Polymers and compositions having branched organosiloxane macromonomers

Abstract

An object of the present invention is to provide a composition capable of forming a cured film having good water repellency and water slippage and excellent resistance while being a non-fluorine material, and a cured film thereof.SOLUTION: There are provided a polymer obtained by reacting a raw material monomer containing a monomer A which is a branched organosiloxane having at least one addition polymerizable functional group and a monomer B which is an addition polymerizable monomer having a reactive group, a composition containing the polymer, and a cured film thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer containing a branched organosiloxane, a composition thereof, and a cured film thereof. [Background technology]

[0002] Organosiloxane compounds are widely used as water repellents because they form a water-repellent surface layer through chemical treatments such as coatings, which reduces wettability and makes them more resilient to water. However, for waterproofing raincoats and umbrellas, and for coating car windshields, not only water repellency but also water slippage, which allows water droplets to slide off easily, is important. While water-repellent materials using organosiloxane compounds are widely used, no reports have addressed their water slippage. (See, for example, Patent Document 1.) Previously, excellent water repellency and water droplet removal properties have been achieved by incorporating fluoroalkyl groups, which exhibit excellent water repellency, into organosiloxane compounds (Patent Documents 2, 3, and 4). Patent Document 5, in particular, demonstrated water slippage by incorporating a fluorine compound as a comonomer. However, fluorine compounds are undesirable from an environmental perspective. Furthermore, for these applications, film resistance to various conditions, such as scratches and heat, is also important, and the simultaneous achievement of water repellency, water slippage, and resistance is essential. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-356651 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-122106 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-144019 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-030039 [Patent Document 5] Patent Publication No. 2021-121653 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a composition that is a non-fluorine-containing material, yet has good water repellency and water sliding properties, and is capable of forming a cured film with excellent durability, and to provide the cured film. [Means for solving the problem]

[0005] In order to solve the above problems, the inventors of the present invention investigated using commonly known linear organosiloxane compounds, but the water-repellent surface formed had good water repellency but insufficient water slippage, and the durability of the film needed to be improved. As a result of further investigation, they found that by using a polymer having a branched organosiloxane structure and a structure having a reactive group, a cured film with good water repellency, water slippage, and durability could be obtained, and they have completed the present invention.

[0006] According to the present invention, there are provided the following polymers, compositions thereof, and cured films thereof. Item 1. A polymer obtained by reacting raw material monomers including monomer A, which is a branched-chain organosiloxane having at least one addition-polymerizable functional group, and monomer B, which is an addition-polymerizable monomer having a reactive group. Item 2. The polymer according to Item 1, wherein the raw material monomers further include an addition-polymerizable monomer C other than monomer A and monomer B. Item 3. The polymer according to Item 1 or 2, wherein the monomer A is represented by the following formula (1): TIFF2026018863000001.tif2583 In formula (1), p is an integer from 10 to 700; a is 2 or 3; R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, alkyl, alkenyl, aryl, or arylalkyl; The alkyl has 1 to 30 carbon atoms, at least one hydrogen may be replaced by halogen, and at least one -CH2- may be replaced by one or more of -O- and cycloalkylene; The alkenyl has 2 to 3 carbon atoms; The aryl is a substituted or unsubstituted aryl having 6 to 20 carbon atoms; The arylalkyl is composed of a substituted or unsubstituted aryl having 6 to 20 carbon atoms and an alkylene having 1 to 30 carbon atoms, in which at least one hydrogen may be substituted with a halogen and at least one -CH2- may be substituted with one or more of -O- and cycloalkylene; X 1 is an addition polymerizable functional group. Item 4. In equation (1), R 1 , R 2 , R 3 , and R 4 are each independently methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, chloromethyl, vinyl, allyl, phenyl, naphthyl, anthracenyl, pyrenyl, styryl, ethyleneoxy, or polyethyleneoxy. Item 5. In equation (1), R 1 , R 2 , R 3 , and R 4 are each independently methyl, propyl, butyl, or phenyl. Item 6. The polymer according to Item 1 or 2, wherein Monomer B is represented by the following formula (2): TIFF2026018863000002.tif1036 In equation (2), W is a monovalent organic group having any one reactive group selected from an alkenyl group, an alkoxycarbonyl group, an acyl group, a hydroxysilyl group, an alkoxysilyl group, a hydrosilyl group, an oxiranyl group, an oxetanyl group, a hydroxy group, a carboxy group, an isocyanato group, an isothiocyanato group, a mercapto group, an amino group, a formyl group, and an acid anhydride residue; X 2 is an addition polymerizable functional group. Item 7. X in Equation (1) 1 , and X in Eq. (2) 2 Item 7. The polymer according to item 3 or 6, wherein is a monovalent organic group containing a radically polymerizable functional group. Item 8. X in Equation (1) 1 , and X in Eq. (2) 2 and each independently represent a monovalent organic group represented by the following formula (3) or (4): TIFF2026018863000003.tif1477 In equation (3), R 6 is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms; Y 1 Ha-(OCH2CH2) q -, -(OCHCH3CH2) r - or -(OCH2CH(CH3)) s - and; q, r, and s are integers from 0 to 3; Z is a single bond or alkylene having 2 to 20 carbon atoms; In equation (4), Y 2 is a single bond or alkylene having 1 to 10 carbon atoms. Item 9. X in Equation (1) 1 , and X in Eq. (2) 2 Item 9. The polymer according to item 8, wherein is a monovalent organic group having a (meth)acryloyloxy group. Item 10. A composition comprising the polymer according to any one of items 1 to 9. Item 11. A composition comprising the polymer according to any one of items 1 to 9 and a curing agent. Item 12. A cured film obtained from the composition according to item 10 or 11. [Effects of the Invention]

