a propyl group, 3,3,4,4,5,5,5-heptafluoropentyl, difluoromonochloropropyl group and the like.
- alkoxy group and the alkoxyalkoxy group include the same groups as described above.
- aminoxy group examples include -ON (R 4 ) 2 and a group selected from the groups represented by the following formulas.
- R 4 is a linear or branched alkyl group having 1 to 5 carbon atoms.
- R 5 has a divalent hydrocarbon group having 2 to 15 carbon atoms or a molecular chain main chain consisting of 3 to 17 carbon atoms and 1 to 3 nitrogen atoms or 1 to 2 oxygen atoms.
- a dialkylaminoxy group in which an alkyl group having 1 to 5 carbon atoms is bonded to a nitrogen atom is preferable, and preferred aminox groups include, for example, a dimethylaminox group, a diethylaminoxi group, and a diplurpyraminoxy group.
- Examples thereof include a xy group, a heptylethylaminoxy group, a heptylpropylaminoxy group, and a heptylbutylaminoxy group, and a diethylaminoxy group is preferable.
- n is 0, 1 or 2, preferably 0 or 2, and more preferably 0.
- R 2 in the above formula is an aminoxy group
- n is 1, at least one of R 2 in the above formula is an aminoxy group.
- p is an integer of 0 or more, and the upper limit of p is not particularly limited, but from the viewpoint of ease of emulsification, p is preferably an integer in the range of 0 to 1000, and an integer in the range of 2 to 200. Is more preferable, and an integer in the range of 4 to 140 is most preferable.
- aminoxy group-containing organosilicon compound examples include an aminoxy group-containing organosilicon compound represented by the following formula.
- Me represents a methyl group
- Et represents an ethyl group
- Pr represents a propyl group.
- the component (b) when the component (b) remains in the oil-in-water silicone emulsion composition, it is a component that contributes to the reaction / cross-linking between the component (A) and the component (B), and is good without a sticky feeling. It is possible to form a cured film having surface hardness and rubber-like elasticity.
- colloidal silica is a component for improving the strength of the cured film and the adhesion to the substrate, and in the composition of the present invention, a relatively large amount of colloidal is compared with the component (A) in terms of solid content.
- silica it is a component that has less surface adhesiveness (tack) and can form a smooth and cured film with excellent friction reduction on the surface of the base material.
- Colloidal silica is available as an aqueous dispersion in which 5-40% by mass of silica particles are colloidally dispersed in water, has many silanol groups on the surface, and has a particle size of generally about 1 nm to 1 ⁇ m. is there.
- Such colloidal silica is preferably a basic aqueous dispersion stabilized by sodium ions or ammonium ions.
- the pH of colloidal silica as a basic aqueous dispersion is preferably 7.0 or higher, more preferably 9.0 or higher.
- the shape of the silica fine particles of colloidal silica is not particularly limited and is generally spherical, but an elongated shape or a pearl necklace shape may be used.
- the blending amount of the component (B) needs to be in the range of 45 to 120 parts by mass in terms of solid content with respect to 100 parts by mass of the component (A), preferably 50 to 120 parts by mass. It is in the range of 110 parts by mass, and particularly preferably in the range of 55 to 100 parts by mass.
- the solid content of colloidal silica is a non-volatile silica particle content
- the blending amount of the component (B) is within the above range, water is removed from the oil-in-water silicone emulsion composition of the present invention. Therefore, smoothness can be imparted to the surface of the cured film mainly composed of the component (A) or the crosslinked reaction product thereof.
- the blending amount of the component (B) is less than the above lower limit, stickiness (tack) may occur on the surface of the cured film.
- the blending amount of the component (B) exceeds the above upper limit, the flexibility, rubber elasticity, followability and adhesion to the surface of the base material of the cured film may be insufficient, and cracks in the obtained cured film may occur. It may peel off and cause stickiness (tack) on the surface of the cured film.
- the colloidal silica of the component (B) can be added during the polymerization or after the polymerization.
- an aqueous dispersion of colloidal silica particles containing water may be added to an emulsion containing the polyorganosiloxane of the component (A), which is a precursor of the component (A).
- An aqueous dispersion of colloidal silica particles may be added to an emulsion containing components and the like to proceed with the emulsion polymerization reaction.
- colloidal silica examples include Snowtex 20, Snowtex 30, etc. manufactured by Nippon Chemical Industrial Co., Ltd .; Adelite AT-20, etc. manufactured by Asahi Denka Kogyo Co., Ltd .; Crevosol 30R9, etc. manufactured by Clariant Japan Co., Ltd .; Examples thereof include Ludox (trademark) HS-40 manufactured by DuPont Co., Ltd .; Cataloid S-20L manufactured by Catalytic Chemical Industry Co., Ltd .; Silica Doll-20 manufactured by Nippon Chemical Industrial Co., Ltd. and the like.
- the ionic emulsifier of the component (C1) is a component that stably emulsifies the component (A) and, if necessary, the component (F) into the component (D).
- the blending amount of the component (C1) is 1 to 100 parts by mass, preferably 1 to 50 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A).
- an anionic surfactant As the ionic emulsifier of the component (C1), an anionic surfactant, a cationic surfactant and an amphoteric surfactant can be used.
- the ionic emulsifier one kind of such a surfactant may be used alone, or two or more kinds of different kinds of surfactants may be used in combination.
- alkylbenzene sulfonates alkyl ether sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylnaphthyl sulfonates, unsaturated aliphatic sulfonates, hydroxylated An aliphatic sulfonate is exemplified.
- alkyltrimethylammonium salts such as octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride; dialkyldimethylammonium salts such as dioctadecyldimethylammonium chloride, dihexadecyldimethylammonium chloride and didecyldimethylammonium chloride.
- alkyltrimethylammonium salts such as octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride
- dialkyldimethylammonium salts such as dioctadecyldimethylammonium chloride, dihexadecyldimethylammonium chloride and didecyldimethylammonium chloride.
- a quaternary ammonium salt surfactant is exemplified.
- amphoteric surfactants examples include alkyl betaine and alkyl imidazoline.
