WO2019054398A1 - Polysiloxane compound and composition - Google Patents
Polysiloxane compound and composition Download PDFInfo
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- WO2019054398A1 WO2019054398A1 PCT/JP2018/033752 JP2018033752W WO2019054398A1 WO 2019054398 A1 WO2019054398 A1 WO 2019054398A1 JP 2018033752 W JP2018033752 W JP 2018033752W WO 2019054398 A1 WO2019054398 A1 WO 2019054398A1
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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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
- C08G77/14—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
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
Definitions
- the present invention relates to a specific polysiloxane compound and a composition containing the specific polysiloxane compound and a polymer.
- Patent Document 1 proposes a polysiloxane compound capable of forming a film excellent in surface lubricity by incorporating it into an organic polymer composition containing polyethylene resin, polypropylene resin and the like.
- An object of the present invention is to provide a polysiloxane compound capable of improving the performance of a film formed of a polymer such as a homopolymer or a copolymer, and a composition containing the polysiloxane compound. .
- the present invention provides a polysiloxane compound having a structure represented by the following formula (X) and a structure represented by the following formula (Y), and a composition containing the polysiloxane compound and a polymer. is there.
- X a structure represented by the following formula
- Y a structure represented by the following formula (Y)
- R 5 is a single bond, an alkylene chain or an oxyalkylene chain
- R 6 is a functional group having a hetero atom.
- a polysiloxane compound capable of improving the performance of a film formed of a polymer such as a homopolymer and a copolymer, and a composition containing the polysiloxane compound.
- the polysiloxane compound has a structure represented by the above formula (X) and a structure represented by the above formula (Y).
- R5 of the formula (Y) is an alkylene chain
- the alkylene chain may be linear or branched.
- the oxygen atom of the oxyalkylene chain may be bonded to Si or R 6.
- the alkylene moiety of the oxyalkylene chain may be linear or branched.
- alkylene moiety of the above-mentioned alkylene chain and oxyalkylene chain examples include an alkylene chain having 1 to 20 carbon atoms, and a methylene chain, ethylene chain, propylene chain, butylene chain, pentylene chain, hexylene chain, It is preferable that it is an alkylene chain having 1 to 12 carbon atoms such as heptylene chain, octylene chain, nonylene chain, decylene chain, undecylene chain, dodecylene chain and the like.
- R6 is not particularly limited as long as it is a functional group having a hetero atom, and examples thereof include functional groups having O, N, S, halogen and the like. Specifically, hydroxyl group, alkoxy group, nitro group, amino group, halo group, ureido group, isocyanate group, mercapto group, alkylthio group, N- (aminoalkyl) amino group, N-phenylamino group, 3,4- And epoxycyclohexyl, 2,3-dihydroxypropyl, alkanoylthio and the like.
- the weight average molecular weight of the polysiloxane compound is not particularly limited, and is, for example, in the range of 1000 to 1,000,000.
- the said weight average molecular weight can be calculated
- the polysiloxane compound includes, for example, (1) at least a phosphorus compound (a1) and a silicon-containing compound (a2 ⁇ ) having at least a glycidyloxy group, two alkoxy groups and -R5-R7 in an aqueous medium at a predetermined temperature.
- a phosphorus compound (a1), a compound (a2 ⁇ ) containing two or more glycidyloxy groups, and two or more compounds It can be produced by a method in which a silicon-containing compound (a3) having an alkoxy group or two or more halo groups and -R5-R7 is reacted at a predetermined temperature (preferably 40 to 80 ° C).
- a predetermined temperature preferably 40 to 80 ° C.
- the structure of the polysiloxane compound can be identified by 1 H NMR analysis, 13 C NMR analysis, 31 P NMR analysis, FT-IR analysis (ATR method) or the like.
- condensation polymerization catalysts such as dibutyltin diacetate, dibutyltin dilaurate, lead naphthenate and the like
- hydrolysis catalysts such as acid catalysts
- polycondensation catalysts and amines which are hydrolysis catalysts You may use a system catalyst etc.
- the phosphorus compound (a1) means a compound in which one oxo group and one or more hydroxyl groups are bonded to a phosphorus atom.
- a phosphorus compound for example, phosphoric acid, phosphorous acid, etidronic acid, phenylphosphonic acid, dodecyl phosphoric acid, 2-butoxyethyl phosphate, nitrilotris (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), 2-phosphonobutane
- phosphoric acid for example, phosphoric acid, phosphorous acid, etidronic acid, phenylphosphonic acid, dodecyl phosphoric acid, 2-butoxyethyl phosphate, nitrilotris (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), 2-phosphonobutane
- 1 type may be used for these phosphorus compounds, and 2 or more types may be used together.
- Silicon-containing compound (a2 ⁇ ) having a glycidyloxy group, two alkoxy groups and -R5-R7 The compound (a2 ⁇ ) is not particularly limited as long as it is a silicon-containing compound which does not correspond to the compound (a1), has a glycidyloxy group, and further has two alkoxy groups and -R5-R7 directly bonded to Si. I will not.
- R7 is, for example, a hydroxyl group, an alkyl group, an alkoxy group, a nitro group, an amino group, a halo group, a ureido group, an isocyanate group, a mercapto group, an alkylthio group, an N- (aminoalkyl) amino group, an N-phenyl group. And amino, 3,4-epoxycyclohexyl, alkanoylthio and the like.
- the compound (a2 ⁇ ) include 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxyoctyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane And 3-glycidoxypropyltriethoxysilane and the like, but not limited thereto.
- One of these compounds may be used, or two or more thereof may be used in combination.
- Compound (a2 ⁇ ) having two or more glycidyloxy groups The compound (a2 ⁇ ) is not particularly limited as long as it does not correspond to the compound (a1) and has two or more glycidyloxy groups.
- the compound (a2 ⁇ ) include succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, 1,4-butanediol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, Pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, etc. Can gel it not intended to
- Silicon-containing compound (a3) having two or more alkoxy groups or two or more halo groups, and -R5-R7 The silicon-containing compound (a3) does not correspond to the compound (a1) and the compound (a2 ⁇ ) in the production of the polysiloxane compound, and has two or more alkoxy groups or two or more halo groups and -R5-R7 It is not particularly limited as long as it is a silicon-containing compound having In addition, when a compound (a3) has 2 or more halo groups, each halo group is a fluoro group, a chloro group, a bromo group etc., for example, and those halo groups may be same or different. .
- silicon-containing compound (a3) examples include vinyltrichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3- (methacryloyloxy) ) Propyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminoprop
- the alkyl moiety of the alkoxy group in is not particularly limited as long as it is linear or branched, but is preferably an alkyl group having 1 to 20 carbon atoms, and a methyl group, an ethyl group, a propyl group, More preferably, it is an alkyl group having 1 to 12 carbon atoms, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group.
- the alkyl moiety in each alkoxy group in the compound (a3) may be the same or different.
- the example in which the phosphorus compound (a1) and the silicon-containing compound (a3) are reacted with the compound (a2 ⁇ ) containing two or more glycidyloxy groups in the production of the polysiloxane compound is exemplified. Not limited to this. For example, after reacting a compound (a2 ⁇ ) containing two or more glycidyloxy groups with a compound having two or more amino groups in an aqueous medium, the phosphorus compound (a1) and the silicon-containing compound (a3) And reacting at a predetermined temperature (preferably 40 to 80.degree. C.) to produce a polysiloxane compound.
- a predetermined temperature preferably 40 to 80.degree. C.
- the polycondensate and the polyoxyethylene group and / or polyoxypropylene group are It can also be produced by reacting the compound having the compound with the compound having a phosphorus compound (a1) and the silicon-containing compound (a3) followed by reaction at a predetermined temperature (preferably 40 to 80 ° C.).
- the polysiloxane compound of the present embodiment is useful in the technical field of forming a film using the above-mentioned polymer, since it can improve the performance of a film formed by a polymer such as a homopolymer or a copolymer. is there.
- composition is a polysiloxane compound having a structure represented by the above formula (X) and a structure represented by the above formula (Y) (hereinafter simply referred to as "polysiloxane compound") in addition to the aqueous medium. And a polymer different from the polysiloxane compound.
- the composition may consist only of an aqueous medium, a polysiloxane compound and a polymer, or may further contain other components.
- composition according to the present embodiment may contain one kind of polysiloxane compound, but may contain two or more kinds of polysiloxane compounds. However, at least one type is a polysiloxane compound having a structure represented by the above formula (X) and a structure represented by the above formula (Y).
- the polymer is not particularly limited as long as it can form a film, and, for example, a known homopolymer or copolymer or a composition containing the same (for example, crosslinked with a homopolymer and / or a copolymer) A composition comprising an agent). These polymers may be contained alone or in combination of two or more in the composition.
- the homopolymer and the copolymer preferably have a weight average molecular weight of 1000 or more.
- the resin is not particularly limited as long as it is a known resin, but, for example, acrylic resin, polyester resin, polyolefin resin, epoxy resin, phenol resin, polyvinyl resin, polyamide resin, polyimide Examples include system resins, polyurethane resins and elastomers.
- the crosslinking agent is not particularly limited as long as it can form a film by crosslinking a homopolymer or copolymer, and examples thereof include polyvalent carboxylic acids or salts thereof, glyoxal, isocyanates, blocked isocyanates, carbodiimides and the like. be able to.
- the aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent (containing 50% by volume or more of water based on the volume of the aqueous medium).
- the water-miscible organic solvent is not particularly limited as long as it is miscible with water, and, for example, ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N'-dimethylformamide and dimethylacetamide Alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone Can be mentioned.
- One of these water-miscible organic solvents may be mixed with water, or two or more may be mixed with water.
- (Compounding amount of each component in the composition) -Polysiloxane compound It is preferable that content of a polysiloxane compound exists in the range of 1 mass% or more and 99 mass% or less with respect to the total solid of a composition. A more preferable content of the polysiloxane compound is in the range of 5% by mass to 99% by mass, and a further preferable content is in the range of 10% by mass to 90% by mass.
- the content of the polymer is preferably in the range of 1% by mass or more and 99% by mass or less based on the total solid content of the composition.
- the more preferable content of the polymer is in the range of 5% by mass to 99% by mass, and the more preferable content is in the range of 10% by mass to 90% by mass.
- composition which concerns on this embodiment can be manufactured by mixing a polysiloxane compound, a polymer, and an aqueous medium.
- the composition of the present embodiment is useful for forming a film.
- the film can be produced by at least conducting the step of bringing the composition of the present embodiment into contact with the surface of the material or the step of drying the contacted composition.
- the material is not particularly limited, and may be a metal material or a nonmetal material. Examples of nonmetal materials include plastics, rubbers, ceramics, glasses, fibers, magnetic materials and the like.
- the weight average molecular weight and number average molecular weight of the polysiloxane compound and the polymer were measured by gel permeation chromatography (GPC) under the following conditions, and converted to polystyrene as a standard sample.
- GPC gel permeation chromatography
- Polysiloxane compound Examples 1A to 24A Based on the compositions shown in Tables 1A and 1B, various compounds and water were mixed and reacted at 60 ° C. for 5 hours. After the reaction, the reaction product was cooled to 25 ° C. to obtain the polysiloxane compounds of Examples 1A to 24A. The weight average molecular weight of each polysiloxane compound is shown in Table 1A and Table 1B.
- Example 1B In a mixed solvent of 180 parts by mass of water and 100 parts by mass of isopropyl alcohol at 25 ° C., 550 parts by mass of methyl methacrylate, 550 parts by mass of ethyl 2- (hydroxymethyl) acrylate and 18 parts by mass of acrylic acid It was dissolved. Furthermore, 1.5 parts by mass of potassium persulfate, 0.06 parts by mass of sodium bisulfite and 1.5 parts by mass of anhydrous sodium acetate were dissolved. Then, the temperature was slowly raised to 65 ° C. in nitrogen gas and allowed to react for 3 hours.
- the reaction solution is cooled to 25 ° C. and filtered to obtain an acrylic resin (polymer b1) solution (solids concentration: 20% by mass; viscosity (30 ° C.): 28.6 mPa ⁇ s; pH: 5.6) Was extracted.
- Example 1B After stirring 83.0 parts by mass of an acrylic resin (polymer b1) and 17.0 parts by mass of the polysiloxane compound of Example 1A in terms of solid content, the water is slowly added so that the total amount of water is 150 parts by mass. In addition, the composition of Example 1B was obtained.
- Example 2B Alcohol component consisting of ethylene glycol (90 mol%) and trimethylolpropane (10 mol%), isophthalic acid (40 mol%), terephthalic acid (41 mol%), sodium dimethyl -5-sulfonate isophthalate (2 mol%) and trianhydride
- a polyester resin was synthesized according to the following method by condensation reaction of an acid component consisting of mellitic acid (17 mol%). After mixing 2 mol of total alcohol component, 1 mol of total acid component and catalyst (0.25 g of calcium acetate, 0.1 g of N-butyltitanate) at 180 ° C. in nitrogen gas, the temperature is raised to 200 ° C. The reaction was allowed to proceed for 2 hours while heating and stirring.
- Example 2B the reaction (polycondensation reaction) was performed at 260 ° C. under reduced pressure (0.5 mmHg) for 3 hours to obtain a polyester resin (polymer b2). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 2B.
- Example 3B 100 parts by mass of a propylene-ethylene- ⁇ -olefin copolymer (68 mol% of propylene component, 8 mol% of ethylene component, 24 mol% of butene component; weight average molecular weight: 60000), 10 parts by mass of maleic anhydride, and 10 parts of methyl methacrylate Parts and 1 part by mass of dicumyl peroxide are reacted for 2 hours while stirring at 180 ° C., and a modified polyolefin resin composition (grafted weight of maleic anhydride: 8.4 mass%; weight average molecular weight: 45000) Obtained.
- Example 3B 100 parts by mass of this modified polyolefin resin composition, 10 parts by mass of dimethylethanolamine and 10 parts by mass of polyoxyethylene alkyl ether sulfate are stirred at 100 ° C. for 2 hours to obtain a polyolefin resin (polymer b3) Obtained. Thereafter, in the same manner as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 3B.