[0007] The use of a branched siloxane as the raw material monomer of the polymer reduces the sliding angle and increases the sliding speed, and the use of a compound having a reactive group as the raw material monomer introduces the reactive group into the side chain of the polymer, which has the effect of improving durability such as scratch resistance. By using the polymer of the present invention, a cured film with good water repellency, water sliding property, and durability can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0009] As used herein, "addition polymerizable" means capable of addition polymerization, "addition polymerizable monomer" means a monomer capable of addition polymerization, and "addition polymerizable functional group" means a functional group capable of addition polymerization. The polymer of the present invention is composed of monomer A and monomer B, or monomer A, monomer B, and monomer C. Monomer A is a branched-chain organosiloxane having at least one addition-polymerizable functional group, monomer B is an addition-polymerizable monomer having a reactive group, and monomer C is an addition-polymerizable monomer other than monomer A and monomer B. The polymer of the present invention has a branched-chain organosiloxane in the main chain or side chain derived from monomer A and a reactive group in the side chain derived from monomer B. Note that "derived from" refers to the polymerized residue when each monomer constitutes the polymer of the present invention.

[0010] <Monomer A: Branched-chain organosiloxane having at least one addition-polymerizable functional group> Monomer A, the raw material monomer for the polymer of the present invention, can be any branched-chain organosiloxane having at least one addition-polymerizable functional group, but is preferably a branched-chain organosiloxane having an addition-polymerizable functional group at one end. A branched-chain organosiloxane having an addition-polymerizable functional group at the end can introduce a siloxane component into the side chain of the polymer. The polymer obtained in this manner exhibits the unique properties of siloxane, such as water repellency, oil repellency, and water slippage.

[0011] Monomer A preferably has a molecular structure represented by the following formula (1). TIFF2026018863000004.tif19150 In formula (1), p is an integer from 10 to 700; a is 2 or 3, R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, alkyl, alkenyl, aryl, or arylalkyl; The alkyl has 1 to 30 carbon atoms, at least one hydrogen may be replaced by halogen, and at least one -CH2- may be replaced by one or more of -O- and cycloalkylene; The alkenyl has 2 to 3 carbon atoms; The aryl is a substituted or unsubstituted aryl having 6 to 20 carbon atoms; The arylalkyl is composed of a substituted or unsubstituted aryl having 6 to 20 carbon atoms and an alkylene having 1 to 30 carbon atoms, in which at least one hydrogen may be substituted with a halogen and at least one -CH2- may be substituted with one or more of -O- and cycloalkylene; X 1 is an addition polymerizable functional group. In addition, multiple R 1R may have the same functional group or different functional groups. 2 and R 3 The same is true for .

[0012] Examples of substituted aryl in the above aryl and arylalkyl include a tolyl group, anisyl group, ethylphenyl group, propylphenyl group, butylphenyl group, xylyl group, and trimethylphenyl group.

[0013] The monomer A used in the present invention is represented by the formula (1) above, R 1 , R 2 , R 3 , and R 4 are each independently preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, chloromethyl, vinyl, allyl, phenyl, naphthyl, anthracenyl, pyrenyl, styryl, ethyleneoxy, or polyethyleneoxy, and more preferably methyl, propyl, butyl, or phenyl.

[0014] The above propyl, butyl, pentyl, hexyl, heptyl and octyl are preferably normal propyl, isopropyl, normal butyl, isobutyl, s-butyl, t-butyl, normal pentyl, normal hexyl, normal heptyl, normal octyl and 2-ethylhexyl.

[0015] The monomer A used in the present invention is a monomer represented by the formula (1) above, wherein X 1 is preferably a monovalent organic group containing a radical polymerizable functional group. Specific examples include monovalent organic groups containing a radical polymerizable functional group such as those represented by the following formula (3) or (4). TIFF2026018863000005.tif1477

[0016] In equation (3), R 6 is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms; Y 1 Ha-(OCH2CH2) q -, -(OCHCH3CH2) r - or -(OCH2CH(CH3)) s - and; q, r, and s are integers of 0 to 3, and Z is a single bond or alkylene having 2 to 20 carbon atoms. 2 is a single bond or alkylene having 1 to 10 carbon atoms.

[0017] X in formula (1) 1 is a monovalent organic group having a (meth)acryloyloxy group (R 6 is more preferably alkyl having 1 carbon atom.

[0018] Only one type of monomer A may be used, or two or more types may be used.

[0019] <Monomer B: Addition-polymerizable monomer having a reactive group> Monomer B, which is a raw material monomer for the polymer of the present invention, is an addition-polymerizable monomer having a reactive group, and is capable of introducing the reactive group into the side chain of the polymer.

[0020] Monomer B preferably has a molecular structure represented by the following formula (2). TIFF2026018863000006.tif6170 In equation (2), W is a monovalent organic group having any one reactive group selected from an alkenyl group, an alkoxycarbonyl group, an acyl group, a hydroxysilyl group, an alkoxysilyl group, a hydrosilyl group, an oxiranyl group, an oxetanyl group, a hydroxy group, a carboxy group, an isocyanato group, an isothiocyanato group, a mercapto group, an amino group, a formyl group, and an acid anhydride residue; and X 2 is an addition polymerizable functional group.

[0021] In this specification, the acid anhydride residue is a monovalent organic group represented by the following formula (I). TIFF2026018863000007.tif2149

[0022] The monomer B used in the present invention is represented by the formula (2) above. 2 is preferably a monovalent organic group containing a radical polymerizable functional group. Specific examples include monovalent organic groups containing a radical polymerizable functional group such as those represented by the following formula (3) or (4). TIFF2026018863000008.tif21112 In equation (3), R 6 is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, Y 1 Ha-(OCH2CH2) q -, -(OCHCH3CH2) r - or -(OCH2CH(CH3)) s wherein q, r, and s are integers from 0 to 3; Z is a single bond or alkylene having 2 to 20 carbon atoms. In equation (4), Y 2 is a single bond or alkylene having 1 to 10 carbon atoms.