- the oil-in-water silicone emulsion composition of the present invention preferably uses the (C1) ionic emulsifier in combination with another nonionic emulsifier.
- nonionic emulsifier As a nonionic emulsifier that can be used in the present invention, a known nonionic surfactant can be used.
- nonionic surfactants glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyethylene-polyoxypropylene
- a polymer-type nonionic emulsifier is exemplified.
- the oil-in-water silicone emulsion composition of the present invention preferably further contains (C2) a polyoxyethylene-polyoxypropylene copolymer type nonionic emulsifier as a nonionic emulsifier.
- the components (A) and (F) can be stably emulsified in the component (D) which is a dispersion medium with a small particle size.
- the component (A) is formed by emulsion polymerization, the emulsion polymerization reaction can proceed stably, and an emulsion of the component (A), which is a highly stable emulsion polymerization reaction product, can be provided.
- the polyoxyethylene-polyoxypropylene copolymerized nonionic emulsifier which is the component (C2), is usually a compound represented by the following general formula (1) or general formula (2).
- a, b, c, d, e and f are the average number of moles of ethylene oxide or propylene oxide added, and are independently numbers from 1 to 350.
- the weight average molecular weight of the component (C2) is preferably 1,000 to 18,000, more preferably 1,500 to 10,000. When the component (C2) is in a solid state, it can be used as an aqueous solution.
- the compound (C2) is a "Pluronic (registered trademark) L” series, a “Pluronic (registered trademark) P” series, and a “Pluronic (registered trademark) F” series manufactured by ADEKA Corporation.
- "Pluronic (registered trademark) TR” series; Emargen PP-290 manufactured by Kao Corporation; Newcol 3240 manufactured by Nippon Emulsifier Co., Ltd. are exemplified, and these are available on the market.
- the blending amount of the component (C2) is 0.1 to 50 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A).
- the component (C2) is used in combination with the component (C1) to emulsify the component (A) or its precursor component, and other optional components such as the component (F), it is obtained as compared with each component alone.
- the particle size of the emulsion particles to be obtained can be reduced, and the stability of the emulsion composition can be improved.
- the total amount of the component (C1) and the component (C2) is generally 1 to 30% by mass of the total amount of the component (A) and the component (F) to be mixed as needed. It is preferably 2 to 20% by mass, more preferably. Further, the ratio of the blending amount of the component (C1) to the blending amount of the component (C2) is preferably in the range of 3: 1 to 100: 1.
- Cyclic siloxane, diorganopolysiloxane with both ends of the molecular chain, diorganopolysiloxane, organoalkoxysilane, etc. are emulsified and dispersed in water using the emulsifiers of the above components (C1) and (C2), and then acid and alkaline, if necessary. It is also possible to carry out the polymerization reaction by adding a catalyst such as a substance, and by using the above emulsifier, one group selected from the group consisting of a hydroxyl group bonded to a silicon atom, an alkoxy group and an alkoxyalkoxy group is selected.
- the amount of water of the component (D) may be sufficient as long as it maintains a stable aqueous emulsion state, and the blending amount is not particularly limited, but is usually 0 to 500 parts by mass with respect to 100 parts by mass of the component (A). , Preferably 10 to 200 parts by mass.
- the component (D) is water added independently of the component (B).
- water is an essential component, but the colloidal silica of the component (B) is in the form of an aqueous dispersion as described above, and when the component (B) is blended.
- the amount of water of component (D) may be 0 parts by mass.
- the amount of water contained from the components (B) and (D) may be in the range of 5 to 95% by mass of the whole composition. It is common.
- the oil-in-water emulsion composition of the present invention has one or more types from the viewpoint of further improving workability such as coatability and storage stability of the composition, particularly dispersion stability of the component (B).
- (E) It is preferable to contain a thickener.
- a thickener containing a water-soluble organic polymer such as a water-soluble acrylic resin or an inorganic thickener such as a clay mineral, the viscosity of water can be increased, and the technical effect of the present invention and the cured film can be obtained.
- the amount of the thickener added is arbitrary, and when the thickener is used, an amount that makes the entire composition within the viscosity range (1,000 mPas or more at 25 ° C.) described later is appropriately selected. Is preferable.
- the thickener used in the present invention is not particularly limited, and examples of the preferred thickener include one or more selected from (E1) a thickener containing a clay mineral and (E2) a thickener containing a water-soluble organic polymer. Will be done.
- the clay mineral may be either a natural product or a synthetic product, and for example, a natural or synthetic smectite clay such as bentonite containing a clay mineral as a main component, the smectite clay and polyacrylic acid, a carboxyvinyl polymer, or the like.
- a natural or synthetic smectite clay such as bentonite containing a clay mineral as a main component, the smectite clay and polyacrylic acid, a carboxyvinyl polymer, or the like.
- examples thereof include a hydrophilic composite composed of an anionic polymer and the like. That is, the component (E) may contain a thickener made of a water-soluble organic polymer other than the clay mineral, and is preferable.
- natural or synthetic smectite clays such as bentonite, montmorillonite, hectorite, saponite, saponite, biderite and nontronite as thickeners containing natural or synthetic (E1) clay minerals; magnesium aluminum silicate; And a composite product of these and a water-soluble organic polymer such as a carboxyvinyl polymer is exemplified, and a smectite clay such as bentonite and montmorillonite is preferable.
- smectite clay for example, smecton SA (manufactured by Kunimine Industries, Ltd.), which is a hydrothermal synthetic product, and Wenger (manufactured by Hojun Co., Ltd.), which is a natural refined product, are available.
- Kunimine Industries, Ltd. which is a hydrothermal synthetic product
- Wenger manufactured by Hojun Co., Ltd.
- the pH of these smectite clays is high.
- the pH is preferably in the range of 5.0 to 9.0.
- the thickener containing the (E2) water-soluble organic polymer examples include water-soluble organic polymers such as high molecular weight polysaccharides and water-soluble acrylic resins, and these may be used alone or as a hydrophilic composite together with clay minerals. It may be used in the form of.
- water-soluble organic polymer containing a carboxylate group is preferable, and for example, polyacrylic acids which are carboxyl-containing addition polymers such as sodium polyacrylate or sodium polymethacrylate are preferably exemplified.