- Examples 4B to 6B As an epoxy resin (polymer b4), polyethylene glycol diglycidyl ether (average polymerization degree: 9; bifunctional; epoxy equivalent: 268; viscosity (30 ° C.): 70 mPa ⁇ s) as a phenol resin (polymer b 5) Acetoacetylated polyvinyl alcohol (saponification degree: 99%; acetoacetylation degree: 9.8%) as polyvinyl resin (hydroxy group equivalent: 120; weight average molecular weight: 100000) as polyvinyl resin (polymer b6); viscosity (30 C.): 12 mPa ⁇ s; weight average molecular weight: 50000)
- the polymer, the polysiloxane compound of Example 1A and water are mixed, and the compositions of Examples 4B to 6B are obtained. Obtained.
- Example 7B 1106 parts by mass of trimellitic anhydride, 1455 parts by mass of 4,4-diphenylmethane diisocyanate, and 2562 parts by mass of 1-methyl-2-pyrrolidone were slowly heated to 130 ° C. while being stirred in nitrogen gas. Thereafter, the reaction is carried out at 130 ° C. for about 6 hours, and the polyamideimide resin solution [solids concentration: 50% by mass; acid value (acid value obtained by combining carboxyl group obtained by ring-opening carboxyl group and acid anhydride group): 40; Viscosity (30 ° C.): 85.0 mPa ⁇ s; number average molecular weight: 17000].
- Example 7B 2700 parts by mass of this polyamideimide resin solution was heated to 50 ° C. while being stirred in nitrogen gas. When the temperature reached 50 ° C., 447.1 parts by mass (4 equivalents) of triethylamine was added to obtain a polyamideimide resin (polymer b7). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 7B.
- Example 8B At 25 ° C., 30 parts by mass of ethylene oxide 2 mol adduct of bisphenol A, 40 parts by mass of polyethylene glycol, 10 parts by mass of N-methyldiethanolamine, 10 parts by mass of diethylene glycol, 10 parts by mass of trimethylolpropane, isophorone diisocyanate 130 parts by mass and 130 parts by mass of methyl ethyl ketone were reacted at 65 to 70 ° C. for 4 hours to obtain a polyurethane resin (polymer b8). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 8B.
- polyurethane resin polymer b8
- Example 9B Aqueous dispersion of acrylonitrile butadiene styrene rubber having carboxyl group and methylol group as elastomer (polymer b9) [solids concentration: 47%; viscosity (30 ° C.): 45 mPa ⁇ s; pH: 8.0; specific gravity: 1 The polymer, the polysiloxane compound of Example 1A, and water were mixed in the same manner as in Example 1B using .01] to obtain a composition of Example 9B.
- Examples 10B to 32B Based on the compositions shown in Tables 3A and 3B, the polymer, the polysiloxane compound and water were mixed in the same manner as in Examples 1B to 9B to produce the compositions of Examples 10B to 32B.
- Comparative Examples 1B to 9B As shown in Table 4, water is slowly added so that the total amount of water is 150 parts by mass with respect to 100 parts by mass of the polymers b1 to b9 in terms of solid content, to manufacture the composition of Comparative Examples 1B to 9B did.
- compositions of Examples 1B to 32B and Comparative Examples 1B to 9B are coated with a bar coat on the surface of the washed GI material, and dried at a plate temperature (PMT) of 150 ° C. to obtain GI materials having various coatings. (No. 1 to 41) were produced. In addition, the coating-film mass after drying was 1000 mg / m ⁇ 2 >.
- the area ratio of white rust is less than 3% ⁇ : The area ratio of white rust is 3% or more and less than 10% ⁇ : The area ratio of white rust is 10% or more and less than 30% x: of white rust Area ratio is 30% or more
- the area ratio of white rust is less than 10% ⁇ : The area ratio of white rust is 10% or more and less than 20% ⁇ : The area ratio of white rust is 20% or more and less than 30% x: of white rust Area ratio is 30% or more
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Abstract
[Problem] To provide: a polysiloxane compound with which it is possible to improve the properties of a film formed from a single polymer, a copolymer, or another such polymer substance; and a composition containing the polysiloxane compound. [Solution] Provided are a polysiloxane compound having a structure represented by formula (X) and a structure represented by formula (Y), and a composition containing the polysiloxane compound and a polymer. In formula (Y), R5 is a single bond, an alkylene chain, or an oxyalkylene chain, and R6 is a functional group having a hetero atom.
Description
本発明は、特定のポリシロキサン化合物と、当該特定のポリシロキサン化合物と重合物とを含有する組成物と、に関する。
The present invention relates to a specific polysiloxane compound and a composition containing the specific polysiloxane compound and a polymer.
近年、様々な性能を有する皮膜を形成させるために各種ポリシロキサン化合物が用いられている。例えば、特許文献１には、ポリエチレン樹脂、ポリプロピレン樹脂等を含有する有機ポリマー組成物に配合させることにより、表面潤滑性に優れた皮膜を形成可能なポリシロキサン化合物が提案されている。
In recent years, various polysiloxane compounds have been used to form films having various performances. For example, Patent Document 1 proposes a polysiloxane compound capable of forming a film excellent in surface lubricity by incorporating it into an organic polymer composition containing polyethylene resin, polypropylene resin and the like.
本発明は、単重合体や共重合体等の重合物で形成される皮膜の性能を向上可能なポリシロキサン化合物と、当該ポリシロキサン化合物を含有する組成物と、を提供することを目的とする。
An object of the present invention is to provide a polysiloxane compound capable of improving the performance of a film formed of a polymer such as a homopolymer or a copolymer, and a composition containing the polysiloxane compound. .
本発明者らは、上記課題を解決すべく鋭意検討を重ねてきた結果、重合物に特定のポリシロキサン化合物を配合させることにより、該重合物で形成される皮膜の性能が向上することを見出し、本発明を完成するに至った。即ち、本発明は、下式（Ｘ）で表される構造と下式（Ｙ）で表される構造とを有するポリシロキサン化合物と、当該ポリシロキサン化合物及び重合物を含有する組成物と、である。
［式（Ｙ）中、Ｒ５は単結合、アルキレン鎖又はオキシアルキレン鎖であり、Ｒ６はヘテロ原子を有する官能基である。］
As a result of intensive studies to solve the above problems, the present inventors have found that the performance of a film formed of the polymer is improved by incorporating a specific polysiloxane compound in the polymer. The present invention has been completed. That is, the present invention provides a polysiloxane compound having a structure represented by the following formula (X) and a structure represented by the following formula (Y), and a composition containing the polysiloxane compound and a polymer. is there.
[In formula (Y), R 5 is a single bond, an alkylene chain or an oxyalkylene chain, and R 6 is a functional group having a hetero atom. ]
本発明によれば、単重合体や共重合体等の重合物で形成される皮膜の性能を向上可能なポリシロキサン化合物と、当該ポリシロキサン化合物を含有する組成物と、を提供することができる。
According to the present invention, it is possible to provide a polysiloxane compound capable of improving the performance of a film formed of a polymer such as a homopolymer and a copolymer, and a composition containing the polysiloxane compound. .
≪ポリシロキサン化合物≫
＜構造＞
ポリシロキサン化合物は、上式（Ｘ）で表される構造と上式（Ｙ）で表される構造とを有する。ここで、本明細書において、式（Ｙ）のＲ５がアルキレン鎖である場合、該アルキレン鎖は、直鎖状であってもよいし、分岐鎖状でもよい。また、本明細書において、Ｒ５がオキシアルキレン鎖である場合、オキシアルキレン鎖の酸素原子が、Ｓｉと結合していてもよいし、Ｒ６と結合していてもよい。なお、オキシアルキレン鎖のアルキレン部分は、直鎖状であってもよいし、分岐鎖状でもよい。上記アルキレン鎖、及び、オキシアルキレン鎖のアルキレン部分としては、例えば、炭素数１～２０のアルキレン鎖を挙げることができるが、メチレン鎖、エチレン鎖、プロピレン鎖、ブチレン鎖、ペンチレン鎖、ヘキシレン鎖、へプチレン鎖、オクチレン鎖、ノニレン鎖、デシレン鎖、ウンデシレン鎖、ドデシレン鎖等の炭素数１～１２のアルキレン鎖であることが好ましい。 «Polysiloxane compound»
<Structure>
The polysiloxane compound has a structure represented by the above formula (X) and a structure represented by the above formula (Y). Here, in the present specification, when R5 of the formula (Y) is an alkylene chain, the alkylene chain may be linear or branched. In the present specification, when R 5 is an oxyalkylene chain, the oxygen atom of the oxyalkylene chain may be bonded to Si or R 6. The alkylene moiety of the oxyalkylene chain may be linear or branched. Examples of the alkylene moiety of the above-mentioned alkylene chain and oxyalkylene chain include an alkylene chain having 1 to 20 carbon atoms, and a methylene chain, ethylene chain, propylene chain, butylene chain, pentylene chain, hexylene chain, It is preferable that it is an alkylene chain having 1 to 12 carbon atoms such as heptylene chain, octylene chain, nonylene chain, decylene chain, undecylene chain, dodecylene chain and the like.
＜構造＞
ポリシロキサン化合物は、上式（Ｘ）で表される構造と上式（Ｙ）で表される構造とを有する。ここで、本明細書において、式（Ｙ）のＲ５がアルキレン鎖である場合、該アルキレン鎖は、直鎖状であってもよいし、分岐鎖状でもよい。また、本明細書において、Ｒ５がオキシアルキレン鎖である場合、オキシアルキレン鎖の酸素原子が、Ｓｉと結合していてもよいし、Ｒ６と結合していてもよい。なお、オキシアルキレン鎖のアルキレン部分は、直鎖状であってもよいし、分岐鎖状でもよい。上記アルキレン鎖、及び、オキシアルキレン鎖のアルキレン部分としては、例えば、炭素数１～２０のアルキレン鎖を挙げることができるが、メチレン鎖、エチレン鎖、プロピレン鎖、ブチレン鎖、ペンチレン鎖、ヘキシレン鎖、へプチレン鎖、オクチレン鎖、ノニレン鎖、デシレン鎖、ウンデシレン鎖、ドデシレン鎖等の炭素数１～１２のアルキレン鎖であることが好ましい。 «Polysiloxane compound»
<Structure>
The polysiloxane compound has a structure represented by the above formula (X) and a structure represented by the above formula (Y). Here, in the present specification, when R5 of the formula (Y) is an alkylene chain, the alkylene chain may be linear or branched. In the present specification, when R 5 is an oxyalkylene chain, the oxygen atom of the oxyalkylene chain may be bonded to Si or R 6. The alkylene moiety of the oxyalkylene chain may be linear or branched. Examples of the alkylene moiety of the above-mentioned alkylene chain and oxyalkylene chain include an alkylene chain having 1 to 20 carbon atoms, and a methylene chain, ethylene chain, propylene chain, butylene chain, pentylene chain, hexylene chain, It is preferable that it is an alkylene chain having 1 to 12 carbon atoms such as heptylene chain, octylene chain, nonylene chain, decylene chain, undecylene chain, dodecylene chain and the like.
本明細書において、Ｒ６としてはヘテロ原子を有する官能基であれば、特に限定されるものではないが、例えば、Ｏ、Ｎ、Ｓ、ハロゲン等を有する官能基を挙げることができる。具体的には、水酸基、アルコキシ基、ニトロ基、アミノ基、ハロ基、ウレイド基、イソシアネート基、メルカプト基、アルキルチオ基、Ｎ－（アミノアルキル）アミノ基、Ｎ－フェニルアミノ基、３，４－エポキシシクロヘキシル基、２，３－ジヒドロキシプロピル基、アルカノイルチオ基等が挙げられる。
In the present specification, R6 is not particularly limited as long as it is a functional group having a hetero atom, and examples thereof include functional groups having O, N, S, halogen and the like. Specifically, hydroxyl group, alkoxy group, nitro group, amino group, halo group, ureido group, isocyanate group, mercapto group, alkylthio group, N- (aminoalkyl) amino group, N-phenylamino group, 3,4- And epoxycyclohexyl, 2,3-dihydroxypropyl, alkanoylthio and the like.
なお、－Ｒ５－Ｒ６としては、例えば、水酸基、アルコキシ基、ニトロ基、アミノ基、ハロ基、ウレイド基、イソシアネート基、メルカプト基、アルキルチオ基、Ｎ－（アミノアルキル）アミノ基、Ｎ－フェニルアミノ基、３，４－エポキシシクロヘキシル基、アルカノイルチオ基、ヒドロキシアルキル基、アルコキシアルキル基、ニトロアルキル基、アミノアルキル基、ハロアルキル基、ウレイドアルキル基、イソシアネートアルキル基、メルカプトアルキル基、アルキルチオアルキル基、Ｎ－（アミノアルキル）アミノアルキル基、Ｎ－フェニルアミノアルキル基、３，４－エポキシシクロヘキシルアルキル基、２，３－ジヒドロキシアルキル基（アルキル部分は、炭素数３以上のアルキル基である）、アルカノイルチオアルキル基、ヒドロキシアルキルオキシ基、アルコキシアルキルオキシ基、ニトロアルキルオキシ基、ニトロオキシアルキル基、アミノアルキルオキシ基、アミノオキシアルキル基、ハロアルキルオキシ基、ハロオキシアルキル基、ウレイドアルキルオキシ基、ウレイドオキシアルキル基、イソシアネートアルキルオキシ基、イソシアネートオキシアルキル基、メルカプトアルキルオキシ基、メルカプトオキシアルキル基、アルキルチオアルキルオキシ基、アルキルチオキシアルキル基、Ｎ－（アミノアルキル）アミノアルキルオキシ基、Ｎ－（アミノアルキル）アミノオキシアルキル基、Ｎ－フェニルアミノアルキルオキシ基、Ｎ－フェニルアミノオキシアルキル基、３，４－エポキシシクロヘキシルアルキルオキシ基、３，４－エポキシシクロヘキシルオキシアルキル基、２，３－ジヒドロキシアルキルオキシ基（アルキル部分は、炭素数４以上のアルキル基である）、２，３－ジヒドロキシプロピルオキシアルキル基、アルカノイルチオアルキルオキシ基、アルカノイルチオキシアルキル基等が挙げられる。
In addition, as -R5-R6, for example, a hydroxyl group, an alkoxy group, a nitro group, an amino group, a halo group, a ureido group, an isocyanate group, a mercapto group, an alkylthio group, an N- (aminoalkyl) amino group, an N-phenylamino Group, 3,4-epoxycyclohexyl group, alkanoylthio group, hydroxyalkyl group, alkoxyalkyl group, nitroalkyl group, aminoalkyl group, haloalkyl group, ureido alkyl group, isocyanate alkyl group, mercaptoalkyl group, alkylthioalkyl group, N -(Aminoalkyl) aminoalkyl group, N-phenylaminoalkyl group, 3,4-epoxycyclohexylalkyl group, 2,3-dihydroxyalkyl group (where the alkyl moiety is an alkyl group having 3 or more carbon atoms), alkanoylthio An alkyl group, Droxyalkyloxy group, alkoxyalkyloxy group, nitroalkyloxy group, nitrooxyalkyl group, aminoalkyloxy group, aminooxyalkyl group, haloalkyloxy group, halooxyalkyl group, ureido alkyloxy group, ureido oxyalkyl group, Isocyanate alkyloxy group, isocyanate oxyalkyl group, mercaptoalkyloxy group, mercaptooxyalkyl group, alkylthioalkyloxy group, alkylthioxyalkyl group, N- (aminoalkyl) aminoalkyloxy group, N- (aminoalkyl) aminooxyalkyl Group, N-phenylaminoalkyloxy group, N-phenylaminooxyalkyl group, 3,4-epoxycyclohexylalkyloxy group, 3,4-epoxycyclohexyl group Oxyalkyl group, 2,3-dihydroxyalkyloxy group (wherein the alkyl moiety is an alkyl group having 4 or more carbon atoms), 2,3-dihydroxypropyloxyalkyl group, alkanoylthioalkyloxy group, alkanoylthiooxyalkyl group, etc. Can be mentioned.