[0023] Examples of the monomer B include a (meth)acrylic acid compound having a reactive group and a (meth)styrene compound having a reactive group. Specific examples of the (meth)acrylic acid compound having a reactive group include alkenyl group-containing (meth)acrylates such as methacrylic acid-5-norbornen-2-ylethyl ester, 2-methacryloyloxylethyl tetracyclo[4.4.0.12,5.17,10]dodec-8-ene-3-carboxylate, 2-methacryoxyethyl-2-norbornene-5-carboxylate, and acrylic acid-5-norbornen-2-ylethyl ester; (Meth)acrylate acid esters such as 2-acetoxyethyl acrylate, 2-acetoxyethyl methacrylate, 2-(methacryloyloxy)ethyl-2-naphthoate, and 2-(benzoyloxy)ethyl methacrylate; Coupling group-containing (meth)acrylates such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane; hydrosilyl group-containing (meth)acrylates such as α-acryloyloxymethylethoxydimethylsilane, 2-methyl-acrylic acid dimethylsilanyl ester, α-methacryloyloxymethylethoxydimethylsilane, α-acryloyloxymethylisopropoxydimethylsilane, and dimethylsilyl acrylate; 3,4-Epoxycyclohexylmethyl methacrylate, methacrylic acid epoxycyclohexylmethyl ester, 3-methacryloyloxymethylcyclohexene oxide, (methyl)propionic acid-6-methyl 3,4-epoxycyclohexylmethyl ester, 2,3-epoxytetrahydrobenzyl alcohol methyl propenoate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl acrylate, 2,3-epoxycyclohexyl methacrylate, 2-(3,4-epoxycyclohexyl)ethyl acrylate, 2-(3,4-epoxycyclohexyl)ethyl methacrylate, 3-methacryloyloxymethyl cyclohexene oxide, 3,4-epoxycyclohexylethyl (methyl)propenoate, acrylic acid-(4,5-epoxy-2-methyl-cyclohexylmethyl ester), 3,4-epoxycyclohexylpropyl ester, 3,4-epoxycyclohexylbutyl methacrylate, 3,4-epoxycyclohexylhexyl ester, 3,4-epoxycyclohexylbutyl ester, 3-acryloyloxymethylcyclohexene oxide, 2,3-epoxycyclohexyl acrylate, (methyl)propionic acid-6-methyl-3,4-epoxycyclohexylmethyl ester, (3-ethyloxetan-3-yl)methyl methacrylate, (Meth)acrylates containing an oxiranyl group or an oxetanyl group, such as glycidyl methacrylate, glycidyl acrylate, δ-methylglycidyl acrylate, 2-(normal propyl)glycidyl methacrylate, 2-ethylglycidyl acrylate, 2-(normal butyl)glycidyl acrylate, acrylic acid (2,3-epoxybutyl ester), acrylic acid (2-ethyl-2,3-epoxy-hexyl ester), and acrylic acid-3-pentyl-oxiranylmethyl ester; hydroxy group-containing (meth)acrylates such as 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, 1-acryloyloxy-3-hydroxyadamantane, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-hydroxy-1-methacryloyloxyadamantane, 4-hydroxybutyl acrylate, 4-hydroxyphenyl methacrylate, 6-hydroxyhexyl methacrylate, and pentaethylene glycol monomethacrylate; Carboxy group-containing (meth)acrylates such as acrylic acid and methacrylic acid; Isocyanate group-containing (meth)acrylates such as isocyanate ethyl methacrylate and acryloxyethyl isocyanate; thioisocyanate group-containing (meth)acrylates such as 2-isothiocyanate ethyl acrylate, isocyanate acid-2-propenyloxyisopropyl ester, 2-(2'-methacryloyloxyethyl)oxyethyl isocyanate, and 2-isothiocyanate ethyl methacrylate; mercapto group-containing (meth)acrylates such as mercaptoethyl methacrylate and mercaptoethyl acrylate; Amino group-containing (meth)acrylates such as 2-aminoethyl acrylate, aminomethyl methacrylate, aminomethyl acrylate, acrylic acid aminomethoxymethyl ester, and 2-aminoethyl methacrylate; formyl group-containing (meth)acrylates such as methacrolein, acrylolein, 2-oxoethyl methacrylate, acryloxyacetaldehyde, 2-(formylmethoxy)ethyl methacrylate, 17-oxo-3,6,9,12,15-pentaoxaheptadecyl methacrylate, methylpropionic acid ethenyloxyethoxyethyl ester, and methylpropionic acid-2-ethenyloxyethoxyethyl ester; (Meth)acrylates containing an acid anhydride residue, such as 2-acryloyloxyethyl succinic anhydride, 2-methacryloyloxyethyl succinic anhydride, 2-methacryloyloxyethyl maleic anhydride, 2-acryloyloxyethyl phthalic anhydride, 2-methacryloyloxyethyl hexahydrophthalic anhydride, and 2-acryloyloxyethyl hexahydrophthalic anhydride; etc.