- the amount of the thickener composed of these water-soluble organic polymers is excessive, the heat resistance and flame retardancy of the cured film obtained by removing water from the oil-in-water silicone emulsion composition of the present invention are impaired. Since there are cases, it is preferable to select the amount to be used according to the application.
- the component (E) may be in the form of an aqueous dispersion of a thickener composed of the clay mineral or the water-soluble organic polymer described above, and in particular, the content of the inorganic thickener which is a clay mineral is 100 water. It is preferably in the range of 0.1 to 10 parts by mass, or in the range of 0.5 to 5 parts by mass with respect to the mass part.
- the oil-in-water silicone emulsion composition of the present invention further comprises an alkoxysilane or an alkoxyalkoxysilane represented by the general formula (F): R 1 a SiX 4-a , from the viewpoint of improving the strength and adhesion of the cured film.
- it preferably contains the alkoxysilane or a partially hydrolyzed condensate of the alkoxysilane.
- R is the same as described above, and among them, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms are preferable, and in particular, It is preferably a methyl group or a phenyl group.
- X is an alkoxy group having 1 to 10 carbon atoms or an alkoxyalkoxy group having 2 to 10 carbon atoms, and the same groups as described above are exemplified. a is 0, 1 or 2, but 0 or 1 is preferable.
- the component (F) is preferably tetraalkoxysilane, alkyltrialkoxysilane, tetraalkoxyalkoxysilane, alkyltrialkoxyalkoxysilane, and more preferably tetraalkoxysilane or alkylalkoxysilane.
- the component (F) may be a partially hydrolyzed condensate of the organoalkoxysilane, organoalkoxyalkoxysilane, tetraalkoxysilane or tetraalkoxyalkoxysilane.
- the component (F) is preferably blended in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of improving the strength of the cured film and the adhesion to the substrate, and 1 to 15 parts by mass. It is more preferable to blend.
- the blending amount of the component (F) is less than 0.1 part by mass with respect to 100 parts by mass of the component (A)
- the strength of the cured film obtained by removing water from the produced aqueous silicone emulsion composition is sufficiently improved.
- it exceeds 50 parts by mass the amount of alcohol produced as a by-product increases, which adversely affects the environment and the human body, and the formability of the cured film may change over time, which is not preferable.
- the oil-in-water silicone emulsion composition of the present invention preferably contains a (G) amine compound as a pH adjuster. Diethylamine is preferable as the amine compound. Since these (G) components also function as a curing catalyst described later when removing water, it is possible to promote the condensation reaction of each component, and in particular, to realize a heavy metal-free curing reactivity such as tin. ..
- the blending amount of the component (G) as a pH adjuster is preferably in the range of 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, based on the entire oil-in-water silicone emulsion composition of the present invention. It is in the range of 2% by mass.
- the oil-in-water silicone emulsion composition of the present invention contains other components as required, such as pigments, defoamers, penetrants, antistatic agents, inorganic powders, preservatives, rust inhibitors, and bis (tri).
- Silane coupling agents other than component (F) such as methoxysilylpropyl) -disulfide, pH adjusters other than component (G), buffers, UV absorbers, curing catalysts, water-soluble resins, organic resin emulsions, pigments and solids.
- Lubricants, dyes, flame retardants and the like can be appropriately blended.
- a component selected from a curing catalyst, a pigment, a solid lubricant, and a flame retardant in practical use.
- the compounding of the curing catalyst is optional, but the components of the composition of the present invention can be compounded for rapid cross-linking and curing by a condensation reaction, and specifically, dibutyltin dilaurate, dibutyltin diacetate, tin octenoate, dibutyl.
- Organic tin compounds such as tin dioctate, tin laurate, dioctyl tin diversate, dioctyl tin diacetate, dibutyl tin bisoleyl malate; organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, dibutoxybis (ethylacetoacetate) titanium; etc.
- Acid compounds such as hydrochloric acid, sulfuric acid, dodecylbenzene sulfonic acid; alkaline compounds such as ammonia and sodium hydroxide; n-hexylamine, guanidine, 1,8-diazabicyclo [5.4.0] undecene (DBU), 1, Amine compounds such as 4-diazabicyclo [2.2.2] octane (DABCO); organic zirconium esters such as zirconium tetrapropylate and zirconium tetrabutyrate; zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetonate bisethylacetate Organic zirconium chelate such as acetate and zirconium tetraacetylacetonate; zirconium-based condensation aid catalyst such as zirconium bis (2-ethylhexanoate) oxide and oxozirconium compound such as zirconium acet
- Aluminum alcoholates such as aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate); diisopropoxyaluminum (ethylacetate acetate) aluminum tris (ethylacetacetate), aluminum tris (acetylacetonate), etc.
- Aluminum chelate compounds Aluminum-based condensation aids such as aluminum acyloxy compounds such as hydroxyaluminum bis (2-ethylhexanoate); Organic acid metal salts such as zinc stearate, zinc octylate, zinc acetate, iron octylate, etc. Condensation reaction catalyst of.
- the above amine compound is a component common to the component (G), and by using these components, it is possible to design a composition containing a metal such as tin (tin) and not containing a curing catalyst, and the environment. It is preferable from the viewpoint of reducing the impact.
- the amount of the condensation reaction catalyst used is not particularly limited, and can be any amount as long as the purpose of promoting the condensation reaction is achieved. The use of the condensation reaction catalyst is optional and does not have to be used in the present composition.
- the oil-in-water silicone emulsion composition of the present invention may contain a pigment or a solid lubricant, and is preferable.
- a solid lubricant typified by phyllosilicate, which is also known as a layered silicate
- the obtained cured film is imparted with anti-friction property to reduce friction and / or blocking, and the friction-reducing property is improved. It can be further improved.
- examples of phyllosilicates suitable for use as solid lubricants in the present invention include mica, talc, such as talc microspheres, kaolinite, smectite, sericite and chlorite.
- pigments examples include inorganic pigments such as aluminum hydroxide, heavy calcium carbonate, light calcium carbonate, titanium oxide, barium sulfate, active white clay, magnesium carbonate, alumina, and aluminum oxide, and for example, polystyrene resin particles and urea-formalin resin particles.