ポリシロキサン化合物の重量平均分子量は、特に限定されず、例えば、１０００～１００００００の範囲内である。上記重量平均分子量は、例えば、ゲル浸透クロマトグラフィー（ＧＰＣ）によって測定したポリスチレン換算の分子量として求めることができる。
The weight average molecular weight of the polysiloxane compound is not particularly limited, and is, for example, in the range of 1000 to 1,000,000. The said weight average molecular weight can be calculated | required as a molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC), for example.
＜ポリシロキサン化合物の製造方法＞
ポリシロキサン化合物は、例えば、（１）水性媒体中で、少なくとも、リン化合物（ａ１）及びグリシジルオキシ基と２個のアルコキシ基と－Ｒ５－Ｒ７とを有するケイ素含有化合物（ａ２α）を所定の温度（好適には、４０～８０℃）にて反応させる方法、（２）水性媒体中で、少なくとも、リン化合物（ａ１）、２個以上のグリシジルオキシ基を含む化合物（ａ２β）及び２個以上のアルコキシ基又は２個以上のハロ基と－Ｒ５－Ｒ７とを有するケイ素含有化合物（ａ３）を所定の温度（好適には、４０～８０℃）にて反応させる方法、により製造することができる。なお、ポリシロキサン化合物の構造は、１Ｈ ＮＭＲ分析、１３Ｃ ＮＭＲ分析、３１Ｐ ＮＭＲ分析、ＦＴ－ＩＲ分析（ＡＴＲ法）等で特定可能である。 <Method of producing polysiloxane compound>
The polysiloxane compound includes, for example, (1) at least a phosphorus compound (a1) and a silicon-containing compound (a2α) having at least a glycidyloxy group, two alkoxy groups and -R5-R7 in an aqueous medium at a predetermined temperature. (Preferably, at 40 to 80 ° C.) (2) In an aqueous medium, at least a phosphorus compound (a1), a compound (a2β) containing two or more glycidyloxy groups, and two or more compounds It can be produced by a method in which a silicon-containing compound (a3) having an alkoxy group or two or more halo groups and -R5-R7 is reacted at a predetermined temperature (preferably 40 to 80 ° C). The structure of the polysiloxane compound can be identified by 1 H NMR analysis, 13 C NMR analysis, 31 P NMR analysis, FT-IR analysis (ATR method) or the like.
ポリシロキサン化合物は、例えば、（１）水性媒体中で、少なくとも、リン化合物（ａ１）及びグリシジルオキシ基と２個のアルコキシ基と－Ｒ５－Ｒ７とを有するケイ素含有化合物（ａ２α）を所定の温度（好適には、４０～８０℃）にて反応させる方法、（２）水性媒体中で、少なくとも、リン化合物（ａ１）、２個以上のグリシジルオキシ基を含む化合物（ａ２β）及び２個以上のアルコキシ基又は２個以上のハロ基と－Ｒ５－Ｒ７とを有するケイ素含有化合物（ａ３）を所定の温度（好適には、４０～８０℃）にて反応させる方法、により製造することができる。なお、ポリシロキサン化合物の構造は、１Ｈ ＮＭＲ分析、１３Ｃ ＮＭＲ分析、３１Ｐ ＮＭＲ分析、ＦＴ－ＩＲ分析（ＡＴＲ法）等で特定可能である。 <Method of producing polysiloxane compound>
The polysiloxane compound includes, for example, (1) at least a phosphorus compound (a1) and a silicon-containing compound (a2α) having at least a glycidyloxy group, two alkoxy groups and -R5-R7 in an aqueous medium at a predetermined temperature. (Preferably, at 40 to 80 ° C.) (2) In an aqueous medium, at least a phosphorus compound (a1), a compound (a2β) containing two or more glycidyloxy groups, and two or more compounds It can be produced by a method in which a silicon-containing compound (a3) having an alkoxy group or two or more halo groups and -R5-R7 is reacted at a predetermined temperature (preferably 40 to 80 ° C). The structure of the polysiloxane compound can be identified by 1 H NMR analysis, 13 C NMR analysis, 31 P NMR analysis, FT-IR analysis (ATR method) or the like.
なお、上記反応を促進させるために、例えば、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ナフテン酸鉛等の縮重合触媒；酸性触媒等の公知の加水分解触媒；重縮合触媒及び加水分解触媒であるアミン系触媒等を用いてもよい。
In order to accelerate the above reaction, for example, condensation polymerization catalysts such as dibutyltin diacetate, dibutyltin dilaurate, lead naphthenate and the like; known hydrolysis catalysts such as acid catalysts; polycondensation catalysts and amines which are hydrolysis catalysts You may use a system catalyst etc.
リン化合物（ａ１）
リン化合物（ａ１）とは、リン原子に１個のオキソ基と１個以上の水酸基とが結合した化合物を意味する。リン化合物としては、例えば、リン酸、亜リン酸、エチドロン酸、フェニルホスホン酸、ドデシルリン酸、リン酸２－ブトキシエチル、ニトリロトリス（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、２－ホスホノブタン－１，２，４－トリカルボン酸等を挙げることができるがこれらに制限されるものではない。なお、これらのリン化合物は１種を用いてもよいし、２種以上を併用してもよい。 Phosphorus compound (a1)
The phosphorus compound (a1) means a compound in which one oxo group and one or more hydroxyl groups are bonded to a phosphorus atom. As a phosphorus compound, for example, phosphoric acid, phosphorous acid, etidronic acid, phenylphosphonic acid, dodecyl phosphoric acid, 2-butoxyethyl phosphate, nitrilotris (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), 2-phosphonobutane There may be mentioned, but not limited to, -1,2,4-tricarboxylic acid and the like. In addition, 1 type may be used for these phosphorus compounds, and 2 or more types may be used together.
リン化合物（ａ１）とは、リン原子に１個のオキソ基と１個以上の水酸基とが結合した化合物を意味する。リン化合物としては、例えば、リン酸、亜リン酸、エチドロン酸、フェニルホスホン酸、ドデシルリン酸、リン酸２－ブトキシエチル、ニトリロトリス（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）、２－ホスホノブタン－１，２，４－トリカルボン酸等を挙げることができるがこれらに制限されるものではない。なお、これらのリン化合物は１種を用いてもよいし、２種以上を併用してもよい。 Phosphorus compound (a1)
The phosphorus compound (a1) means a compound in which one oxo group and one or more hydroxyl groups are bonded to a phosphorus atom. As a phosphorus compound, for example, phosphoric acid, phosphorous acid, etidronic acid, phenylphosphonic acid, dodecyl phosphoric acid, 2-butoxyethyl phosphate, nitrilotris (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), 2-phosphonobutane There may be mentioned, but not limited to, -1,2,4-tricarboxylic acid and the like. In addition, 1 type may be used for these phosphorus compounds, and 2 or more types may be used together.
グリシジルオキシ基と２個のアルコキシ基と－Ｒ５－Ｒ７とを有するケイ素含有化合物（ａ２α）
化合物（ａ２α）は、化合物（ａ１）に該当せず、且つ、グリシジルオキシ基を有し、更に２個のアルコキシ基と－Ｒ５－Ｒ７とがＳｉに直接結合したケイ素含有化合物である限り特に限定されない。 Silicon-containing compound (a2α) having a glycidyloxy group, two alkoxy groups and -R5-R7
The compound (a2α) is not particularly limited as long as it is a silicon-containing compound which does not correspond to the compound (a1), has a glycidyloxy group, and further has two alkoxy groups and -R5-R7 directly bonded to Si. I will not.
化合物（ａ２α）は、化合物（ａ１）に該当せず、且つ、グリシジルオキシ基を有し、更に２個のアルコキシ基と－Ｒ５－Ｒ７とがＳｉに直接結合したケイ素含有化合物である限り特に限定されない。 Silicon-containing compound (a2α) having a glycidyloxy group, two alkoxy groups and -R5-R7
The compound (a2α) is not particularly limited as long as it is a silicon-containing compound which does not correspond to the compound (a1), has a glycidyloxy group, and further has two alkoxy groups and -R5-R7 directly bonded to Si. I will not.
本明細書においてＲ７は、例えば、水酸基、アルキル基、アルコキシ基、ニトロ基、アミノ基、ハロ基、ウレイド基、イソシアネート基、メルカプト基、アルキルチオ基、Ｎ－（アミノアルキル）アミノ基、Ｎ－フェニルアミノ基、３，４－エポキシシクロヘキシル基、アルカノイルチオ基等が挙げられる。
In the present specification, R7 is, for example, a hydroxyl group, an alkyl group, an alkoxy group, a nitro group, an amino group, a halo group, a ureido group, an isocyanate group, a mercapto group, an alkylthio group, an N- (aminoalkyl) amino group, an N-phenyl group. And amino, 3,4-epoxycyclohexyl, alkanoylthio and the like.
なお、－Ｒ５－Ｒ７としては、例えば、水酸基、アルキル基、アルコキシ基、ニトロ基、アミノ基、ハロ基、ウレイド基、イソシアネート基、メルカプト基、アルキルチオ基、Ｎ－（アミノアルキル）アミノ基、Ｎ－フェニルアミノ基、３，４－エポキシシクロヘキシル基、アルカノイルチオ基、ヒドロキシアルキル基、アルコキシアルキル基、ニトロアルキル基、アミノアルキル基、ハロアルキル基、ウレイドアルキル基、イソシアネートアルキル基、メルカプトアルキル基、アルキルチオアルキル基、Ｎ－（アミノアルキル）アミノアルキル基、Ｎ－フェニルアミノアルキル基、３，４－エポキシシクロヘキシルアルキル基、アルカノイルチオアルキル基、ヒドロキシアルキルオキシ基、アルコキシアルキルオキシ基、ニトロアルキルオキシ基、ニトロオキシアルキル基、アミノアルキルオキシ基、アミノオキシアルキル基、ハロアルキルオキシ基、ハロオキシアルキル基、ウレイドアルキルオキシ基、ウレイドオキシアルキル基、イソシアネートアルキルオキシ基、イソシアネートオキシアルキル基、メルカプトアルキルオキシ基、メルカプトオキシアルキル基、アルキルチオアルキルオキシ基、アルキルチオキシアルキル基、Ｎ－（アミノアルキル）アミノアルキルオキシ基、Ｎ－（アミノアルキル）アミノオキシアルキル基、Ｎ－フェニルアミノアルキルオキシ基、Ｎ－フェニルアミノオキシアルキル基、３，４－エポキシシクロヘキシルアルキルオキシ基、３，４－エポキシシクロヘキシルオキシアルキル基、アルカノイルチオアルキルオキシ基、アルカノイルチオキシアルキル基等が挙げられる。
As -R5-R7, for example, hydroxyl group, alkyl group, alkoxy group, nitro group, amino group, halo group, ureido group, isocyanate group, mercapto group, alkylthio group, N- (aminoalkyl) amino group, N -Phenylamino group, 3,4-epoxycyclohexyl group, alkanoylthio group, hydroxyalkyl group, alkoxyalkyl group, nitroalkyl group, aminoalkyl group, haloalkyl group, ureido alkyl group, isocyanate alkyl group, mercaptoalkyl group, alkylthioalkyl group Group, N- (aminoalkyl) aminoalkyl group, N-phenylaminoalkyl group, 3,4-epoxycyclohexylalkyl group, alkanoylthioalkyl group, hydroxyalkyloxy group, alkoxyalkyloxy group, nitroalkyl Xy group, nitrooxyalkyl group, aminoalkyloxy group, aminooxyalkyl group, haloalkyloxy group, halooxyalkyl group, ureido alkyloxy group, ureido oxyalkyl group, isocyanate alkyloxy group, isocyanate oxyalkyl group, mercaptoalkyloxy Group, mercaptooxyalkyl group, alkylthioalkyloxy group, alkylthioxyalkyl group, N- (aminoalkyl) aminoalkyloxy group, N- (aminoalkyl) aminooxyalkyl group, N-phenylaminoalkyloxy group, N-phenyl Aminooxyalkyl group, 3,4-epoxycyclohexylalkyloxy group, 3,4-epoxycyclohexyloxyalkyl group, alkanoylthioalkyloxy group, alkanoylthio Shiarukiru group, and the like.