[0024] Specific examples of the (meth)styrene compound having a reactive group include: alkenyl group-containing (meta)styrenes such as 1,2-divinylbenzene, 1,4-divinylbenzene, 1,3-divinylbenzene, 1-allyl-4-vinylbenzene, 1-allyl-2-vinylbenzene, 1-allyl-3-vinylbenzene, 1,3-bis(1-methylethenyl)benzene, 1,4-diisopropenylbenzene, 1-allyl-2-isopropenylbenzene, and para-(1-methylethenyl)allylbenzene; Methyl 4-vinylbenzoate, Methyl 3-vinylbenzoate, Methyl 2-vinylbenzoate, Methyl 3-(cyclopropylmethyl)-5-vinylbenzoate, Methyl 3-cyclopropyl-5-vinylbenzoate, Ethyl 4-vinylbenzoate, Ethyl 2-vinylbenzoate, Ethyl 3-vinylbenzoate, Propyl 4-vinylbenzoate, Butyl 4-vinylbenzoate, Methyl 4-(prop-1-en-2-yl)benzoate, 2-Methyl-4-(prop-1-en-2-yl)benzoic acid Ester bond-containing (meta)styrenes such as methyl, 3-bromo-5-(prop-1-en-2-yl)benzoate, 3-fluoro-4-(prop-1-en-2-yl)benzoate, 2-chloro-4-isopropenylbenzoate, 3-isopropenyl-4-trifluoromethylbenzoate, 4-isopropenyl-3-trifluoromethylbenzoate, 4-(prop-1-en-2-yl)benzoate, and 3-isopropenylbenzoate; acyl group-containing (meth)styrenes such as 1-(4-vinylphenyl)ethanone, 2-acetylstyrene, 1-(3-vinylphenyl)ethan-1-one, 4-vinylbenzophenone, phenyl(2-vinylphenyl)methanone, 4-(2-naphthoyl)styrene, 1-(4-vinylphenyl)propan-1-one, 1-(2-vinylphenyl)propan-1-one, 1-(3-vinylphenyl)propan-1-one, 1-(4-vinylphenyl)butan-1-one, 4-vinylvalerophenone, 4-isopropenylacetophenone, 1-(3-isopropenylphenyl)ethanone, 1-(4-vinylphenyl)-2-methylpropan-1-one, 1-(4-(prop-1-en-2-yl)phenyl)propan-2-one, and 1-[4-(1-methylvinyl)phenyl]propanone; Coupling group-containing (meth)styrenes such as 4-trimethoxysilylstyrene, 4-triethoxysilylstyrene, diethoxy(methyl)(4-vinylphenyl)silane, and dimethoxy(methyl)(4-vinylphenyl)silane; hydrosilyl group-containing (meth)styrenes such as dimethyl(4-vinylphenyl)silane, dimethyl(2-vinylphenyl)silane, (3-vinylphenyl)diethylsilane, and (4-vinylphenyl)diethylsilane; oxiranyl group- or oxetanyl group-containing (meta)styrenes such as 2-(4-vinylbenzyl)oxirane, 4-glycidylmethylstyrene, 4-(epoxyisopropyl)styrene, para-(2-(3,4-epoxycyclohexynyl)ethyl)styrene, 4-[5-(3-ethyloxacyclobut-3-ylmethoxy)pentyloxy]styrene, 4-[6-(3-ethyloxacyclobut-3-ylmethoxy)hexyloxy]styrene, 4-[7-(3-ethyloxetan-3-ylmethoxy)heptyloxy]styrene, 3-ethyl-3-((4-vinylphenoxy)methyl)oxetane, 3-methyl-3-(4-vinylbenzoyloxymethyl)oxetane, and 1-(1-methyl-1,2-epoxyethyl)-3-(1-methylethaneenyl)benzene; hydroxy group-containing (meth)styrenes such as 2-(2-vinylphenyl)ethan-1-ol, 2-(4-vinylphenyl)ethanol, 2-(3-vinylphenyl)ethanol, 3-(2-vinylphenyl)propan-1-ol, 3-(4-vinylphenyl)-1-propanol, and 2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propane; Carboxy group-containing (meth)styrenes such as 4-vinylbenzoic acid, 3-vinylbenzoic acid, 4-(prop-1-en-2-yl)benzoic acid, and 3-(prop-1-en-2-yl)benzoic acid; Isocyanate group-containing (meta)styrenes such as 1-vinyl-4-(2-isocyanatopropan-2-yl)benzene, 4-vinylphenyl isocyanate, 1-vinyl-4-(isocyanatomethyl)benzene, 1-isocyanato-2-vinylbenzene, 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene, 3-isopropenylcumyl isocyanate, and meta-isopropenylbenzyl isocyanate; isothiocyanate group-containing (meth)styrenes such as 1-isocyanate-4-vinylbenzene, 1-isothiocyanate-2-vinylbenzene, 1-fluoro-2-isothiocyanate-3-vinylbenzene, 4-vinylphenyl isothiocyanate, and 2-methyl-5-vinylphenyl isothiocyanate; mercapto group-containing (meta)styrenes such as 4-vinylthiophenol, 3-vinylthiophenol, 4-vinylphenylmethanethiol, and 4-(2-mercaptoethyl)styrene; amino group-containing (meta)styrenes such as 4-vinylaniline, 3-vinylaniline, 2-vinylaniline, 4-vinylbenzylamine, N-benzyl-2-vinylaniline, 4-ethenylbenzylnaphthylamine, 2-vinylbenzylamine, 3-vinylbenzylamine, 4-vinyl-β-phenylethylamine, 2-(3-vinylphenyl)ethylamine, 2-(2-vinylphenyl)ethylamine, N-benzyl-p-vinylphenethylamine, 1-(4-vinylphenyl)-2-phenylethylamine, and N-benzyl-2-(2-ethenylphenyl)ethylamine; Formyl group-containing (meth)styrenes such as 4-vinylbenzaldehyde, 3-vinylbenzaldehyde, 2-vinylbenzaldehyde, 2-(2-vinylphenyl)acetaldehyde, (3-vinylphenyl)acetaldehyde, 4-(prop-1-en-2-yl)benzaldehyde, 3-isopropenylbenzaldehyde, 3-methyl-4-(prop-1-en-2-yl)benzaldehyde, and 2-methyl-4-(1-methylethenyl)benzaldehyde; etc.

[0025] The monomer B used in the present invention is represented by the formula (2) above. 2 It is also preferred that is a monovalent organic group having a (meth)acryloyloxy group.

[0026] Only one type of monomer B may be used, or two or more types may be used.

[0027] <Monomer C: Any addition-polymerizable monomer> In the polymer of the present invention, in addition to the monomer A and monomer B, an addition-polymerizable monomer C other than the monomer A and monomer B can also be used in any proportion as needed to control the glass transition temperature, hardness, thermal decomposition property, compatibility, leveling property, and the contents of the addition-polymerizable monomer A having a siloxane group and the addition-polymerizable monomer B having a reactive group in the polymer.