- Organic pigments such as polyolefin particles can be selected.
- the oil-in-water silicone emulsion composition of the present invention When the oil-in-water silicone emulsion composition of the present invention is applied to applications such as airbag coating, it may further contain a flame retardant in practice.
- the composition according to the present invention is suitable for surface coating of airbags and the like because it forms a flammable dry coating film that reduces friction and / or blocking on the surface of the substrate. Due to its nature, it is important that it is difficult to ignite and does not support combustion, and it is generally necessary to add a flame retardant in order to pass the rigorous flammability test applicable to the application.
- FMVSS # 302 US Federal Motor Vehicles Safety Standards Test
- the composition according to the present invention is suitable for an airbag or a coating agent used for applications requiring nonflammability / flame retardancy such as a top coat of a coating fabric formed on the airbag, and the effect of the flame retardant. Is often most effective when present in the topcoat.
- An example of a preferred flame retardant is preferably unsurface treated aluminum trihydrate.
- the flame retardant include other metal hydroxides such as magnesium hydroxide, metal oxides such as ferrite oxides and titanium oxide, carbonates such as zinc carbonate, and carbon black.
- the content of these flame retardant components may be in the range of 2 to 40% by mass, preferably 5 to 25% by mass with respect to the entire composition, and at least a part of the flame retardant is aluminum trihydrate. A certain component may be selected and is preferable.
- the oil-in-water silicone emulsion composition of the present invention preferably has a viscosity of 1000 mPa ⁇ s or more from the viewpoint of uniform coating property and workability. Viscosity is measured at 25 ° C. with a shear modulus of 1s-1 using a Wells-Brookfield Cone / Plate Viscometer equipped with a 2 ° tapered cone with a diameter of 20 mm (Wells-Brookfield Cone / Plate Viscometer). ASTM D4287). Unless otherwise indicated, the viscosities described herein have been measured in the same manner as described above. The viscosity is the overall viscosity of the oil-in-water silicone emulsion composition containing a solid lubricant, a thickener and the like, if necessary.
- the average particle size (average primary particle size) of the silicone emulsion particles in the oil-in-water silicone emulsion composition of the present invention is 50 to 50 from the viewpoint of storage stability, formability of cured film, and stability when diluted with water. It may be in the range of 600 nm, preferably 300 nm or less, and particularly preferably 250 nm or less.
- the average particle size of the emulsion particles can be measured by a dynamic light scattering method or the like.
- the oil-in-water silicone emulsion composition of the present invention Step (I): Component (A), component (C1), optionally part of component (C2) and component (D), homomixer, homogenizer, colloid mill, combination mixer, in-line continuous emulsification
- An emulsifier such as a machine, vacuum emulsifier, ultrasonic emulsifier, continuous mixer, and Step (II):
- the emulsion can be produced by a production method including a step of blending and dispersing the component (B) and the residual component (D) in the emulsion obtained in the above step.
- the component (B), the component (E), the component (F) and the component (G) may be blended in any of the above steps, if necessary, and are split and blended in both steps. May be good.
- the polyorganosiloxane as the component (A) may be obtained by an emulsion polymerization reaction.
- the method for producing an oil-in-water silicone emulsion composition of the present invention contains at least two hydroxyl groups or hydrolyzable groups bonded to (a) silicon atoms, which are precursors of component (A), in one molecule.
- the above-mentioned (C1) component and optionally the above-mentioned (C2) component are polyorganosiloxane having a plurality of polyorganosiloxanes and (b) an organosilicon group-containing organosilicon compound having an average of two aminoxy groups bonded to a silicon atom in one molecule. It may have a step of obtaining a polyorganosiloxane obtained by emulsification and polymerization in the presence of.
- the aqueous dispersion containing the component (A) which is the polyorganosiloxane after emulsion polymerization, contains the component (A), the component (C1), optionally the component (C2), and a part of the water (D).
- step (II) It is an emulsified and dispersed emulsion, and may be carried out simultaneously with the above step (I) or as a part of the step (I).
- step (II) may be performed subsequently, and the component (B), the component (E), the component (F) and the component (G) are contained in the emulsion before the emulsion polymerization reaction, if necessary. May be added to.
- the oil-in-water silicone emulsion composition of the present invention may be reduced so that the total content of the siloxane oligomer composed of 4 to 5 siloxane units is 2% by mass or less, if necessary. % Or less, 0.5% by mass or less may be used.
- the siloxane oligomer consisting of 4 to 5 siloxane units include 4 to pentameric cyclic siloxane oligomers such as octaorganotetracyclosiloxane and decaorganopentacyclosiloxane; hydroxydiorganosyloxy group-blocking tetraorganoji at both ends of the molecular chain.
- Examples thereof include 4- to pentameric linear siloxane oligomers such as siloxane and hydroxydiorganosyloxy group-blocking hexaorganotrisiloxane at both ends of the molecular chain.
- the content of the siloxane oligomer in the oil-in-water silicone emulsion composition of the present invention can be measured by gas chromatography.
- oil-in-water silicone emulsion composition surface treatment agent / surface modifier
- the above-mentioned oil-in-water silicone emulsion composition is applied to the surface of a base material and removed by evaporation / heating or the like to have rubber-like elasticity, no adhesiveness on the surface, and friction reduction property. Since it forms a cured film of, it can be used as a surface treatment agent for the purpose of modifying the surface of the base material.
- the surface treatment method of the present invention is characterized in that the surface of the base material is surface-treated with a surface treatment agent containing the above-mentioned oil-in-water silicone emulsion composition, and at least a part of the surface of the base material is covered with the above-mentioned cured film.
- the surface treatment agent may be the above-mentioned oil-in-water silicone emulsion composition or a water-diluted product thereof, or may optionally contain other additives.
- the base material to which the surface treatment agent of the present invention can be applied is not particularly limited, and metal, ceramic, concrete, cement, mortar, paper, fiber, natural fiber woven fabric, synthetic fiber woven fabric, non-woven fabric, cloth, and plastic.
- Glass, rubber, wood, stone, and other composite materials of the base material are exemplified.