化合物（ａ２α）の具体例としては、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシオクチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン等を挙げることができるがこれらに制限されるものではない。これらの化合物は１種を用いてもよいし、２種以上を併用してもよい。
Specific examples of the compound (a2α) include 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxyoctyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane And 3-glycidoxypropyltriethoxysilane and the like, but not limited thereto. One of these compounds may be used, or two or more thereof may be used in combination.
２個以上のグリシジルオキシ基を有する化合物（ａ２β）
化合物（ａ２β）は、化合物（ａ１）に該当せず、且つ、２個以上のグリシジルオキシ基を有する限り、特に限定されない。 Compound (a2β) having two or more glycidyloxy groups
The compound (a2β) is not particularly limited as long as it does not correspond to the compound (a1) and has two or more glycidyloxy groups.
化合物（ａ２β）は、化合物（ａ１）に該当せず、且つ、２個以上のグリシジルオキシ基を有する限り、特に限定されない。 Compound (a2β) having two or more glycidyloxy groups
The compound (a2β) is not particularly limited as long as it does not correspond to the compound (a1) and has two or more glycidyloxy groups.
化合物（ａ２β）の具体例としては、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、エチレングリコールジグリシジルエーテル、１，３－プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、レゾルシノールジグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル、グリセロールトリグリシジルエーテル、トリメチロールエタントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、グリセロールアルキレンオキサイド付加物のトリグリシジルエーテル等を挙げることができるがこれらに制限されるものではない。これらの化合物は、１種を用いてもよいし、２種以上を併用してもよい。
Specific examples of the compound (a2β) include succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, 1,4-butanediol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, Pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, etc. Can gel it not intended to be limited thereto. One of these compounds may be used, or two or more thereof may be used in combination.
２個以上のアルコキシ基又は２個以上のハロ基と、－Ｒ５－Ｒ７と、を有するケイ素含有化合物（ａ３）
ケイ素含有化合物（ａ３）は、ポリシロキサン化合物の製造において、化合物（ａ１）及び化合物（ａ２α）に該当せず、且つ、２個以上のアルコキシ基又は２個以上のハロ基と－Ｒ５－Ｒ７とを有するケイ素含有化合物である限り特に限定されない。なお、化合物（ａ３）が２以上のハロ基を有する場合、各ハロ基は、例えば、フルオロ基、クロロ基、ブロモ基等であり、それらのハロ基は同一であっても異なっていてもよい。 Silicon-containing compound (a3) having two or more alkoxy groups or two or more halo groups, and -R5-R7
The silicon-containing compound (a3) does not correspond to the compound (a1) and the compound (a2α) in the production of the polysiloxane compound, and has two or more alkoxy groups or two or more halo groups and -R5-R7 It is not particularly limited as long as it is a silicon-containing compound having In addition, when a compound (a3) has 2 or more halo groups, each halo group is a fluoro group, a chloro group, a bromo group etc., for example, and those halo groups may be same or different. .
ケイ素含有化合物（ａ３）は、ポリシロキサン化合物の製造において、化合物（ａ１）及び化合物（ａ２α）に該当せず、且つ、２個以上のアルコキシ基又は２個以上のハロ基と－Ｒ５－Ｒ７とを有するケイ素含有化合物である限り特に限定されない。なお、化合物（ａ３）が２以上のハロ基を有する場合、各ハロ基は、例えば、フルオロ基、クロロ基、ブロモ基等であり、それらのハロ基は同一であっても異なっていてもよい。 Silicon-containing compound (a3) having two or more alkoxy groups or two or more halo groups, and -R5-R7
The silicon-containing compound (a3) does not correspond to the compound (a1) and the compound (a2α) in the production of the polysiloxane compound, and has two or more alkoxy groups or two or more halo groups and -R5-R7 It is not particularly limited as long as it is a silicon-containing compound having In addition, when a compound (a3) has 2 or more halo groups, each halo group is a fluoro group, a chloro group, a bromo group etc., for example, and those halo groups may be same or different. .
ケイ素含有化合物（ａ３）としては、例えば、ビニルトリクロロシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、３－（メタクリロイルオキシ）プロピルトリメトキシシラン、３，３，３－トリフルオロプロピルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－クロロプロピルトリメトキシシラン、トリメトキシシラン、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、オクチルトリメトキシシラン、フェニルトリメトキシシラン、ジメトキシジメチルシラン、フェニルメチルジメトキシシラン等のシランカップリング剤が挙げられるがこれらに制限されるものではない。これらのケイ素含有化合物は１種を用いてもよいし、２種以上を併用してもよい。
Examples of the silicon-containing compound (a3) include vinyltrichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3- (methacryloyloxy) ) Propyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-merka Topropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane And silane coupling agents such as dimethoxydimethylsilane and phenylmethyldimethoxysilane, but not limited thereto. These silicon-containing compounds may be used alone or in combination of two or more.
なお、Ｒ７もしくは－Ｒ５－Ｒ７のアルキル基；Ｒ６、－Ｒ５－Ｒ６、Ｒ７、もしくは－Ｒ５－Ｒ７に含まれるアルキル部分；または化合物（ａ２α）もしくは２個以上のアルコキシ基を有する化合物（ａ３）におけるアルコキシ基のアルキル部分は、直鎖状または分岐鎖状であれば特に制限されるものではないが、炭素数１～２０のアルキル基であることが好ましく、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の炭素数１～１２のアルキル基であることがより好ましい。上記化合物（ａ３）における各アルコキシ基におけるアルキル部分は、同一であってもよいし、異なっていてもよい。
In addition, an alkyl group of R7 or -R5-R7; an alkyl moiety contained in R6, -R5-R6, R7 or -R5-R7; or a compound (a2α) or a compound having two or more alkoxy groups (a3) The alkyl moiety of the alkoxy group in is not particularly limited as long as it is linear or branched, but is preferably an alkyl group having 1 to 20 carbon atoms, and a methyl group, an ethyl group, a propyl group, More preferably, it is an alkyl group having 1 to 12 carbon atoms, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. The alkyl moiety in each alkoxy group in the compound (a3) may be the same or different.
また、上記（２）では、ポリシロキサン化合物の製造に際し、リン化合物（ａ１）及びケイ素含有化合物（ａ３）と２個以上のグリシジルオキシ基を含む化合物（ａ２β）とを反応させるものを例示したが、これには限られない。例えば、水性媒体中で、２個以上のグリシジルオキシ基を含む化合物（ａ２β）と、２個以上のアミノ基を有する化合物とを反応させた後、リン化合物（ａ１）及びケイ素含有化合物（ａ３）を加えて所定の温度（好適には、４０～８０℃）にて反応させることにより、ポリシロキサン化合物を製造することができる。また、水性媒体中で、２個以上のグリシジルオキシ基を含む化合物（ａ２β）を縮重合させて縮重合体を得た後、当該縮重合体とポリオキシエチレン基及び／又はポリオキシプロピレン基を有する化合物とを反応させて、続いてリン化合物（ａ１）及びケイ素含有化合物（ａ３）を加えて所定の温度（好適には、４０～８０℃）にて反応させることでも製造することができる。
Also, in the above (2), the example in which the phosphorus compound (a1) and the silicon-containing compound (a3) are reacted with the compound (a2β) containing two or more glycidyloxy groups in the production of the polysiloxane compound is exemplified. Not limited to this. For example, after reacting a compound (a2β) containing two or more glycidyloxy groups with a compound having two or more amino groups in an aqueous medium, the phosphorus compound (a1) and the silicon-containing compound (a3) And reacting at a predetermined temperature (preferably 40 to 80.degree. C.) to produce a polysiloxane compound. In addition, after a compound (a2β) containing two or more glycidyloxy groups is polycondensed in an aqueous medium to obtain a polycondensate, the polycondensate and the polyoxyethylene group and / or polyoxypropylene group are It can also be produced by reacting the compound having the compound with the compound having a phosphorus compound (a1) and the silicon-containing compound (a3) followed by reaction at a predetermined temperature (preferably 40 to 80 ° C.).
＜ポリシロキサン化合物の用途＞
本実施形態のポリシロキサン化合物は、単重合体や共重合体等の重合物によって形成される皮膜の性能を向上可能であることから、上記重合物を用いて皮膜を形成させる技術分野に有用である。 <Application of Polysiloxane Compound>
The polysiloxane compound of the present embodiment is useful in the technical field of forming a film using the above-mentioned polymer, since it can improve the performance of a film formed by a polymer such as a homopolymer or a copolymer. is there.
本実施形態のポリシロキサン化合物は、単重合体や共重合体等の重合物によって形成される皮膜の性能を向上可能であることから、上記重合物を用いて皮膜を形成させる技術分野に有用である。 <Application of Polysiloxane Compound>
The polysiloxane compound of the present embodiment is useful in the technical field of forming a film using the above-mentioned polymer, since it can improve the performance of a film formed by a polymer such as a homopolymer or a copolymer. is there.
≪組成物≫
本実施形態に係る組成物は、水性媒体以外に、上式（Ｘ）で表される構造と上式（Ｙ）で表される構造とを有するポリシロキサン化合物（以下、単に「ポリシロキサン化合物」という）と、ポリシロキサン化合物とは異なる重合物と、を含む。該組成物は、水性媒体と、ポリシロキサン化合物と、重合物のみからなるものであってもよいし、更にその他の成分を含むものであってもよい。 «Composition»
The composition according to the present embodiment is a polysiloxane compound having a structure represented by the above formula (X) and a structure represented by the above formula (Y) (hereinafter simply referred to as "polysiloxane compound") in addition to the aqueous medium. And a polymer different from the polysiloxane compound. The composition may consist only of an aqueous medium, a polysiloxane compound and a polymer, or may further contain other components.
本実施形態に係る組成物は、水性媒体以外に、上式（Ｘ）で表される構造と上式（Ｙ）で表される構造とを有するポリシロキサン化合物（以下、単に「ポリシロキサン化合物」という）と、ポリシロキサン化合物とは異なる重合物と、を含む。該組成物は、水性媒体と、ポリシロキサン化合物と、重合物のみからなるものであってもよいし、更にその他の成分を含むものであってもよい。 «Composition»
The composition according to the present embodiment is a polysiloxane compound having a structure represented by the above formula (X) and a structure represented by the above formula (Y) (hereinafter simply referred to as "polysiloxane compound") in addition to the aqueous medium. And a polymer different from the polysiloxane compound. The composition may consist only of an aqueous medium, a polysiloxane compound and a polymer, or may further contain other components.
＜成分・配合＞
（ポリシロキサン化合物）
本実施形態に係る組成物は、１種のポリシロキサン化合物が含まれていればよいが、２種以上のポリシロキサン化合物が含まれていてもよい。但し、少なくとも１種は、上式（Ｘ）で表される構造と上式（Ｙ）で表される構造とを有するポリシロキサン化合物である。 <Component / Composition>
(Polysiloxane compound)
The composition according to the present embodiment may contain one kind of polysiloxane compound, but may contain two or more kinds of polysiloxane compounds. However, at least one type is a polysiloxane compound having a structure represented by the above formula (X) and a structure represented by the above formula (Y).
（ポリシロキサン化合物）
本実施形態に係る組成物は、１種のポリシロキサン化合物が含まれていればよいが、２種以上のポリシロキサン化合物が含まれていてもよい。但し、少なくとも１種は、上式（Ｘ）で表される構造と上式（Ｙ）で表される構造とを有するポリシロキサン化合物である。 <Component / Composition>
(Polysiloxane compound)
The composition according to the present embodiment may contain one kind of polysiloxane compound, but may contain two or more kinds of polysiloxane compounds. However, at least one type is a polysiloxane compound having a structure represented by the above formula (X) and a structure represented by the above formula (Y).
（重合物）
重合物としては、皮膜を形成できるものであれば特に限定されず、例えば、公知の単重合体もしくは共重合体またはそれを含有する組成物（例えば、単重合体及び／又は共重合体と架橋剤とを含む組成物）を挙げることができる。これらの重合物は、当該組成物中に１種のみ含まれていてもよいし、２種以上含まれていてもよい。 (Polymer)
The polymer is not particularly limited as long as it can form a film, and, for example, a known homopolymer or copolymer or a composition containing the same (for example, crosslinked with a homopolymer and / or a copolymer) A composition comprising an agent). These polymers may be contained alone or in combination of two or more in the composition.
重合物としては、皮膜を形成できるものであれば特に限定されず、例えば、公知の単重合体もしくは共重合体またはそれを含有する組成物（例えば、単重合体及び／又は共重合体と架橋剤とを含む組成物）を挙げることができる。これらの重合物は、当該組成物中に１種のみ含まれていてもよいし、２種以上含まれていてもよい。 (Polymer)
The polymer is not particularly limited as long as it can form a film, and, for example, a known homopolymer or copolymer or a composition containing the same (for example, crosslinked with a homopolymer and / or a copolymer) A composition comprising an agent). These polymers may be contained alone or in combination of two or more in the composition.
単重合体や共重合体としては、特に限定されず、例えば、ポリエチレングリコール、セルロース誘導体、キトサン誘導体、又は樹脂等を挙げることができる。単重合体や共重合体は重量平均分子量が１０００以上のものであることが好ましい。樹脂としては、公知の樹脂であれば特に制限されるものではないが、例えば、アクリル系樹脂、ポリエステル系樹脂 、ポリオレフィン系樹脂、エポキシ系樹脂、フェノール系樹脂、ポリビニル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリウレタン系樹脂及びエラストマー等を挙げることができる。
It does not specifically limit as a homopolymer or a copolymer, For example, polyethylene glycol, a cellulose derivative, a chitosan derivative, or resin etc. can be mentioned. The homopolymer and the copolymer preferably have a weight average molecular weight of 1000 or more. The resin is not particularly limited as long as it is a known resin, but, for example, acrylic resin, polyester resin, polyolefin resin, epoxy resin, phenol resin, polyvinyl resin, polyamide resin, polyimide Examples include system resins, polyurethane resins and elastomers.
架橋剤としては、単重合体や共重合体を架橋させて皮膜を形成できるものであれば特に限定されず、例えば、多価カルボン酸又はその塩、グリオキサール、イソシアネート、ブロックイソシアネート、カルボジイミド等を挙げることができる。
The crosslinking agent is not particularly limited as long as it can form a film by crosslinking a homopolymer or copolymer, and examples thereof include polyvalent carboxylic acids or salts thereof, glyoxal, isocyanates, blocked isocyanates, carbodiimides and the like. be able to.