[0028] Monomer C includes a (meth)acrylic acid compound having no reactive group and a (meth)styrene compound having no reactive group. Specific examples of such a (meth)acrylic acid compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2- Alkyl (meth)acrylates such as ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and toluyl (meth)acrylate; arylalkyl (meth)acrylates such as benzyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, and 3-methoxybutyl (meth)acrylate;, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth)acrylate, 2,2,3,3-tetrafluoro-t-pentyl (meth)acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth)acrylate, 2,2,3,4,4,4-hexafluoro-t-hexyl (meth)acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis(trifluoromethyl)pentyl (meth)acrylate, 2,2,3,3,4,4-hexafluoro 2,2,2,2',2',2'-Hexafluoroisopropyl (meth)acrylate, 2,2,3,3,4,4,4-Heptafluorobutyl (meth)acrylate, 2,2,3,3,4,4,5,5-Octafluoropentyl (meth)acrylate, 2,2,3,3,4,4,5,5,5-Nonafluoropentyl (meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl (meth)acrylate, 3,3,4,4,5,5,6,6,7,7 ,8,8-dodecafluorooctyl (meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl (meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluorodecyl (meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl ( fluoroalkyl (meth)acrylates such as 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-octadecafluoroundecyl (meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-nonadecafluoroundecyl (meth)acrylate, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-eicosafluorododecyl (meth)acrylate;1H,1H-perfluoro-3,6-dioxaheptyl (meth)acrylate, 1H,1H-perfluoro-3,6-dioxaoctyl (meth)acrylate, 1H,1H-perfluoro-3,6-dioxadecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9-trioxadecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9-trioxaundecanyl (meth)acrylate , 1H,1H-perfluoro-3,6,9-trioxatridecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9,12-tetraoxatridecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9,12-tetraoxatetradecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9,12-tetraoxahexadecanyl (meth)acrylate, 1H,1H-per Fluoro-3,6,9,12,15-pentaoxahexadecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9,12,15-pentaoxaheptadecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9,12,15-pentaoxanonadecanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9,12,15,18-hexaoxaicosanyl (meth)acrylate Fluorine-containing polyether methacrylates such as 1H,1H-perfluoro-3,6,9,12,15,18-hexaoxadocosanyl (meth)acrylate, 1H,1H-perfluoro-3,6,9,12,15,18,21-heptaoxatricosanyl (meth)acrylate, and 1H,1H-perfluoro-3,6,9,12,15,18,21-heptaoxapentacosanyl (meth)acrylate; and the like.

[0029] Specific examples of the (meth)styrene compound having no reactive group include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene; fluorostyrenes such as fluoroalkylstyrenes such as p-trifluoromethylstyrene, p-heptafluoropropylstyrene, and p-pentafluoroethylstyrene; and the like.

[0030] In addition, the addition-polymerizable monomer C also includes compounds having a hydrophilic group. For example, oxyalkylene group-containing monomers such as methoxypolyethylene glycol mono(meth)acrylate can be mentioned.

[0031] OnlyM monomer C may be used alone or in combination of two or more.

[0032] <The polymer of the present invention> The polymer of the present invention is a polymer having a branched organosiloxane structure derived from monomer A in the side chain and a reactive group derived from monomer B. It can be synthesized using the above monomer A, which is an essential raw material monomer, monomer B, and monomer C, which is an optional raw material monomer. It may be a sequential polymer such as a block copolymer, a random copolymer, or a graft copolymer, but a random copolymer is preferred.

[0033] The polymer of the present invention can be obtained by polymerizing monomer A, which is a branched organopolysiloxane having one addition-polymerizable functional group in the molecule, addition-polymerizable monomer B having a reactive group, and, if necessary, addition-polymerizable monomer C other than monomer A and monomer B. After obtaining the polymer once, other reactive groups may be introduced through the reactive groups in the side chain and used. For example, after obtaining a polymer as a precursor using an addition-polymerizable monomer having a hydroxy group in monomer B, 2-isocyanatoethyl acrylate can be reacted with the hydroxy group introduced into the side chain to introduce a polymerizable unsaturated bond into the side chain.

[0034] When the composition of the raw material monomers of the polymer of the present invention is represented by the molar fraction (%) of monomer A in the raw material monomers as a, the molar fraction (%) of monomer B as b, and the molar fraction (%) of monomer C as c, it satisfies 0 < a < 100, 0 < b < 100, 0 ≤ c < 100, and a + b + c = 100. Monomer A is preferably 0 < a < 80, more preferably 0.5 < a < 50. Monomer B is preferably 0 < b < 80, more preferably 5 < b < 50.

[0035] The weight average molecular weight of the polymer of the present invention varies depending on the content of monomer B, but is approximately 1,000 to 1,000,000 as a guideline. On the other hand, the molecular weight distribution (Mw / Mn) of the polymer of the present invention is approximately 1.01 to 2.5 as a guideline.

[0036] The polymerization reaction is preferably radical copolymerization in view of simplicity and versatility. The addition polymerization can be carried out using a polymerization initiator, examples of which include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-butyronitrile), dimethyl-2,2'-azobisisobutyrate, and 1,1'-azobis(cyclohexane-1-carbonitrile); peroxides such as benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxyneodecanoate; and dithiocarbamates such as tetraethylthiuram disulfide. Further, examples of the polymerization reaction include living radical polymerization and active energy ray polymerization.

[0037] Living radical polymerization is typified by atom transfer radical polymerization; reversible addition-fragmentation chain transfer; iodine transfer polymerization; and iniferter polymerization, and can be carried out using polymerization initiators described in the following cited documents A to C. Reference A: Radical Polymerization Handbook, edited by Mikio Kamachi and Tsuyoshi Endo, published August 10, 1999, by NTS Publishing. ·Citation B: HANDBOOK OF RADICAL POLYMERIZATION, K. Matyjaszewski, TP Davi s, Eds., John Wiley and Sons, Canada 2002. Reference C: JP 2005-105265 A Active energy ray polymerization can be carried out using the compound described in Reference D as an active energy ray polymerization initiator. Reference D: Photopolymer Forum, Photosensitive Materials List Book, March 31, 1996, published by Bunshin Publishing.