- the surface treatment agent of the present invention can form a hardened film having rubber-like elasticity on the surface of the base material, having no adhesiveness on the surface, and reducing friction by removing water.
- Functional fabrics such as emergency chute of aircraft and hot air balloons, and surface treatment of building materials such as concrete can improve its function.
- water repellency, weather resistance, chemical resistance, soft texture, etc. due to the silicone elastic body can be imparted to the surface of various base materials, and further, heat resistance and heat resistance derived from the silicone elastic body can be imparted. Expected to improve flame retardancy.
- the method of surface-treating the surface of the base material with the above-mentioned oil-in-water silicone emulsion composition includes (I) a step of applying the oil-in-water silicone emulsion composition on the surface of the base material, and (II) on the surface of the base material. It is preferable that the step comprises removing water in the oil-in-water silicone emulsion composition to form a cured film.
- a coating method and a coating method used for paints and coating agents can be used without particular limitation, and brush coating, spray coating, dipping, flow coater, and dispenser can be used. Examples thereof include coating, roller coating such as a gravure roller, knife coating, spin coating, etc., and not only one coating but also a plurality of coatings may be repeated. Further, before painting, the surface of the object to be coated / the object to be coated may be cleaned in advance; dried, and primed. Further, the coating / coating amount is not particularly limited, and a thin coating may be applied to a functional fabric such as an airbag or a surface coated with silicone rubber thereof to reduce the weight, and the surface of the base material may be coated. It may be applied thickly to form a thick and durable cured film.
- Moisture removal in step (II) may be left at room temperature and air-dried, may be left at an atmospheric temperature adjusted to 20 to 200 ° C., or may be irradiated with infrared rays, ultraviolet rays or other high-energy rays. Good.
- the viscosity is a measured value at 25 ° C.
- the part representing the blending amount means the mass part
- the% representing the content means mass%.
- Me represents a methyl group
- Et represents an ethyl group.
- the average particle size of the emulsion particles was measured by a dynamic light scattering method at 25 ° C. using a submicron particle analyzer (COOLTER MODEL N4 MD manufactured by Coulter Electronics), and calculated by monodisperse mode analysis.
- the viscosity of the emulsion composition was measured at 25 ° C. using a Wells-Brookfield Cone / Plate Viscometer with a 20 mm diameter 2 ° taper cone at a shear modulus of 1s-1. Measured (ASTM D4287)
- Example 1 (a) 92.5 parts of hydroxydimethylsiloxy group-blocking polydimethylsiloxane at both ends of the molecular chain having a viscosity of 2,400 mPa ⁇ s, Equation (1): 7.5 parts of an aminoxane group-containing polysiloxane represented by Et2NO (Me2SiO) 7NEt2. (C2) 7.5 parts of a polyoxyethylene-polyoxypropylene copolymer type nonionic emulsifier (Adeka product name Pluronic (registered trademark) F108) that has been mixed and homogenized in advance, and (C1) a 40% aqueous solution of sodium alkanesulfonate.