このような重合物にポリシロキサン化合物を配合させることにより、該重合物によって形成される皮膜の性能を向上することが可能となる。
By blending a polysiloxane compound with such a polymer, it becomes possible to improve the performance of a film formed by the polymer.
（水性媒体）
水性媒体としては、水又は水と水混和性有機溶媒との混合物（水性媒体の体積を基準として５０体積％以上の水を含有するもの）であれば特に限定されるものではない。水混和性有機溶媒としては、水と混和するものであれば特に限定されるものではなく、例えば、アセトン、メチルエチルケトン等のケトン系溶媒；Ｎ，Ｎ’－ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶媒；メタノール、エタノール、イソプロパノール等のアルコール系溶媒；エチレングリコールモノブチルエーテル、エチレングリコールモノへキシルエーテル等のエーテル系溶媒；１－メチル－２－ピロリドン、１－エチル－２－ピロリドン等のピロリドン系溶媒等が挙げられる。これらの水混和性有機溶媒は１種を水と混合させてもよいし、２種以上を水に混合させてもよい。 (Aqueous medium)
The aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent (containing 50% by volume or more of water based on the volume of the aqueous medium). The water-miscible organic solvent is not particularly limited as long as it is miscible with water, and, for example, ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N'-dimethylformamide and dimethylacetamide Alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone Can be mentioned. One of these water-miscible organic solvents may be mixed with water, or two or more may be mixed with water.
水性媒体としては、水又は水と水混和性有機溶媒との混合物（水性媒体の体積を基準として５０体積％以上の水を含有するもの）であれば特に限定されるものではない。水混和性有機溶媒としては、水と混和するものであれば特に限定されるものではなく、例えば、アセトン、メチルエチルケトン等のケトン系溶媒；Ｎ，Ｎ’－ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶媒；メタノール、エタノール、イソプロパノール等のアルコール系溶媒；エチレングリコールモノブチルエーテル、エチレングリコールモノへキシルエーテル等のエーテル系溶媒；１－メチル－２－ピロリドン、１－エチル－２－ピロリドン等のピロリドン系溶媒等が挙げられる。これらの水混和性有機溶媒は１種を水と混合させてもよいし、２種以上を水に混合させてもよい。 (Aqueous medium)
The aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent (containing 50% by volume or more of water based on the volume of the aqueous medium). The water-miscible organic solvent is not particularly limited as long as it is miscible with water, and, for example, ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N'-dimethylformamide and dimethylacetamide Alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone Can be mentioned. One of these water-miscible organic solvents may be mixed with water, or two or more may be mixed with water.
（組成物における各成分の配合量）
・ポリシロキサン化合物
ポリシロキサン化合物の含有量は、組成物の全固形分に対して、１質量％以上、９９質量％以下の範囲内であることが好ましい。ポリシロキサン化合物のより好ましい含有量は、５質量％以上、９９質量％以下の範囲内であり、更に好ましい含有量は、１０質量％以上、９０質量％以下の範囲内である。 (Compounding amount of each component in the composition)
-Polysiloxane compound It is preferable that content of a polysiloxane compound exists in the range of 1 mass% or more and 99 mass% or less with respect to the total solid of a composition. A more preferable content of the polysiloxane compound is in the range of 5% by mass to 99% by mass, and a further preferable content is in the range of 10% by mass to 90% by mass.
・ポリシロキサン化合物
ポリシロキサン化合物の含有量は、組成物の全固形分に対して、１質量％以上、９９質量％以下の範囲内であることが好ましい。ポリシロキサン化合物のより好ましい含有量は、５質量％以上、９９質量％以下の範囲内であり、更に好ましい含有量は、１０質量％以上、９０質量％以下の範囲内である。 (Compounding amount of each component in the composition)
-Polysiloxane compound It is preferable that content of a polysiloxane compound exists in the range of 1 mass% or more and 99 mass% or less with respect to the total solid of a composition. A more preferable content of the polysiloxane compound is in the range of 5% by mass to 99% by mass, and a further preferable content is in the range of 10% by mass to 90% by mass.
・重合物
重合物の含有量は、組成物の全固形分に対して、１質量％以上、９９質量％以下の範囲内であることが好ましい。重合物のより好ましい含有量は、５質量％以上、９９質量％以下の範囲内であり、更に好ましい含有量は、１０質量％以上、９０質量％以下の範囲内である。 Polymer The content of the polymer is preferably in the range of 1% by mass or more and 99% by mass or less based on the total solid content of the composition. The more preferable content of the polymer is in the range of 5% by mass to 99% by mass, and the more preferable content is in the range of 10% by mass to 90% by mass.
重合物の含有量は、組成物の全固形分に対して、１質量％以上、９９質量％以下の範囲内であることが好ましい。重合物のより好ましい含有量は、５質量％以上、９９質量％以下の範囲内であり、更に好ましい含有量は、１０質量％以上、９０質量％以下の範囲内である。 Polymer The content of the polymer is preferably in the range of 1% by mass or more and 99% by mass or less based on the total solid content of the composition. The more preferable content of the polymer is in the range of 5% by mass to 99% by mass, and the more preferable content is in the range of 10% by mass to 90% by mass.
＜組成物の製造方法＞
本実施形態に係る組成物は、ポリシロキサン化合物と重合物と水性媒体を混合することにより製造可能である。 <Method of producing composition>
The composition which concerns on this embodiment can be manufactured by mixing a polysiloxane compound, a polymer, and an aqueous medium.
本実施形態に係る組成物は、ポリシロキサン化合物と重合物と水性媒体を混合することにより製造可能である。 <Method of producing composition>
The composition which concerns on this embodiment can be manufactured by mixing a polysiloxane compound, a polymer, and an aqueous medium.
＜組成物の用途＞
本実施形態の組成物は皮膜の形成に有用である。該皮膜は、少なくとも、本実施形態の組成物を材料の表面又は表面上に接触させる工程と、接触させた組成物を乾燥する工程とを行うことにより製造できる。ここで、前記材料は、特に限定されず、金属材料であっても非金属材料であってもよい。非金属材料としては、プラスチック、ゴム、セラミック、ガラス、繊維、磁性材料等が挙げられる。 <Application of Composition>
The composition of the present embodiment is useful for forming a film. The film can be produced by at least conducting the step of bringing the composition of the present embodiment into contact with the surface of the material or the step of drying the contacted composition. Here, the material is not particularly limited, and may be a metal material or a nonmetal material. Examples of nonmetal materials include plastics, rubbers, ceramics, glasses, fibers, magnetic materials and the like.
本実施形態の組成物は皮膜の形成に有用である。該皮膜は、少なくとも、本実施形態の組成物を材料の表面又は表面上に接触させる工程と、接触させた組成物を乾燥する工程とを行うことにより製造できる。ここで、前記材料は、特に限定されず、金属材料であっても非金属材料であってもよい。非金属材料としては、プラスチック、ゴム、セラミック、ガラス、繊維、磁性材料等が挙げられる。 <Application of Composition>
The composition of the present embodiment is useful for forming a film. The film can be produced by at least conducting the step of bringing the composition of the present embodiment into contact with the surface of the material or the step of drying the contacted composition. Here, the material is not particularly limited, and may be a metal material or a nonmetal material. Examples of nonmetal materials include plastics, rubbers, ceramics, glasses, fibers, magnetic materials and the like.
以下、実施例及び比較例により、本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。なお、以下で使用した金属材料は市販品の中から任意に選定したものであり、ポリシロキサン化合物と重合物とを含有する組成物における実際の用途を限定するものではない。なお、以下において、実施例の後に「Ａ」を付したもの（例えば実施例１Ａ）は、ポリシロキサン化合物の実施例を意味する。また、実施例及び比較例の後に「Ｂ」を付したもの（例えば実施例１Ｂ）は、組成物の実施例及び比較例をそれぞれ意味する。
Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the metal material used below is arbitrarily selected from commercial products, and does not limit the actual use in the composition containing a polysiloxane compound and a polymer. In addition, what attached "A" after the Example (for example, Example 1A) means the Example of a polysiloxane compound. Moreover, what attached "B" after an Example and a comparative example (for example, Example 1 B) means the Example of a composition, and a comparative example, respectively.
ポリシロキサン化合物や重合物の重量平均分子量や数平均分子量は、下の条件でゲル浸透クロマトグラフィー（ＧＰＣ）により測定し、標準試料であるポリスチレンで換算した。
（条件）
・カラム：セミミクロカラム２本；東ソー（株）製；２本を接続して使用
・標準試料：ＰＳｔＱｕｉｃｋ Ｂ；東ソー(株)製
・溶媒：Ｎ，Ｎ’－ジメチルホルムアミド（ＤＭＦ）
・検出機器：ＲＩ、ＵＶ The weight average molecular weight and number average molecular weight of the polysiloxane compound and the polymer were measured by gel permeation chromatography (GPC) under the following conditions, and converted to polystyrene as a standard sample.
(conditions)
・ Column: Semi-micro column 2; Tosoh Co., Ltd. product; 2 connected and used ・ Standard sample: PStQuick B; Tosoh Co., Ltd. product ・ Solvent: N, N'- dimethylformamide (DMF)
・ Detection equipment: RI, UV
（条件）
・カラム：セミミクロカラム２本；東ソー（株）製；２本を接続して使用
・標準試料：ＰＳｔＱｕｉｃｋ Ｂ；東ソー(株)製
・溶媒：Ｎ，Ｎ’－ジメチルホルムアミド（ＤＭＦ）
・検出機器：ＲＩ、ＵＶ The weight average molecular weight and number average molecular weight of the polysiloxane compound and the polymer were measured by gel permeation chromatography (GPC) under the following conditions, and converted to polystyrene as a standard sample.
(conditions)
・ Column: Semi-micro column 2; Tosoh Co., Ltd. product; 2 connected and used ・ Standard sample: PStQuick B; Tosoh Co., Ltd. product ・ Solvent: N, N'- dimethylformamide (DMF)
・ Detection equipment: RI, UV
≪ポリシロキサン化合物の原料≫
＜化合物（ａ１）＞
（ａ１－１）：リン酸
（ａ１－２）：亜リン酸
（ａ１－３）：エチドロン酸
（ａ１－４）：フェニルホスホン酸
（ａ１－５）：ドデシルリン酸
（ａ１－６）：リン酸２－ブトキシエチル
（ａ１－７）：ニトリロトリス（メチレンホスホン酸）
（ａ１－８）：２－ホスホノブタン－１，２，４－トリカルボン酸
（ａ１－９）：エチレンジアミンテトラ（メチレンホスホン酸） «Raw materials for polysiloxane compounds»
<Compound (a1)>
(A1-1): phosphoric acid (a1-2): phosphorous acid (a1-3): etidronic acid (a1-4): phenylphosphonic acid (a1-5): dodecyl phosphoric acid (a1-6): phosphoric acid 2-butoxyethyl (a1-7): nitrilotris (methylene phosphonic acid)
(A1-8): 2-phosphonobutane-1,2,4-tricarboxylic acid (a1-9): ethylenediaminetetra (methylene phosphonic acid)
＜化合物（ａ１）＞
（ａ１－１）：リン酸
（ａ１－２）：亜リン酸
（ａ１－３）：エチドロン酸
（ａ１－４）：フェニルホスホン酸
（ａ１－５）：ドデシルリン酸
（ａ１－６）：リン酸２－ブトキシエチル
（ａ１－７）：ニトリロトリス（メチレンホスホン酸）
（ａ１－８）：２－ホスホノブタン－１，２，４－トリカルボン酸
（ａ１－９）：エチレンジアミンテトラ（メチレンホスホン酸） «Raw materials for polysiloxane compounds»
<Compound (a1)>
(A1-1): phosphoric acid (a1-2): phosphorous acid (a1-3): etidronic acid (a1-4): phenylphosphonic acid (a1-5): dodecyl phosphoric acid (a1-6): phosphoric acid 2-butoxyethyl (a1-7): nitrilotris (methylene phosphonic acid)
(A1-8): 2-phosphonobutane-1,2,4-tricarboxylic acid (a1-9): ethylenediaminetetra (methylene phosphonic acid)
＜化合物（ａ２）＞
（ａ２－１）：３－グリシドキシプロピルトリメトキシシラン
（ａ２－２）：コハク酸ジグリシジルエステル
（ａ２－３）：３－グリシドキシオクチルトリメトキシシラン
（ａ２－４）：レゾルシノールジグリシジルエーテル
（ａ２－５）：１，６－ヘキサンジオールジグリシジルエーテル <Compound (a2)>
(A2-1): 3-glycidoxypropyltrimethoxysilane (a2-2): succinic acid diglycidyl ester (a2-3): 3-glycidoxyoctyltrimethoxysilane (a2-4): resorcinol diglycidyl Ether (a2-5): 1,6-hexanediol diglycidyl ether
（ａ２－１）：３－グリシドキシプロピルトリメトキシシラン
（ａ２－２）：コハク酸ジグリシジルエステル
（ａ２－３）：３－グリシドキシオクチルトリメトキシシラン
（ａ２－４）：レゾルシノールジグリシジルエーテル
（ａ２－５）：１，６－ヘキサンジオールジグリシジルエーテル <Compound (a2)>
(A2-1): 3-glycidoxypropyltrimethoxysilane (a2-2): succinic acid diglycidyl ester (a2-3): 3-glycidoxyoctyltrimethoxysilane (a2-4): resorcinol diglycidyl Ether (a2-5): 1,6-hexanediol diglycidyl ether
＜化合物（ａ３）＞
（ａ３－１）：テトラエトキシシラン
（ａ３－２）：メチルトリメトキシシラン
（ａ３－３）：フェニルトリメトキシシラン
（ａ３－４）：オクチルトリメトキシシラン
（ａ３－５）：３，３，３－トリフルオロプロピルトリメトキシシラン
（ａ３－６）：Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン
（ａ３－７）：３－アミノプロピルトリメトキシシラン
（ａ３－８）：Ｎ－フェニル－３－アミノプロピルトリメトキシシラン
（ａ３－９）：３－メルカプトプロピルトリメトキシシラン <Compound (a3)>
(A3-1): tetraethoxysilane (a3-2): methyltrimethoxysilane (a3-3): phenyltrimethoxysilane (a3-4): octyltrimethoxysilane (a3-5): 3, 3, 3 -Trifluoropropyltrimethoxysilane (a3-6): N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (a3-7): 3-aminopropyltrimethoxysilane (a3-8): N- Phenyl-3-aminopropyltrimethoxysilane (a3-9): 3-mercaptopropyltrimethoxysilane
（ａ３－１）：テトラエトキシシラン
（ａ３－２）：メチルトリメトキシシラン
（ａ３－３）：フェニルトリメトキシシラン
（ａ３－４）：オクチルトリメトキシシラン
（ａ３－５）：３，３，３－トリフルオロプロピルトリメトキシシラン
（ａ３－６）：Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン
（ａ３－７）：３－アミノプロピルトリメトキシシラン
（ａ３－８）：Ｎ－フェニル－３－アミノプロピルトリメトキシシラン
（ａ３－９）：３－メルカプトプロピルトリメトキシシラン <Compound (a3)>
(A3-1): tetraethoxysilane (a3-2): methyltrimethoxysilane (a3-3): phenyltrimethoxysilane (a3-4): octyltrimethoxysilane (a3-5): 3, 3, 3 -Trifluoropropyltrimethoxysilane (a3-6): N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (a3-7): 3-aminopropyltrimethoxysilane (a3-8): N- Phenyl-3-aminopropyltrimethoxysilane (a3-9): 3-mercaptopropyltrimethoxysilane
≪ポリシロキサン化合物≫
＜実施例１Ａ～２４Ａ＞
表１Ａ及び表１Ｂに示した組成に基づき、各種化合物と、水とを配合し、６０℃で５時間反応させた。反応後、２５℃に冷却し、実施例１Ａ～２４Ａのポリシロキサン化合物を得た。なお、各ポリシロキサン化合物の重量平均分子量を表１Ａ及び表１Ｂに示す。 «Polysiloxane compound»
Examples 1A to 24A
Based on the compositions shown in Tables 1A and 1B, various compounds and water were mixed and reacted at 60 ° C. for 5 hours. After the reaction, the reaction product was cooled to 25 ° C. to obtain the polysiloxane compounds of Examples 1A to 24A. The weight average molecular weight of each polysiloxane compound is shown in Table 1A and Table 1B.