[0038] The amount of the polymerization initiator used in the above addition polymerization may be about 0.01 to 10 mol % based on the total number of moles of the monomers.

[0039] Examples of solvents used in the above polymerization reaction include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, Examples of suitable solvents include propylene carbonate, amide solvents (N,N-dimethylformamide, N,N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFC) solvents (HFCs with 2 to 4, 5, or 6 or more carbon atoms), perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine-containing solvents (fluoroethers, fluoropolyethers, fluoroketones, fluoroalcohols), aromatic fluorine-containing solvents (α,α,α-trifluorotoluene, hexafluorobenzene), and water. These solvents may be used alone or in combination. The amount of solvent used should be sufficient to achieve a monomer concentration of approximately 10 to 80% by weight.

[0040] The reaction temperature is not particularly limited, and may be approximately 0 to 200°C, preferably room temperature to approximately 150°C. The polymerization reaction can be carried out under reduced pressure, normal pressure, or increased pressure, depending on the type of monomer and type of solvent. The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. This is to prevent the generated radicals from being deactivated by contact with oxygen, which would result in a decrease in the polymerization rate, and to obtain a polymer with an appropriately controlled molecular weight. Furthermore, the polymerization reaction is preferably carried out in a polymerization system from which dissolved oxygen has been removed under reduced pressure (the polymerization reaction may be carried out under reduced pressure after the dissolved oxygen has been removed under reduced pressure).

[0041] The polymer obtained in the solution may be purified or isolated by a conventional method, or may be used as the solution for forming a coating film or the like.

[0042] <Resin composition> The composition of the present invention is a composition containing the polymer of the present invention. The polymer of the present invention may be used alone or in combination of two or more.

[0043] The resin composition of the present invention preferably contains a curing agent capable of forming a crosslinked structure by reaction of the reactive group of monomer B of the polymer of the present invention. The curing agent capable of forming a crosslinked structure can form a crosslinked structure by reacting reactive groups derived from monomer B of the polymer with each other, or by reacting a reactive group derived from monomer B of the polymer with a reactive group of the curing agent, thereby forming a cured film with excellent resistance properties such as scratch resistance and heat resistance. When a polymer is used in which another reactive group has been introduced via a reactive group in a side chain derived from monomer B after the polymer has been obtained, a crosslinked structure can be formed by reacting the other introduced reactive groups with each other, or by reacting the other introduced reactive group with a reactive group of the curing agent, thereby forming a cured film with excellent resistance properties such as scratch resistance and heat resistance.

[0044] Examples of such curing agents capable of forming a crosslinked structure through the reaction of reactive groups include compounds having two or more reactive functional groups per molecule, coupling agents, epoxy curing agents, photopolymerization initiators, and hydrosilylation reaction catalysts.

[0045] Examples of compounds having two or more reactive functional groups per molecule include: When the reactive group of monomer B contains an alkenyl group, a compound having two or more alkenyl groups, hydrosilyl groups, and mercapto groups per molecule; When an alkoxycarbonyl group or an acyl group is contained, the compound has two or more hydrosilyl groups, hydroxy groups, carboxy groups, mercapto groups, or amino groups per molecule; In the case of containing a hydroxysilyl group or an alkoxysilyl group, a compound having two or more hydroxysilyl groups, alkoxysilyl groups, hydrosilyl groups, or hydroxy groups per molecule; When a hydrosilyl group is contained, it is a compound having two or more alkenyl groups, ester groups, acyl groups, hydroxysilyl groups, alkoxysilyl groups, hydroxy groups, carboxy groups, mercapto groups, amino groups, or formyl groups per molecule; When an oxiranyl group or an oxetanyl group is contained, the compound has two or more hydroxy groups, carboxy groups, mercapto groups, or amino groups per molecule; When a hydroxy group is contained, it is a compound having two or more hydroxysilyl groups, alkoxysilyl groups, hydrosilyl groups, oxiranyl groups, oxetanyl groups, hydroxy groups, carboxy groups, isocyanato groups, isothiocyanato groups, or amino groups per molecule; When a carboxy group is contained, it is a compound having two or more ester, hydroxysilyl, alkoxysilyl, oxiranyl, oxetanyl, hydroxy, carboxy, isocyanato, isothiocyanato, or amino groups per molecule; If it contains an isocyanato group or an isothiocyanato group, it is a compound having two or more hydroxyl groups, carboxyl groups, mercapto groups, or amino groups per molecule; When a mercapto group is contained, the compound has two or more alkenyl groups, esters, hydroxysilyl groups, alkoxysilyl groups, hydrosilyl groups, oxiranyl groups, oxetanyl groups, carboxy groups, isocyanato groups, or isothiocyanato groups per molecule; When an amino group is contained, the compound has two or more ester, acyl, alkoxysilyl, hydrosilyl, oxiranyl, oxetanyl, carboxy, isocyanato, isothiocyanato, formyl, or acid anhydride groups per molecule; If a formyl group is contained, it is a compound having two or more hydrosilyl or amino groups per molecule; If it contains an acid anhydride residue, it may contain a hydroxy group, a carboxy group, a mercapto group, or an amino group. Examples include compounds having two or more of these per molecule.