- Pluronic registered trademark
- the viscosity of the organopolysiloxane (A) obtained by emulsion polymerization after the reaction was measured by the following procedure.
- Example 2 The silicone emulsion (No. 2) and the coating film composition were prepared in the same procedure as in Example 1 except that the total amount of silica particles was changed to 65.7 parts, and evaluated in the same procedure as in Example 1. Was done. The evaluation results are shown in Table 1.
- Example 3 The silicone emulsion (No. 3) and the coating film composition were prepared in the same procedure as in Example 1 except that the total amount of silica particles was changed to 73.2 parts, and evaluated in the same procedure as in Example 1. Was done. The evaluation results are shown in Table 1.
- the oil-in-water silicone emulsion composition of the present invention has good storage stability even when colloidal silica is blended, and has rubber-like elasticity when water is removed after coating or impregnating the substrate. Since it forms a cured film with excellent strength, it is used for water-based paints and inks, paper coating agents used for heat-sensitive paper and inkjet paper, mold release agents for molds and rubber, automobile weather strips, gaskets, rubber hoses, etc. It is useful as a resin coating agent, a fiber treatment agent used for clothing and airbags, a release agent, cosmetics, a building material, and the like.
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Abstract
Description
(A)成分は、ケイ素原子に結合した水酸基、アルコキシ基およびアルコキシアルコキシ基からなる群から選択される基を1分子中に少なくとも2個有し、25℃における粘度が100,000~20,000,000mPa・sの範囲であるポリオルガノシロキサンであり、本発明の水中油型シリコーンエマルジョン組成物の主成分である。(A)成分のポリオルガノシロキサンの分子構造は、直鎖状、環状、分岐状、樹枝状、網目状の何れであってもよいが、直鎖状または一部分岐を有する直鎖状であることが好ましい。水酸基、アルコキシ基およびアルコキシアルコキシ基からなる群から選択される基は分子鎖末端に存在してもよく、分子鎖側鎖に存在してもよく、その両方に存在してもよい。アルコキシ基としては、メトキシ基,エトキシ基,n-プロポキシ基,イソプロポキシ基、n-ブトキシ基、t-ブトキシ基、ヘキシルオキシ基、シクロヘキシルオキシ基、オクチルオキシ基、デシルオキシ基などの炭素原子数1~10のアルコキシ基であることが好ましく、アルコキシアルコキシ基としては、メトキシメトキシ基、メトキシエトキシ基、エトキシメトキシ基、メトキシプロポキシ基などの炭素原子数2~10アルコキシアルコキシ基であることが好ましい。
R2R1 2SiO(R1R3SiO)n(R1 2SiO)pSiR1 2R2
で示される。上式中、R1は前記と同じであり、中でも炭素原子数1~10のアルキル基、炭素原子数6~10のアリール基、炭素原子数2~10のアルケニル基であることが好ましく、特には、メチル基またはフェニル基であることが好ましい。R3はアミノキシ基である。nが0のときR2はアミノキシ基であり;nが1のときR2のうち一個はアミノキシ基であり、残余のR2は炭素原子数1~10の非置換一価炭化水素基、炭素原子数1~10ハロゲン置換一価炭化水素基、水酸基、炭素原子数1~10アルコキシ基および炭素原子数2~10アルコキシアルコキシ基からなる群から選ばれる基であり;nが2のときR2は炭素原子数1~10の非置換一価炭化水素基、炭素原子数1~10ハロゲン置換一価炭化水素基、水酸基、炭素原子数1~10アルコキシ基および炭素原子数2~10アルコキシアルコキシ基からなる群から選ばれる基である。
(Et2NO)Me2SiOSiMe2(ONEt2)
(Et2NO)Me2SiO(Me2SiO)12SiMe2(ONEt2)
(Et2NO)Me2SiO(Me2SiO)40SiMe2(ONEt2)
(Et2NO)Me2SiO(Me2SiO)80SiMe2(ONEt2)
Me2Si(ONEt2)2
Me3SiO(MeSi(ONEt2)O)2SiMe3
Me3SiO(Me2SiO)4(MeSi(ONEt2)O)2SiMe3
Me3SiO(Me2SiO)15(MeSi(ONEt2)O)2SiMe3
Me3SiO(Me2SiO)3(MeSi(ONEt2)O)7SiMe3
(B)コロイダルシリカは、硬化皮膜の強度や基材に対する密着性を向上させるための成分であり、本発明の組成物において、固形分換算で、(A)成分に対して比較的大量のコロイダルシリカを含むことで、表面粘着性(タック)が少なく、基材表面に滑らかで摩擦低減性に優れる硬化皮膜を形成可能な成分である。
(C1)成分のイオン性乳化剤は、(A)成分および必要に応じて(F)成分を(D)成分中に安定に乳化させる成分である。(C1)成分の配合量は(A)成分100質量部に対して1~100質量部であり、1~50質量部であることが好ましく、1~20質量部であることがより好ましい。
特に、本発明の水中油型シリコーンエマルジョン組成物は、ノニオン性乳化剤として、(C2)ポリオキシエチレン-ポリオキシプロピレン共重合型ノニオン乳化剤をさらに含むことが好ましい。前記の(C1)成分と(C2)成分を併用することで、(A)成分および(F)成分を、分散媒である(D)成分中に小粒子径で安定に乳化することができ、特に、(A)成分を乳化重合により形成させる場合に、乳化重合反応を安定して進行させ、安定性の高い乳化重合反応物である、(A)成分の乳化物を与えることができる。