＜実施例１Ａ～２４Ａ＞
表１Ａ及び表１Ｂに示した組成に基づき、各種化合物と、水とを配合し、６０℃で５時間反応させた。反応後、２５℃に冷却し、実施例１Ａ～２４Ａのポリシロキサン化合物を得た。なお、各ポリシロキサン化合物の重量平均分子量を表１Ａ及び表１Ｂに示す。 «Polysiloxane compound»
Examples 1A to 24A
Based on the compositions shown in Tables 1A and 1B, various compounds and water were mixed and reacted at 60 ° C. for 5 hours. After the reaction, the reaction product was cooled to 25 ° C. to obtain the polysiloxane compounds of Examples 1A to 24A. The weight average molecular weight of each polysiloxane compound is shown in Table 1A and Table 1B.
≪ポリシロキサン化合物と重合物とを含有する組成物≫
表２に示した組成に基づき、実施例１Ｂ～９Ｂの組成物を製造した。以下に詳細を示す。
＜実施例１Ｂ＞
２５℃にて、水１８０質量部とイソプロピルアルコール１００質量部との混合溶媒に、メタクリル酸メチル５５０質量部と、２－（ヒドロキシメチル）アクリル酸エチル５５０質量部と、アクリル酸１８質量部とを溶解させた。更に、過硫酸カリウム１．５質量部と、亜硫酸水素ナトリウム０．０６質量部と、無水酢酸ナトリウム１．５質量部とを溶解させた。次いで、窒素ガス中でゆっくりと６５℃まで昇温し、３時間反応させた。反応後、反応溶液を２５℃まで冷却し、ろ過してアクリル樹脂（重合物ｂ１）溶液（固形分濃度：２０質量％；粘度（３０℃）：２８．６ｍＰａ・ｓ；ｐＨ：５．６）を抽出した。 «Composition Containing Polysiloxane Compound and Polymer»
Based on the compositions shown in Table 2, the compositions of Examples 1B-9B were prepared. Details are shown below.
Example 1B
In a mixed solvent of 180 parts by mass of water and 100 parts by mass of isopropyl alcohol at 25 ° C., 550 parts by mass of methyl methacrylate, 550 parts by mass of ethyl 2- (hydroxymethyl) acrylate and 18 parts by mass of acrylic acid It was dissolved. Furthermore, 1.5 parts by mass of potassium persulfate, 0.06 parts by mass of sodium bisulfite and 1.5 parts by mass of anhydrous sodium acetate were dissolved. Then, the temperature was slowly raised to 65 ° C. in nitrogen gas and allowed to react for 3 hours. After the reaction, the reaction solution is cooled to 25 ° C. and filtered to obtain an acrylic resin (polymer b1) solution (solids concentration: 20% by mass; viscosity (30 ° C.): 28.6 mPa · s; pH: 5.6) Was extracted.
表２に示した組成に基づき、実施例１Ｂ～９Ｂの組成物を製造した。以下に詳細を示す。
＜実施例１Ｂ＞
２５℃にて、水１８０質量部とイソプロピルアルコール１００質量部との混合溶媒に、メタクリル酸メチル５５０質量部と、２－（ヒドロキシメチル）アクリル酸エチル５５０質量部と、アクリル酸１８質量部とを溶解させた。更に、過硫酸カリウム１．５質量部と、亜硫酸水素ナトリウム０．０６質量部と、無水酢酸ナトリウム１．５質量部とを溶解させた。次いで、窒素ガス中でゆっくりと６５℃まで昇温し、３時間反応させた。反応後、反応溶液を２５℃まで冷却し、ろ過してアクリル樹脂（重合物ｂ１）溶液（固形分濃度：２０質量％；粘度（３０℃）：２８．６ｍＰａ・ｓ；ｐＨ：５．６）を抽出した。 «Composition Containing Polysiloxane Compound and Polymer»
Based on the compositions shown in Table 2, the compositions of Examples 1B-9B were prepared. Details are shown below.
Example 1B
In a mixed solvent of 180 parts by mass of water and 100 parts by mass of isopropyl alcohol at 25 ° C., 550 parts by mass of methyl methacrylate, 550 parts by mass of ethyl 2- (hydroxymethyl) acrylate and 18 parts by mass of acrylic acid It was dissolved. Furthermore, 1.5 parts by mass of potassium persulfate, 0.06 parts by mass of sodium bisulfite and 1.5 parts by mass of anhydrous sodium acetate were dissolved. Then, the temperature was slowly raised to 65 ° C. in nitrogen gas and allowed to react for 3 hours. After the reaction, the reaction solution is cooled to 25 ° C. and filtered to obtain an acrylic resin (polymer b1) solution (solids concentration: 20% by mass; viscosity (30 ° C.): 28.6 mPa · s; pH: 5.6) Was extracted.
固形分換算で、アクリル樹脂（重合物ｂ１）８３．０質量部と実施例１Ａのポリシロキサン化合物１７．０質量部とを撹拌した後、水の総量が１５０質量部となるように水をゆっくり加え、実施例１Ｂの組成物を得た。
After stirring 83.0 parts by mass of an acrylic resin (polymer b1) and 17.0 parts by mass of the polysiloxane compound of Example 1A in terms of solid content, the water is slowly added so that the total amount of water is 150 parts by mass. In addition, the composition of Example 1B was obtained.
＜実施例２Ｂ＞
エチレングリコール（９０ｍｏｌ％）及びトリメチロールプロパン（１０ｍｏｌ％）からなるアルコール成分と、イソフタル酸（４０ｍｏｌ％）、テレフタル酸（４１ｍｏｌ％）、イソフタル酸ジメチル－５－スルホン酸ナトリウム（２ｍｏｌ％）及び無水トリメリット酸（１７ｍｏｌ％）からなる酸成分と、の縮合反応によるポリエステル樹脂を次の方法で合成した。２ｍｏｌの全アルコール成分と１ｍｏｌの全酸成分と触媒（酢酸カルシウム０．２５ｇ、Ｎ－ブチルチタネート０．１ｇ）とを、窒素ガス中で１８０℃にて混合した後、２００℃に昇温し、加熱撹拌しながら２時間反応させた。反応後、２６０℃、減圧下（０．５ｍｍＨｇ）にて３時間反応（重縮合反応）させることにより、ポリエステル樹脂（重合物ｂ２）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例２Ｂの組成物を得た。 Example 2B
Alcohol component consisting of ethylene glycol (90 mol%) and trimethylolpropane (10 mol%), isophthalic acid (40 mol%), terephthalic acid (41 mol%), sodium dimethyl -5-sulfonate isophthalate (2 mol%) and trianhydride A polyester resin was synthesized according to the following method by condensation reaction of an acid component consisting of mellitic acid (17 mol%). After mixing 2 mol of total alcohol component, 1 mol of total acid component and catalyst (0.25 g of calcium acetate, 0.1 g of N-butyltitanate) at 180 ° C. in nitrogen gas, the temperature is raised to 200 ° C. The reaction was allowed to proceed for 2 hours while heating and stirring. After the reaction, the reaction (polycondensation reaction) was performed at 260 ° C. under reduced pressure (0.5 mmHg) for 3 hours to obtain a polyester resin (polymer b2). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 2B.
エチレングリコール（９０ｍｏｌ％）及びトリメチロールプロパン（１０ｍｏｌ％）からなるアルコール成分と、イソフタル酸（４０ｍｏｌ％）、テレフタル酸（４１ｍｏｌ％）、イソフタル酸ジメチル－５－スルホン酸ナトリウム（２ｍｏｌ％）及び無水トリメリット酸（１７ｍｏｌ％）からなる酸成分と、の縮合反応によるポリエステル樹脂を次の方法で合成した。２ｍｏｌの全アルコール成分と１ｍｏｌの全酸成分と触媒（酢酸カルシウム０．２５ｇ、Ｎ－ブチルチタネート０．１ｇ）とを、窒素ガス中で１８０℃にて混合した後、２００℃に昇温し、加熱撹拌しながら２時間反応させた。反応後、２６０℃、減圧下（０．５ｍｍＨｇ）にて３時間反応（重縮合反応）させることにより、ポリエステル樹脂（重合物ｂ２）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例２Ｂの組成物を得た。 Example 2B
Alcohol component consisting of ethylene glycol (90 mol%) and trimethylolpropane (10 mol%), isophthalic acid (40 mol%), terephthalic acid (41 mol%), sodium dimethyl -5-sulfonate isophthalate (2 mol%) and trianhydride A polyester resin was synthesized according to the following method by condensation reaction of an acid component consisting of mellitic acid (17 mol%). After mixing 2 mol of total alcohol component, 1 mol of total acid component and catalyst (0.25 g of calcium acetate, 0.1 g of N-butyltitanate) at 180 ° C. in nitrogen gas, the temperature is raised to 200 ° C. The reaction was allowed to proceed for 2 hours while heating and stirring. After the reaction, the reaction (polycondensation reaction) was performed at 260 ° C. under reduced pressure (0.5 mmHg) for 3 hours to obtain a polyester resin (polymer b2). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 2B.
＜実施例３Ｂ＞
プロピレン－エチレン－α－オレフィン共重合体（プロピレン成分６８ｍｏｌ％、エチレン成分８ｍｏｌ％、ブテン成分２４ｍｏｌ％；重量平均分子量：６００００）１００質量部と、無水マレイン酸１０質量部と、メタクリル酸メチル１０質量部と、ジクミルパーオキサイド１質量部とを、１８０℃で撹拌しながら２時間反応させ、変性ポリオレフィン樹脂組成物（無水マレイン酸のグラフト質量：８．４質量％；重量平均分子量：４５０００）を得た。
この変性ポリオレフィン樹脂組成物１００質量部と、ジメチルエタノールアミン１０質量部と、ポリオキシエチレンアルキルエーテル硫酸塩１０質量部とを、１００℃で２時間攪拌することにより、ポリオレフィン樹脂（重合物ｂ３）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例３Ｂの組成物を得た。 Example 3B
100 parts by mass of a propylene-ethylene-α-olefin copolymer (68 mol% of propylene component, 8 mol% of ethylene component, 24 mol% of butene component; weight average molecular weight: 60000), 10 parts by mass of maleic anhydride, and 10 parts of methyl methacrylate Parts and 1 part by mass of dicumyl peroxide are reacted for 2 hours while stirring at 180 ° C., and a modified polyolefin resin composition (grafted weight of maleic anhydride: 8.4 mass%; weight average molecular weight: 45000) Obtained.
100 parts by mass of this modified polyolefin resin composition, 10 parts by mass of dimethylethanolamine and 10 parts by mass of polyoxyethylene alkyl ether sulfate are stirred at 100 ° C. for 2 hours to obtain a polyolefin resin (polymer b3) Obtained. Thereafter, in the same manner as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 3B.
プロピレン－エチレン－α－オレフィン共重合体（プロピレン成分６８ｍｏｌ％、エチレン成分８ｍｏｌ％、ブテン成分２４ｍｏｌ％；重量平均分子量：６００００）１００質量部と、無水マレイン酸１０質量部と、メタクリル酸メチル１０質量部と、ジクミルパーオキサイド１質量部とを、１８０℃で撹拌しながら２時間反応させ、変性ポリオレフィン樹脂組成物（無水マレイン酸のグラフト質量：８．４質量％；重量平均分子量：４５０００）を得た。
この変性ポリオレフィン樹脂組成物１００質量部と、ジメチルエタノールアミン１０質量部と、ポリオキシエチレンアルキルエーテル硫酸塩１０質量部とを、１００℃で２時間攪拌することにより、ポリオレフィン樹脂（重合物ｂ３）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例３Ｂの組成物を得た。 Example 3B
100 parts by mass of a propylene-ethylene-α-olefin copolymer (68 mol% of propylene component, 8 mol% of ethylene component, 24 mol% of butene component; weight average molecular weight: 60000), 10 parts by mass of maleic anhydride, and 10 parts of methyl methacrylate Parts and 1 part by mass of dicumyl peroxide are reacted for 2 hours while stirring at 180 ° C., and a modified polyolefin resin composition (grafted weight of maleic anhydride: 8.4 mass%; weight average molecular weight: 45000) Obtained.