[0046] Specific examples of compounds having two or more reactive functional groups per molecule include: Vinylcyclohexene dioxide, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, epichlorohydrin-modified ethylene glycol di(meth)acrylate, epichlorohydrin-modified diethylene glycol di(meth)acrylate, epichlorohydrin-modified triethylene glycol di(meth)acrylate, epichlorohydrin-modified tetraethylene glycol di(meth)acrylate, epichlorohydrin-modified polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin-modified propylene Glycol di(meth)acrylate, epichlorohydrin-modified dipropylene glycol di(meth)acrylate, epichlorohydrin-modified tripropylene glycol di(meth)acrylate, epichlorohydrin-modified tetrapropylene glycol di(meth)acrylate, epichlorohydrin-modified polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, Propylene oxide-modified trimethylolpropane tri(meth)acrylate, epichlorohydrin-modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, epichlorohydrin-modified glycerol tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, epichlorohydrin-modified 1,6-Hexanediol di(meth)acrylate, methoxylated cyclohexyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, diglycerin tetra(meth)acrylate, diglycerin ethylene oxide-modified acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol tetra(meth)acrylate Acrylates, alkyl-modified dipentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, polybasic acid-modified (meth)acrylic oligomer, allylated cyclohexyl di(meth)acrylate, bis[(meth)acryloxyneopentyl glycol] adipate, bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, ethylene oxide-modified bisphenol F di(meth)acrylate, bisphenol S di(meth)acrylate, ethylene oxide-modified bisphenol S di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol (meth)acrylate, dicyclopentanyl diacrylate, polyester diacrylate, polyester triacrylate, polyester tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, ethylene oxide-modified phosphate di(meth)acrylate, ethylene oxide-modified phosphate tri(meth)acrylate, epichlorohydrin-modified phthalic acid di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, triglycerol di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, ethylene oxide-modified isocyanuric acid diacrylate, ethylene oxide-modified isocyanuric acid triacrylate, caprolactone-modified tris[(meth)acryloxyethyl]isocyanurate, (meth)acrylated isocyanurate, phenyl glycidyl ether acrylate, hexamethylene diisocyanate, urethane prepolymer, phenyl glycidyl ether acrylate, toluene diisocyanate Compounds having two or more alkenyl groups, such as urethane prepolymers, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymers, pentaerythritol triacrylate toluene diisocyanate urethane prepolymers, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymers, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymers, non-yellowing oligourethane acrylates, (meth)acrylic acid modified phenol novolac epoxy resins, (meth)acrylic acid modified cresol novolac epoxy resins, and carboxylic acid-containing urethane acrylate oligomers; Compounds having two or more mercapto groups, such as pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and trimethylolpropane tris(3-mercaptobutyrate); Compounds having two or more isocyanate groups, such as 2,4-toluene diisocyanate, tolylene-3,4-diisocyanate, 2,6-toluene diisocyanate, tolylene-2,3-diisocyanate, 2,4,6-trimethylbenzene-1,3-diyl diisocyanate, toluene-2,5-diisocyanate, tetramethylxylene diisocyanate, toluene-3,5-diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, 4,6-dimethyl-m-xylene diisocyanate, di(4-isocyanatophenyl)methane, 2,2'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, tris(6-isocyanatohexyl)isocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate; Compounds having two or more thioisocyanate groups, such as 1,6-hexanedithioisocyanate, dibutyltin dithioisocyanate, 1,4-phenyldithioisocyanate, and disodium 4,4'-diisothiocyanato-2,2'-stilbenedisulfonate; 1,2,4,5-Cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-biphthalic anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-( compounds having two or more acid anhydride residues, such as ethyne-1,2-diyl)diphthalic anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3,5,6-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4'-biphthalic anhydride, 4,4'-biphthalic anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride; Compounds having two or more esters, such as dimethyl glutarate, diethyl glutarate, diethyl adipate, dimethyl adipate, diethyl 2,5-dibromoadipate, dimethyl pimelate, dimethyl-2,6-dibromoheptanedioate, diethyl 2,6-dibromoheptanedioate, diethyl pimelate, diisopropyl adipate, dimethyl isophthalate, dimethyl phthalate, and dimethyl terephthalate; Compounds with two or more carboxy groups, such as isophthalic acid, terephthalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and the like; Compounds having two or more formyl groups, such as glutaraldehyde, isophthalaldehyde, terephthalaldehyde, and 2-methylpentadial; Compounds having two or more hydroxysilyl groups, such as tetramethyl-1,3-disiloxanediol, dimethylsilanediol, diphenylsilanediol, 1,3-dimethyl-1,3-diphenyldisiloxane-1,3-diol, 1,3-dihydroxy-1,1-dimethyl-3,3-diphenylsiloxane, 1,1,3,3-tetraphenyldisiloxane-1,3-diol, 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol, and 1,1,3,3,5,5-hexaphenyltrisiloxane-1,5-diol; Compounds having two or more alkoxysilyl groups, such as dimethoxymethylphenylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, tetramethyl-1,3-dimethoxydisiloxane, 1,3-dimethoxy-1,3-dimethyl-diphenylsiloxane, 1,1-dimethyl-1,2-dimethoxy-1,1-diphenyldisiloxane, 1,5-dimethoxy-1,1,3,3,5,5-hexaphenyltrisiloxane, and 1,5-dimethoxy-1,1,3,3,5,5-hexamethyltrisiloxane; Compounds having two or more hydrosilyl groups, such as 1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl-1,3-diphenyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane; Compounds having two or more hydroxy groups, such as 2,6-bis(hydroxymethyl)-4-methylphenol, 4,6-bis(hydroxymethyl)-2-methylphenol, 2,6-dihydroxymethyl-3-methylphenol, 1,1-bis(2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl)butane, 1,1-bis(4-hydroxy-3,5-dihydroxymethylphenyl)butane, and bisphenol A; Compounds having two or more acyl groups, such as acetylacetone, 3,5-heptanedione, 5-methylhexane-2,4-dione, 2,2-dimethyl-3-oxopentanal, 4-methyl-2,5-heptanedione, 3,6-octanedione, acetonylacetone, 2,6-heptanedione, 3,8-decanedione, 2,7-octanedione, 3,8-decanedione, 1,3-diacetylbenzene, 1,3,5-benzenetriscarbonyl chloride, terephthaloyl dichloride, benzene-1,3-dicarbonyl dichloride, phthaloyl dichloride, and 5-methylisophthaloyl chloride; Compounds having two or more amino groups, such as hydrazine, hexamethylenediamine, 1,3-diaminobenzene, and 1,4-diaminobenzene; Hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexyl San-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g., Celloxide 2021P; trade name; manufactured by Daicel Corporation), 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane (e.g., CELLOXIDE 3000; trade name; manufactured by Daicel Corporation), a mixture of 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol (e.g., TECHMORE VG3101L (trade name; manufactured by Printec Co., Ltd.), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane, 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl ether, 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150; trade name; manufactured by Daicel Corporation), 3,3',5,5'-tetramethyl-4,4'-biphenol diglycidyl ether (e.g., YX4000H; trade name; manufactured by Mitsubishi Chemical Corporation), 4,4'-isopropylidenediphenol Examples of such glycerides include hydrogenated polycondensates of 2,3-epoxypropane and 1-chloro-2,3-epoxypropane (e.g., YX8034, trade name, manufactured by Mitsubishi Chemical Corporation), α-2,3-epoxypropoxyphenyl-ω-hydropoly[2-(2,3-epoxypropoxy)benzylidene-2,3-epoxypropoxyphenylene] (e.g., EPPN-501H, trade name, manufactured by Nippon Kayaku Co., Ltd.), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol, as well as compounds having two or more oxiranyl or oxetanyl groups.