HO(CH2CH2O)a(CH(CH3)CH2O)b(CH2CH2O)CH (1)
HO(CH(CH3)CH2O)d(CH2CH2O)e(CH(CH3)CH2O)fH (2)
一般式(1)、(2)において、a、b、c、d、e及びfは、エチレンオキシドないしプロピレンオキシドの平均付加モル数であり、それぞれ独立して、1~350の数である。(C2)成分の重量平均分子量は、1,000~18,000が好ましく、より好ましくは1,500~10,000である。(C2)成分が固体状である場合は、水溶液にして使用することも可能である。
(D)成分の水は、安定な水性エマルジョン状態を保つのに十分な量であればよく、配合量は特に限定されないが、通常、(A)成分100質量部に対して0~500質量部、好ましくは10~200質量部配合される。
本発明の水中油型エマルジョン組成物には、さらに、その塗布性等の作業性の向上と組成物の保存安定性、特に(B)成分の分散安定性を改善する見地から、1種類以上の(E)増粘剤を含有することが好ましい。特に、水溶性アクリル樹脂などの水溶性有機ポリマーまたは粘土鉱物等の無機系の増粘剤を含む増粘剤を使用することで、水の粘度を高め、本発明の技術的効果および硬化皮膜の耐熱性/難燃性を実質的に損なうことなく、本発明の水中油型エマルジョン組成物またはそれを含む表面処理剤の基材への塗布性および作業性を改善することができる利点がある。(E)増粘剤の添加量は、任意であり、増粘剤を用いる場合には、組成物全体が、後述する粘度範囲(25℃で1,000mPas以上)となる量を適宜選択することが好ましい。
本発明の水中油型シリコーンエマルジョン組成物は、硬化被膜の強度や密着性の向上の点から、さらに、(F)一般式:R1 aSiX4-aで示されるアルコキシシランもしくはアルコキシアルコキシシラン、または前記アルコキシシランもしくはアルコキシアルコキシシランの部分加水分解縮合物を含有することが好ましい。式中Rは前記と同様であり、中でも、炭素原子数1~10のアルキル基、炭素原子数6~10のアリール基、炭素原子数2~10のアルケニル基であることが好ましく、特には、メチル基またはフェニル基であることが好ましい。Xは炭素原子数1~10のアルコキシ基または炭素原子数2~10のアルコキシアルコキシ基であり、前記と同様の基が例示される。aは0,1または2であるが、0か1が好ましい。特に、(F)成分は、テトラアルコキシシラン、アルキルトリアルコキシシラン、テトラアルコキシアルコキシシラン、アルキルトリアルコキシアルコキシシランであることが好ましく、テトラアルコキシシランまたはアルキルアルコキシシランであることがより好ましい。
本発明の水中油型シリコーンエマルジョン組成物は、(G)アミン化合物をpH調整剤として配合することが好ましい。アミン化合物としては、ジエチルアミンが好ましい。これらの(G)成分は、水分除去時に、後述する硬化触媒としても機能するため、各成分の縮合反応を促進し、特に、錫等の重金属フリーの硬化反応性を実現することが可能である。
本発明の水中油型シリコーンエマルジョン組成物には、必要に応じて他の成分、例えば、顔料、消泡剤,浸透剤,帯電防止剤,無機粉体,防腐剤,防錆剤,ビス(トリメトキシシリルプロピル)-ジスルフィドなどの(F)成分以外のシランカップリング剤,(G)成分以外のpH調整剤,緩衝剤,紫外線吸収剤、硬化触媒、水溶性樹脂、有機樹脂エマルジョン、顔料および固形潤滑剤、染料、難燃剤などを適宜配合することができる。なお、本発明の水中油型シリコーンエマルジョン組成物をコーティング用途に使用する場合、実用上、硬化触媒、顔料および固形潤滑剤、難燃剤から選ばれる成分を配合することが特に好ましい。
硬化触媒の配合は任意であるが、本発明の組成物の成分を縮合反応により素早く架橋硬化させるために配合するができ、具体的にはジブチル錫ジラウレート、ジブチル錫ジアセテート、オクテン酸錫、ジブチル錫ジオクテート、ラウリン酸錫、ジオクチル錫ジバーサテート、ジオクチル錫ジアセテート、ジブチル錫ビスオレイルマレート等の有機錫化合物;テトラブチルチタネート、テトラプロピルチタネート、ジブトキシビス(エチルアセトアセテート)チタン等の有機チタン化合物;その他、塩酸、硫酸、ドデシルベンゼンスルホン酸等の酸性化合物;アンモニア、水酸化ナトリウム等のアルカリ性化合物;n-ヘキシルアミン、グアニジン、1,8-ジアザビシクロ[5.4.0]ウンデセン(DBU)、1,4-ジアザビシクロ[2.2.2]オクタン(DABCO)等のアミン系化合物;ジルコニウムテトラプロピレート、ジルコニウムテトラブチレート等の有機ジルコニウムエステル;ジルコニウムトリブトキシアセチルアセトネート、ジルコニウムブトキシアセチルアセトネートビスエチルアセトアセテート、ジルコニウムテトラアセチルアセトネート等の有機ジルコニウムキレート;ジルコニウムビス(2-エチルヘキサノエート)オキサイド、ジルコニウムアセチルアセトネート(2-エチルヘキサノエート)オキサイド等のオキソジルコニウム化合物等のジルコニウム系縮合助触媒;アルミニウムトリエチレート、アルミニウムトリイソプロピレート、アルミニウムトリ(sec-ブチレート)等のアルミニウムアルコレート;ジイソプロポキシアルミニウム(エチルアセトアセテート)アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)等のアルミニウムキレート化合物;ヒドロキシアルミニウムビス(2-エチルヘキサノエート)等のアルミニウムアシロキシ化合物等のアルミニウム系縮合助触媒;ステアリン酸亜鉛、オクチル酸亜鉛、酢酸亜鉛、オクチル酸鉄等の有機酸金属塩などの縮合反応触媒を挙げることができる。なお、これらの硬化触媒は水溶性である場合を除き、予め界面活性剤を用いて水中に乳化分散したエマルジョンの形態にしておくことが望ましい。また、上記のアミン化合物は(G)成分と共通する成分であり、これらの成分を使用することで、スズ(錫)等の金属を含有する硬化触媒を含まない組成も設計可能であり、環境影響の低減の見地から、好ましい。なお、本発明の組成物において、縮合反応触媒の使用量は特に限定されず、縮合反応促進の目的が達成される範囲で任意の量であることができる。なお、縮合反応触媒の使用は任意であり、本組成物において使用しなくてもよい
本発明の水中油型シリコーンエマルジョン組成物は、顔料または固形潤滑剤を配合してもよく、かつ、好ましい。特に、層状ケイ酸塩としても既知のフィロシリケートに代表される固形潤滑剤を配合することで、得られる硬化皮膜に摩擦および/またはブロッキングを低減する減摩性を付与し、その摩擦低減性をさらに改善することができる。
本発明の水中油型シリコーンエマルジョン組成物を、エアバッグコーティング等の用途に適用する場合、実用上、さらに、難燃剤を含んでもよい。例えば、本発明にかかる組成物は、基材表面の摩擦および/またはブロッキングを低減する減摩性の乾燥塗膜を形成するためエアバッグ等の表面コーティングに適するが、エアバッグ等の基材は、その性質上、着火しにくく、燃焼を支援しないことが重要であり、当該用途に適用され得る厳しい可燃性試験を通過するために、一般的に難燃剤の添加が必要である。本発明の水中油型シリコーンエマルジョン組成物をシリコーンゴムを被覆したエアバッグ等の基材上に塗布(=上塗り)される場合には、一般的に可燃性が抑制されるが、難燃剤を含まない上塗りが有機樹脂を被覆したエアバッグに塗布される場合には、米国連邦自動車安全規格試験(US Federal Motor Vehicles Safety StandardsTest)FMVSS#302(これ以降は、「FMVSS#302」と称する)等の可燃性試験を通過しないことがある場合があり、難燃剤の添加が実用上重要である。