100 parts by mass of this modified polyolefin resin composition, 10 parts by mass of dimethylethanolamine and 10 parts by mass of polyoxyethylene alkyl ether sulfate are stirred at 100 ° C. for 2 hours to obtain a polyolefin resin (polymer b3) Obtained. Thereafter, in the same manner as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 3B.
＜実施例４Ｂ～６Ｂ＞
エポキシ樹脂（重合物ｂ４）として、ポリエチレングリコールジグリシジルエーテル（平均重合度：９；２官能；エポキシ当量：２６８；粘度（３０℃）：７０ｍＰａ・ｓ）を、フェノール樹脂（重合物ｂ５）として、ポリビニルフェノール（水酸基当量：１２０；重量平均分子量：１０００００）を、ポリビニル樹脂（重合物ｂ６）として、アセトアセチル化ポリビニルアルコール(鹸化度：９９％；アセトアセチル化度：９．８％；粘度（３０℃）：１２ｍＰａ・ｓ；重量平均分子量：５００００)をそれぞれ用い、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例４Ｂ～６Ｂの組成物を得た。 Examples 4B to 6B
As an epoxy resin (polymer b4), polyethylene glycol diglycidyl ether (average polymerization degree: 9; bifunctional; epoxy equivalent: 268; viscosity (30 ° C.): 70 mPa · s) as a phenol resin (polymer b 5) Acetoacetylated polyvinyl alcohol (saponification degree: 99%; acetoacetylation degree: 9.8%) as polyvinyl resin (hydroxy group equivalent: 120; weight average molecular weight: 100000) as polyvinyl resin (polymer b6); viscosity (30 C.): 12 mPa · s; weight average molecular weight: 50000) In the same manner as in Example 1B, the polymer, the polysiloxane compound of Example 1A and water are mixed, and the compositions of Examples 4B to 6B are obtained. Obtained.
エポキシ樹脂（重合物ｂ４）として、ポリエチレングリコールジグリシジルエーテル（平均重合度：９；２官能；エポキシ当量：２６８；粘度（３０℃）：７０ｍＰａ・ｓ）を、フェノール樹脂（重合物ｂ５）として、ポリビニルフェノール（水酸基当量：１２０；重量平均分子量：１０００００）を、ポリビニル樹脂（重合物ｂ６）として、アセトアセチル化ポリビニルアルコール(鹸化度：９９％；アセトアセチル化度：９．８％；粘度（３０℃）：１２ｍＰａ・ｓ；重量平均分子量：５００００)をそれぞれ用い、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例４Ｂ～６Ｂの組成物を得た。 Examples 4B to 6B
As an epoxy resin (polymer b4), polyethylene glycol diglycidyl ether (average polymerization degree: 9; bifunctional; epoxy equivalent: 268; viscosity (30 ° C.): 70 mPa · s) as a phenol resin (polymer b 5) Acetoacetylated polyvinyl alcohol (saponification degree: 99%; acetoacetylation degree: 9.8%) as polyvinyl resin (hydroxy group equivalent: 120; weight average molecular weight: 100000) as polyvinyl resin (polymer b6); viscosity (30 C.): 12 mPa · s; weight average molecular weight: 50000) In the same manner as in Example 1B, the polymer, the polysiloxane compound of Example 1A and water are mixed, and the compositions of Examples 4B to 6B are obtained. Obtained.
＜実施例７Ｂ＞
無水トリメリット酸１１０６質量部と、４，４－ジフェニルメタンジイソシアネート１４５５質量部と、１－メチル－２－ピロリドン２５６２質量部とを、窒素ガス中で撹拌しながらゆっくりと１３０℃まで昇温した。その後、１３０℃で約６時間反応させ、ポリアミドイミド樹脂溶液［固形分濃度：５０質量％；酸価（カルボキシル基及び酸無水物基を開環させたカルボキシル基を合わせた酸価）：４０；粘度（３０℃）：８５．０ｍＰａ・ｓ；数平均分子量：１７０００］を得た。
このポリアミドイミド樹脂溶液２７００質量部を、窒素ガス中で撹拌しながら５０℃まで昇温した。５０℃に達したところでトリエチルアミンを４４７．１質量部（４当量）添加し、ポリアミドイミド樹脂（重合物ｂ７）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例７Ｂの組成物を得た。 Example 7B
1106 parts by mass of trimellitic anhydride, 1455 parts by mass of 4,4-diphenylmethane diisocyanate, and 2562 parts by mass of 1-methyl-2-pyrrolidone were slowly heated to 130 ° C. while being stirred in nitrogen gas. Thereafter, the reaction is carried out at 130 ° C. for about 6 hours, and the polyamideimide resin solution [solids concentration: 50% by mass; acid value (acid value obtained by combining carboxyl group obtained by ring-opening carboxyl group and acid anhydride group): 40; Viscosity (30 ° C.): 85.0 mPa · s; number average molecular weight: 17000].
2700 parts by mass of this polyamideimide resin solution was heated to 50 ° C. while being stirred in nitrogen gas. When the temperature reached 50 ° C., 447.1 parts by mass (4 equivalents) of triethylamine was added to obtain a polyamideimide resin (polymer b7). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 7B.
無水トリメリット酸１１０６質量部と、４，４－ジフェニルメタンジイソシアネート１４５５質量部と、１－メチル－２－ピロリドン２５６２質量部とを、窒素ガス中で撹拌しながらゆっくりと１３０℃まで昇温した。その後、１３０℃で約６時間反応させ、ポリアミドイミド樹脂溶液［固形分濃度：５０質量％；酸価（カルボキシル基及び酸無水物基を開環させたカルボキシル基を合わせた酸価）：４０；粘度（３０℃）：８５．０ｍＰａ・ｓ；数平均分子量：１７０００］を得た。
このポリアミドイミド樹脂溶液２７００質量部を、窒素ガス中で撹拌しながら５０℃まで昇温した。５０℃に達したところでトリエチルアミンを４４７．１質量部（４当量）添加し、ポリアミドイミド樹脂（重合物ｂ７）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例７Ｂの組成物を得た。 Example 7B
1106 parts by mass of trimellitic anhydride, 1455 parts by mass of 4,4-diphenylmethane diisocyanate, and 2562 parts by mass of 1-methyl-2-pyrrolidone were slowly heated to 130 ° C. while being stirred in nitrogen gas. Thereafter, the reaction is carried out at 130 ° C. for about 6 hours, and the polyamideimide resin solution [solids concentration: 50% by mass; acid value (acid value obtained by combining carboxyl group obtained by ring-opening carboxyl group and acid anhydride group): 40; Viscosity (30 ° C.): 85.0 mPa · s; number average molecular weight: 17000].
2700 parts by mass of this polyamideimide resin solution was heated to 50 ° C. while being stirred in nitrogen gas. When the temperature reached 50 ° C., 447.1 parts by mass (4 equivalents) of triethylamine was added to obtain a polyamideimide resin (polymer b7). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 7B.
＜実施例８Ｂ＞
２５℃にて、ビスフェノールＡのエチレンオキサイド２ｍｏｌ付加物３０質量部と、ポリエチレングリコール４０質量部と、Ｎ－メチルジエタノールアミン１０質量部と、ジエチレングリコール１０質量部と、トリメチロールプロパン１０質量部と、イソホロンジイソシアネート１３０質量部と、メチルエチルケトン１３０質量部とを、６５～７０℃で４時間反応させてポリウレタン樹脂（重合物ｂ８）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例８Ｂの組成物を得た。 Example 8B
At 25 ° C., 30 parts by mass of ethylene oxide 2 mol adduct of bisphenol A, 40 parts by mass of polyethylene glycol, 10 parts by mass of N-methyldiethanolamine, 10 parts by mass of diethylene glycol, 10 parts by mass of trimethylolpropane, isophorone diisocyanate 130 parts by mass and 130 parts by mass of methyl ethyl ketone were reacted at 65 to 70 ° C. for 4 hours to obtain a polyurethane resin (polymer b8). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 8B.
２５℃にて、ビスフェノールＡのエチレンオキサイド２ｍｏｌ付加物３０質量部と、ポリエチレングリコール４０質量部と、Ｎ－メチルジエタノールアミン１０質量部と、ジエチレングリコール１０質量部と、トリメチロールプロパン１０質量部と、イソホロンジイソシアネート１３０質量部と、メチルエチルケトン１３０質量部とを、６５～７０℃で４時間反応させてポリウレタン樹脂（重合物ｂ８）を得た。その後、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例８Ｂの組成物を得た。 Example 8B
At 25 ° C., 30 parts by mass of ethylene oxide 2 mol adduct of bisphenol A, 40 parts by mass of polyethylene glycol, 10 parts by mass of N-methyldiethanolamine, 10 parts by mass of diethylene glycol, 10 parts by mass of trimethylolpropane, isophorone diisocyanate 130 parts by mass and 130 parts by mass of methyl ethyl ketone were reacted at 65 to 70 ° C. for 4 hours to obtain a polyurethane resin (polymer b8). Thereafter, as in Example 1B, the polymer, the polysiloxane compound of Example 1A, and water were mixed to obtain a composition of Example 8B.
＜実施例９Ｂ＞
エラストマー（重合物ｂ９）として、カルボキシル基及びメチロール基を有するアクリロニトリルブタジエンスチレンゴムの水分散体［固形分濃度：４７％；粘度（３０℃）：４５ｍＰａ・ｓ；ｐＨ：８．０；比重：１．０１］を用い、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例９Ｂの組成物を得た。 Example 9B
Aqueous dispersion of acrylonitrile butadiene styrene rubber having carboxyl group and methylol group as elastomer (polymer b9) [solids concentration: 47%; viscosity (30 ° C.): 45 mPa · s; pH: 8.0; specific gravity: 1 The polymer, the polysiloxane compound of Example 1A, and water were mixed in the same manner as in Example 1B using .01] to obtain a composition of Example 9B.
エラストマー（重合物ｂ９）として、カルボキシル基及びメチロール基を有するアクリロニトリルブタジエンスチレンゴムの水分散体［固形分濃度：４７％；粘度（３０℃）：４５ｍＰａ・ｓ；ｐＨ：８．０；比重：１．０１］を用い、実施例１Ｂと同様に、重合物と実施例１Ａのポリシロキサン化合物と水とを混合し、実施例９Ｂの組成物を得た。 Example 9B
Aqueous dispersion of acrylonitrile butadiene styrene rubber having carboxyl group and methylol group as elastomer (polymer b9) [solids concentration: 47%; viscosity (30 ° C.): 45 mPa · s; pH: 8.0; specific gravity: 1 The polymer, the polysiloxane compound of Example 1A, and water were mixed in the same manner as in Example 1B using .01] to obtain a composition of Example 9B.
＜実施例１０Ｂ～３２Ｂ＞
表３Ａ及び３Ｂに示した組成に基づき、実施例１Ｂ～９Ｂと同様に、重合物とポリシロキサン化合物と水とを混合し、実施例１０Ｂ～３２Ｂの組成物を製造した。 Examples 10B to 32B
Based on the compositions shown in Tables 3A and 3B, the polymer, the polysiloxane compound and water were mixed in the same manner as in Examples 1B to 9B to produce the compositions of Examples 10B to 32B.
表３Ａ及び３Ｂに示した組成に基づき、実施例１Ｂ～９Ｂと同様に、重合物とポリシロキサン化合物と水とを混合し、実施例１０Ｂ～３２Ｂの組成物を製造した。 Examples 10B to 32B
Based on the compositions shown in Tables 3A and 3B, the polymer, the polysiloxane compound and water were mixed in the same manner as in Examples 1B to 9B to produce the compositions of Examples 10B to 32B.
＜比較例１Ｂ～９Ｂ＞
表４に示すように、固形分換算で、１００質量部の重合物ｂ１～ｂ９に対し、水の総量が１５０質量部となるように水をゆっくり加え、比較例１Ｂ～９Ｂの組成物を製造した。 Comparative Examples 1B to 9B
As shown in Table 4, water is slowly added so that the total amount of water is 150 parts by mass with respect to 100 parts by mass of the polymers b1 to b9 in terms of solid content, to manufacture the composition of Comparative Examples 1B to 9B did.
表４に示すように、固形分換算で、１００質量部の重合物ｂ１～ｂ９に対し、水の総量が１５０質量部となるように水をゆっくり加え、比較例１Ｂ～９Ｂの組成物を製造した。 Comparative Examples 1B to 9B
As shown in Table 4, water is slowly added so that the total amount of water is 150 parts by mass with respect to 100 parts by mass of the polymers b1 to b9 in terms of solid content, to manufacture the composition of Comparative Examples 1B to 9B did.
≪試験板の作製≫
溶融亜鉛めっき鋼板であるＧＩ材［亜鉛付着量片面当たり６０ｇ／ｍ２（両面メッキ）；ＪＩＳ Ｇ ３３０２：２０１２］の表面上に、アルカリ性脱脂剤［ファインクリーナーＦＣ－Ｅ６４０６；日本パーカライジング（株）製；濃度：２０ｇ／Ｌ；温度：６０℃］を１０秒間スプレーすることにより、脱脂処理を行った後、水を１０秒間スプレーすることにより水洗した。 «Preparation of test plate»
An alkaline degreaser [Fine Cleaner FC-E 6406; made by Nihon Parkerizing Co., Ltd.] on the surface of a GI material [zinc adhesion amount 60 g / m 2 (double-sided plating); JIS G 3302: 2012] which is a hot-dip galvanized steel sheet Concentration: 20 g / L; temperature: 60 ° C.] for 10 seconds to carry out a degreasing treatment, followed by water washing by spraying water for 10 seconds.