本発明の水中油型シリコーンエマルジョン組成物は、均一塗布性および作業性の見地から、その粘度が1000mPa・s以上であることが好ましい。粘度は、20mm直径の2°テーパーコーンを具えたウェルズ-ブルックフィールドコーン/プレート粘度計(Wells-Brookfield Cone/Plate Viscometer)を使用し、1s-1のせん断率で、25℃で測定される(ASTM D4287)。特に示さない限り、本明細書に記載する粘度は、上記と同じ手法で測定されたものである。また、上記粘度は、必要に応じて固形潤滑剤、増粘剤等を含む水中油型シリコーンエマルジョン組成物の全体粘度である。
本発明の水中油型シリコーンエマルジョン組成物は、
工程(I):(A)成分、(C1)成分、必要に応じて、任意で(C2)成分および(D)成分の一部をホモミキサー、ホモジナイザー、コロイドミル、コンビミキサー、インライン式連続乳化機,真空乳化機,超音波乳化機、連続混合装置などの乳化機を用いて乳化分散する工程、および、
工程(II):前記工程で得られた乳化物に(B)成分および残余の(D)成分を配合し分散させる工程
を含む製造方法で製造することができる。
上記の水中油型シリコーンエマルジョン組成物は、基材表面に塗布し、水分を蒸発/加熱等により除去することで、ゴム状の弾性を有し、かつ、表面に粘着性がなく、摩擦低減性の硬化皮膜を形成するため、基材表面の改質を目的とした表面処理剤として利用することができる。
各実験例の水中油型シリコーンエマルジョン組成物(塗膜形成性組成物)を、織られたナイロンエアバッグファブリックの被覆表面にグラビアローラコーティングによって塗布し、140℃で熱硬化し、以下の項目について、評価を行った。
・均一性:塗膜組成物を20g/m2塗布した際の塗膜の均一性を目視により評価した。
・減摩性:初期減摩製の指標としては、塗膜組成物を25g/m2塗布した際の動摩擦係数を測定することにより、評価を行った。
・スクラビング後の減摩性:指で10回スクラビングした後、指で触感によって評価した。
(a)粘度2,400mPa・sの分子鎖両末端ヒドロキシジメチルシロキシ基封鎖ポリジメチルシロキサン92.5部、
(b)式(1): Et2NO(Me2SiO)7NEt2 で示されるアミノキシ基含有ポリシロキサン7.5部を、
(C2)あらかじめ混合し均一にしたポリオキシエチレン-ポリオキシプロピレン共重合体型ノニオン系乳化剤(アデカ製 製品名プルロニック(登録商標)F108)7.5部、(C1)アルカンスルホン酸ナトリウムの40%水溶液12.5部の分散液と均一に混合し、乳化機で乳化を行った。
(D)水86部、(B-1)コロイダルシリカ(日産化学製 商品名スノーテックス30、有効成分30%、pH10、表面がナトリウムで安定化されているコロイダルシリカ)44.0部、(G)ジエチルアミン1.25部を得られた乳化物に投入し、均一に混合した。さらに、(F)メチルトリエトキシシラン2.5部を加えて均一に混合し、2週間室温で静置した後、(B-2)コロイダルシリカ(日産化学製 商品名スノーテックス30、有効成分30%、pH10、表面がナトリウムで安定化されているコロイダルシリカ)をさらに125部投入し、均一に混合することで、水中油型シリコーンエマルジョン(No.1)を調製した。シリカ粒子の総量は、50.7部であった。
シリカ粒子の総量を65.7部に変更した以外は、実施例1と同様の手順で、シリコーンエマルジョン(No.2)、および塗膜組成物を調整し、実施例1と同様の手順で評価を行った。評価結果を表1に示す。
シリカ粒子の総量を73.2部に変更した以外は、実施例1と同様の手順で、シリコーンエマルジョン(No.3)、および塗膜組成物を調整し、実施例1と同様の手順で評価を行った。評価結果を表1に示す。
シリカ粒子の総量を24.75部に変更した以外は、実施例1と同様の手順で、シリコーンエマルジョン(No.C1)、および塗膜組成物を調整し、実施例1と同様の手順で評価を行った。評価結果を表1に示す。
シリカの粒子の総量を35.7部に変更した以外は、実施例1と同様の手順で、シリコーンエマルジョン(No.C2)、および塗膜組成物を調整し、実施例1と同様の手順で評価を行った。
実施例1~3の水中油型シリコーンエマルジョン組成物(=塗膜組成物)は、コロイダルシリカの固形分が本発明の範囲内にあり、均一性に優れる塗膜を形成し、かつ、初期~スクラビング後の減摩性にすぐれ、滑らかな硬化皮膜を基材上に形成することが出来た。一方、比較例1、2においては、実施例に比べて、塗膜の均一性が不十分かつ、減摩性に劣り、また、塗膜の表面粘着性(タック)の低減を実現できないものである。
Claims (12)
- (A)ケイ素原子に結合した水酸基または加水分解性基を1分子中に少なくとも2個有し、25℃における粘度が100,000~20,000,000mPa・sの範囲であるポリオルガノシロキサン100質量部、
(B)コロイダルシリカ(固形分換算) 45~120質量部、
(C1)イオン性乳化剤1~100質量部、
(D)水 0~500質量部(但し、コロイダルシリカ中の水分を除く)
を含有してなる、水中油型シリコーンエマルジョン組成物。 - さらに、(C2)ポリオキシエチレン-ポリオキシプロピレン共重合型ノニオン乳化剤 0.1~50質量部を含有する、請求項1に記載の水中油型シリコーンエマルジョン組成物。
- 組成物全体の25℃における粘度が1,000mPa・s以上である、請求項1または請求項2に記載の水中油型シリコーンエマルジョン組成物。
- さらに、(E)増粘剤を含有する、請求項1~3のいずれか1項に記載の水中油型シリコーンエマルジョン組成物。
- (E)成分が、(E1)粘土鉱物を含む増粘剤および(E2)水溶性有機ポリマーを含む増粘剤から選ばれる1種類以上である、請求項4に記載の水中油型シリコーンエマルジョン組成物。
- さらに、(F)R1 aSiX4-a (式中、R1は非置換一価炭化水素基または置換一価炭化水素基であり、Xはアルコキシ基またはアルコキシアルコキシ基であり、aは0,1または2である)で示されるアルコキシシランもしくはアルコキシアルコキシシラン、または前記アルコキシシランもしくはアルコキシアルコキシシランの部分加水分解縮合物 0.1~50質量部を含有する、請求項1~5のいずれか1項に記載の水中油型シリコーンエマルジョン組成物。
- さらに、(G)アミン化合物を含有する、請求項1~6のいずれか1項に記載の水中油型シリコーンエマルジョン組成物。
- エマルジョン粒子の平均一次粒子径が50~600nmの範囲である、請求項1~7のいずれか1項に記載の水中油型シリコーンエマルジョン組成物。
- (A)成分が、(A)成分の前駆体である(a)ケイ素原子に結合した水酸基または加水分解性基を1分子中に少なくとも2個有するポリオルガノシロキサンおよび(b)ケイ素原子に結合したアミノキシ基を1分子中に平均で2個有するアミノキシ基含有有機ケイ素化合物を前記の(C1)成分、および、任意で前記の(C2)成分の存在下で乳化重合させてなるポリオリガノシロキサンである、請求項1~8のいずれか1項に記載の水中油型シリコーンエマルジョン組成物。
- 請求項1~9のいずれか1項に記載の水中油型シリコーンエマルジョン組成物を含有する、表面処理剤。
- 基材表面を、請求項1~9のいずれか1項に記載の水中油型シリコーンエマルジョン組成物またはそれを含有する請求項10の表面処理剤により表面処理することを特徴とする、表面処理方法。
- 請求項1~9のいずれか1項に記載の水中油型シリコーンエマルジョン組成物またはそれを含有する請求項10の表面処理剤により表面処理されてなる基材。
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