溶融亜鉛めっき鋼板であるＧＩ材［亜鉛付着量片面当たり６０ｇ／ｍ２（両面メッキ）；ＪＩＳ Ｇ ３３０２：２０１２］の表面上に、アルカリ性脱脂剤［ファインクリーナーＦＣ－Ｅ６４０６；日本パーカライジング（株）製；濃度：２０ｇ／Ｌ；温度：６０℃］を１０秒間スプレーすることにより、脱脂処理を行った後、水を１０秒間スプレーすることにより水洗した。 «Preparation of test plate»
An alkaline degreaser [Fine Cleaner FC-E 6406; made by Nihon Parkerizing Co., Ltd.] on the surface of a GI material [zinc adhesion amount 60 g / m 2 (double-sided plating); JIS G 3302: 2012] which is a hot-dip galvanized steel sheet Concentration: 20 g / L; temperature: 60 ° C.] for 10 seconds to carry out a degreasing treatment, followed by water washing by spraying water for 10 seconds.
水洗したＧＩ材の表面上に、実施例１Ｂ～３２Ｂ及び比較例１Ｂ～９Ｂの組成物をバーコートで塗布し、到達板温度（ＰＭＴ）１５０℃で乾燥して、各種塗膜を有するＧＩ材（Ｎｏ．１～４１）を作製した。なお、乾燥後の塗膜質量は１０００ｍｇ／ｍ２であった。
The compositions of Examples 1B to 32B and Comparative Examples 1B to 9B are coated with a bar coat on the surface of the washed GI material, and dried at a plate temperature (PMT) of 150 ° C. to obtain GI materials having various coatings. (No. 1 to 41) were produced. In addition, the coating-film mass after drying was 1000 mg / m < 2 >.
≪各種評価試験≫
＜貯蔵安定性＞
上記塗膜の形成に用いた実施例１Ｂ～３２Ｂ及び比較例１Ｂ～９Ｂの組成物を２５℃及び４０℃にて３ヵ月間密閉保管し、下記の評価基準に基づいて貯蔵安定性を評価した。その結果を表５及び表６に示す。
（評価基準）
○：沈殿又は相分離しない
△：相分離する
×：沈殿又はゲル化する «Various evaluation tests»
<Storage stability>
The compositions of Examples 1B to 32B and Comparative Examples 1B to 9B used for forming the coating film were sealed and stored at 25 ° C. and 40 ° C. for 3 months, and the storage stability was evaluated based on the following evaluation criteria . The results are shown in Tables 5 and 6.
(Evaluation criteria)
○: precipitation or phase separation Δ: phase separation x: precipitation or gelation
＜貯蔵安定性＞
上記塗膜の形成に用いた実施例１Ｂ～３２Ｂ及び比較例１Ｂ～９Ｂの組成物を２５℃及び４０℃にて３ヵ月間密閉保管し、下記の評価基準に基づいて貯蔵安定性を評価した。その結果を表５及び表６に示す。
（評価基準）
○：沈殿又は相分離しない
△：相分離する
×：沈殿又はゲル化する «Various evaluation tests»
<Storage stability>
The compositions of Examples 1B to 32B and Comparative Examples 1B to 9B used for forming the coating film were sealed and stored at 25 ° C. and 40 ° C. for 3 months, and the storage stability was evaluated based on the following evaluation criteria . The results are shown in Tables 5 and 6.
(Evaluation criteria)
○: precipitation or phase separation Δ: phase separation x: precipitation or gelation
＜平面部耐食性＞
Ｎｏ．１～４１の各種塗膜を有するＧＩ材に対して、ＪＩＳ Ｚ ２３７１：２０００による中性塩水噴霧試験を実施した。具体的には、Ｎｏ．１～４１の各種塗膜を有するＧＩ材の表面上に中性塩水を４８時間噴霧した後、該ＧＩ材の表面上を乾燥させた。乾燥させた各種ＧＩ材の表面上に発生した白錆の面積割合を目視で測定し、以下の評価基準に従って平面部耐食性を評価した。その結果を表５及び表６に示す。
（評価基準）
◎：白錆の面積割合が３％未満である
○：白錆の面積割合が３％以上１０％未満である
△：白錆の面積割合が１０％以上３０％未満である
×：白錆の面積割合が３０％以上である <Plane corrosion resistance>
No. A neutral salt spray test according to JIS Z 2371: 2000 was carried out on GI materials having various coatings of 1 to 41. Specifically, no. After neutral salt water was sprayed for 48 hours on the surface of GI material having various coatings of 1 to 41, the surface of the GI material was dried. The area ratio of white rust generated on the surfaces of various dried GI materials was visually measured, and the flat surface corrosion resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6.
(Evaluation criteria)
:: The area ratio of white rust is less than 3% ○: The area ratio of white rust is 3% or more and less than 10% Δ: The area ratio of white rust is 10% or more and less than 30% x: of white rust Area ratio is 30% or more
Ｎｏ．１～４１の各種塗膜を有するＧＩ材に対して、ＪＩＳ Ｚ ２３７１：２０００による中性塩水噴霧試験を実施した。具体的には、Ｎｏ．１～４１の各種塗膜を有するＧＩ材の表面上に中性塩水を４８時間噴霧した後、該ＧＩ材の表面上を乾燥させた。乾燥させた各種ＧＩ材の表面上に発生した白錆の面積割合を目視で測定し、以下の評価基準に従って平面部耐食性を評価した。その結果を表５及び表６に示す。
（評価基準）
◎：白錆の面積割合が３％未満である
○：白錆の面積割合が３％以上１０％未満である
△：白錆の面積割合が１０％以上３０％未満である
×：白錆の面積割合が３０％以上である <Plane corrosion resistance>
No. A neutral salt spray test according to JIS Z 2371: 2000 was carried out on GI materials having various coatings of 1 to 41. Specifically, no. After neutral salt water was sprayed for 48 hours on the surface of GI material having various coatings of 1 to 41, the surface of the GI material was dried. The area ratio of white rust generated on the surfaces of various dried GI materials was visually measured, and the flat surface corrosion resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6.
(Evaluation criteria)
:: The area ratio of white rust is less than 3% ○: The area ratio of white rust is 3% or more and less than 10% Δ: The area ratio of white rust is 10% or more and less than 30% x: of white rust Area ratio is 30% or more
＜加工部耐食性＞
Ｎｏ．１～４１の各種塗膜を有するＧＩ材に対して、エリクセン試験（７ｍｍ押し出し）を行った後、ＪＩＳ Ｚ ２３７１：２０００による中性塩水噴霧試験を実施した。具体的には、Ｎｏ．１～４１の各種塗膜を有するＧＩ材の表面上に中性塩水を２４時間噴霧した後、該ＧＩ材の表面上を乾燥させた。乾燥させた各種ＧＩ材の表面上に発生した白錆の面積割合を目視で測定し、以下の評価基準に従って加工部耐食性を評価した。その結果を表５及び表６に示す。
（評価基準）
◎：白錆の面積割合が１０％未満である
○：白錆の面積割合が１０％以上２０％未満である
△：白錆の面積割合が２０％以上３０％未満である
×：白錆の面積割合が３０％以上である <Processed part corrosion resistance>
No. An Erichsen test (7 mm extrusion) was performed on GI materials having various coatings of 1 to 41, and then a neutral salt spray test according to JIS Z 2371: 2000 was performed. Specifically, no. After neutral salt water was sprayed for 24 hours on the surface of GI material having various coatings of 1 to 41, the surface of the GI material was dried. The area ratio of white rust generated on the surface of various dried GI materials was visually measured, and the corrosion resistance of the processed portion was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6.
(Evaluation criteria)
:: The area ratio of white rust is less than 10% ○: The area ratio of white rust is 10% or more and less than 20% Δ: The area ratio of white rust is 20% or more and less than 30% x: of white rust Area ratio is 30% or more
Ｎｏ．１～４１の各種塗膜を有するＧＩ材に対して、エリクセン試験（７ｍｍ押し出し）を行った後、ＪＩＳ Ｚ ２３７１：２０００による中性塩水噴霧試験を実施した。具体的には、Ｎｏ．１～４１の各種塗膜を有するＧＩ材の表面上に中性塩水を２４時間噴霧した後、該ＧＩ材の表面上を乾燥させた。乾燥させた各種ＧＩ材の表面上に発生した白錆の面積割合を目視で測定し、以下の評価基準に従って加工部耐食性を評価した。その結果を表５及び表６に示す。
（評価基準）
◎：白錆の面積割合が１０％未満である
○：白錆の面積割合が１０％以上２０％未満である
△：白錆の面積割合が２０％以上３０％未満である
×：白錆の面積割合が３０％以上である <Processed part corrosion resistance>
No. An Erichsen test (7 mm extrusion) was performed on GI materials having various coatings of 1 to 41, and then a neutral salt spray test according to JIS Z 2371: 2000 was performed. Specifically, no. After neutral salt water was sprayed for 24 hours on the surface of GI material having various coatings of 1 to 41, the surface of the GI material was dried. The area ratio of white rust generated on the surface of various dried GI materials was visually measured, and the corrosion resistance of the processed portion was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6.
(Evaluation criteria)
:: The area ratio of white rust is less than 10% ○: The area ratio of white rust is 10% or more and less than 20% Δ: The area ratio of white rust is 20% or more and less than 30% x: of white rust Area ratio is 30% or more
＜耐酸性＞
Ｎｏ．１～４１の各種塗膜を有するＧＩ材を、１質量％の硫酸水溶液中に１分間浸漬した後、水洗して乾燥した。その後、塗膜剥離の有無及びＧＩ材表面の変色（腐食）を目視で観察し、以下の評価基準に従って耐酸性を評価した。その結果を表５及び表６に示す。
（評価基準）
◎：塗膜剥離が見られず、ＧＩ材表面の変色も見られない
○：部分的に塗膜剥離が見られ、ＧＩ材表面の変色が見られる
△：ほぼ全面に塗膜剥離が見られ、ＧＩ材表面に顕著な変色が見られる
×：ほとんどの塗膜が剥離し、ほとんど残存していない <Acid resistant>
No. A GI material having various coatings of 1 to 41 was immersed in a 1% by mass aqueous sulfuric acid solution for 1 minute, washed with water and dried. Then, the presence or absence of coating film peeling and discoloration (corrosion) of GI material surface were observed visually, and acid resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6.
(Evaluation criteria)
:: No peeling of coating film observed, no discoloration of GI material surface observed ○: Partial peeling of coating film observed, discoloration of GI material surface observed Δ: Coating film peeling observed almost all over the surface And noticeable discoloration on the surface of GI material x: Most of the coating film peeled off and hardly remained
Ｎｏ．１～４１の各種塗膜を有するＧＩ材を、１質量％の硫酸水溶液中に１分間浸漬した後、水洗して乾燥した。その後、塗膜剥離の有無及びＧＩ材表面の変色（腐食）を目視で観察し、以下の評価基準に従って耐酸性を評価した。その結果を表５及び表６に示す。
（評価基準）
◎：塗膜剥離が見られず、ＧＩ材表面の変色も見られない
○：部分的に塗膜剥離が見られ、ＧＩ材表面の変色が見られる
△：ほぼ全面に塗膜剥離が見られ、ＧＩ材表面に顕著な変色が見られる
×：ほとんどの塗膜が剥離し、ほとんど残存していない <Acid resistant>
No. A GI material having various coatings of 1 to 41 was immersed in a 1% by mass aqueous sulfuric acid solution for 1 minute, washed with water and dried. Then, the presence or absence of coating film peeling and discoloration (corrosion) of GI material surface were observed visually, and acid resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6.
(Evaluation criteria)
:: No peeling of coating film observed, no discoloration of GI material surface observed ○: Partial peeling of coating film observed, discoloration of GI material surface observed Δ: Coating film peeling observed almost all over the surface And noticeable discoloration on the surface of GI material x: Most of the coating film peeled off and hardly remained
Claims (2)
- 下式（Ｘ）で表される構造と下式（Ｙ）で表される構造とを有するポリシロキサン化合物。
［式（Ｙ）中、Ｒ５は単結合、アルキレン鎖又はオキシアルキレン鎖であり、Ｒ６はヘテロ原子を有する官能基である。］ A polysiloxane compound having a structure represented by the following formula (X) and a structure represented by the following formula (Y).
[In formula (Y), R 5 is a single bond, an alkylene chain or an oxyalkylene chain, and R 6 is a functional group having a hetero atom. ] - 請求項１記載のポリシロキサン化合物と重合物とを含有する組成物。 A composition comprising the polysiloxane compound according to claim 1 and a polymer.
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| JP2017-175558 | 2017-09-13 | ||
| JP2017-175557 | 2017-09-13 | ||
| JP2017175558A JP2019052206A (en) | 2017-09-13 | 2017-09-13 | Composition |
| JP2017175557A JP2019052205A (en) | 2017-09-13 | 2017-09-13 | Polysiloxane compound |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6475567A (en) * | 1987-09-18 | 1989-03-22 | Kanegafuchi Chemical Ind | Cold curing polymer composition |
| JP2003171467A (en) * | 2001-12-05 | 2003-06-20 | Nippon Unicar Co Ltd | Phosphorylated polyorganosiloxane, method for producing the same, flame-retardant and resin composition |
| JP2005179606A (en) * | 2003-12-24 | 2005-07-07 | National Institute Of Advanced Industrial & Technology | Inorganic-organic hybrid material and method for producing the same |
| JP2007196224A (en) * | 2006-01-20 | 2007-08-09 | Samsung Electro Mech Co Ltd | Siloxane dispersion agent and nanoparticle paste composition containing the same |
-
2018
- 2018-09-11 TW TW107131868A patent/TW201920381A/en unknown
- 2018-09-12 WO PCT/JP2018/033752 patent/WO2019054398A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6475567A (en) * | 1987-09-18 | 1989-03-22 | Kanegafuchi Chemical Ind | Cold curing polymer composition |
| JP2003171467A (en) * | 2001-12-05 | 2003-06-20 | Nippon Unicar Co Ltd | Phosphorylated polyorganosiloxane, method for producing the same, flame-retardant and resin composition |
| JP2005179606A (en) * | 2003-12-24 | 2005-07-07 | National Institute Of Advanced Industrial & Technology | Inorganic-organic hybrid material and method for producing the same |
| JP2007196224A (en) * | 2006-01-20 | 2007-08-09 | Samsung Electro Mech Co Ltd | Siloxane dispersion agent and nanoparticle paste composition containing the same |
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