[0047] When the reactive group of the monomer B contains a hydroxysilyl group or an alkoxysilyl group, it is also preferable to use a coupling agent. Examples of coupling agents include silane-based coupling agents such as 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (e.g., trade name: Sila-Ace S510, manufactured by JNC Corporation), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (e.g., trade name: Sila-Ace S530, manufactured by JNC Corporation), 3-mercaptopropyltrimethoxysilane (e.g., trade name: Sila-Ace S810, manufactured by JNC Corporation), and a polymer of 3-glycidyl-oxypropyl-trimethoxysilane (e.g., trade name: CoatOSil MP200, manufactured by Momentive Performance Materials LLC); aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate; and titanate-based coupling agents such as tetraisopropylbis(dioctylphosphite)titanate.

[0048] When the reactive group of monomer B contains an oxiranyl group or an oxetanyl group, it is also preferable to use an epoxy curing agent. Examples of epoxy curing agents include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride; aromatic polycarboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride; styrene-maleic anhydride polymers, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and the San-Aid SI series.

[0049] When a crosslinked structure is formed by a photopolymerization reaction, a photopolymerization initiator is required. The crosslinked structure may be formed by reacting reactive groups on polymer side chains with each other, by a compound having two or more of the above-mentioned reactive functional groups per molecule, or by both. Examples of photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (e.g., trade names: Omnirad 907, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (for example, trade name: Omnirad 369, IGM Resins BV), ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (for example, trade name: IRGACURE OXE01, BASF Japan Ltd.), ethanone, 1-[9H-ethyl-6-(2-methylbenzoyl)-9-carbazol-3-yl]-, 1-(O-acetyloxime) (for example, trade name: IRGACURE OXE02, BASF Japan Ltd.), IRGACURE OXE03 (for example, trade name; manufactured by BASF Japan Ltd.), 1,2-propanedione-1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-acetyloxime) (for example, trade name;ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), ADEKA ARCLES NCI-831 (trade name; manufactured by ADEKA Corporation), ADEKA OPTOMER N-1919 (trade name; manufactured by ADEKA Corporation), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine )-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzoxazole (aminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole midazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, and bis(η; 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, tris(pentafluorophenyl)borane, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate [4-(phenylthio)phenyl]sulfonium trifluorotris(pentafluoroethyl)phosphate, diphenyl[4-(phenylthio)phenyl]sulfonium trifluorotris(pentafluoroethyl)phosphate, (9-oxo-9H-thioxanthen-2-yl)[4-[(9-oxo-9H-thioxanthen-2-yl)thio]phenyl](phenyl)sulfonium trifluorotris(perfluoroethyl)phosphate(V), (4-isopropylphenyl)(p-tolyl)iodonium trifluorotris(perfluoroethyl)phosphate(V), and the like.

[0050] When forming a crosslinked structure by a hydrosilylation reaction, a hydrosilylation catalyst is required. The crosslinked structure may be formed by reacting reactive groups on polymer side chains with each other, or by forming a crosslinked structure via a compound having two or more of the above-mentioned reactive functional groups per molecule, or by both. Examples of the hydrosilylation catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Examples of platinum-based catalysts include chloroplatinic acid, Karstedt catalysts, and Wilkinson complexes.

[0051] Alternatively, the polymers of the present invention may be combined so that the reactive groups derived from the monomer B react with each other to form a composition without containing the above-mentioned curing agent.

[0052] Other components may be added to the composition of the present invention depending on the purpose, such as viscosity adjustment, wettability of the coating film, storage stability, etc. Components contained in the composition other than the polymer and curing agent include solvents, surfactants, fillers, rheology modifiers, stabilizers, color pigments, etc.

[0053] The solvent is not particularly limited, and the solvent used in synthesizing the polymer of the present invention can be used. It is preferable to appropriately adjust the ratio of the solvent to the polymer to be used according to the viscosity and molecular weight of the polymer to be used so that the composition viscosity is suitable for coating.

[0054] Examples of the surfactant include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, silicone surfactants, and fluorine surfactants.

[0055] The polymer of the present invention can be added to thermosetting or thermoplastic resins. Addition of the polymer can impart water-slip properties, water repellency, and the like to the resin. Specific examples of thermosetting resins include phenolic resins, melamine resins, urea resins, alkyd resins, epoxy resins, unsaturated polyester resins, and polyurethanes. Specific examples of thermoplastic resins include polyethylene, polypropylene, polyvinyl acetate, polyurethane, polylactic acid, polytetrafluoroethylene (PTFE), ABS resin, AS resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polyamide, nylon, polyacetal, polycarbonate, modified polyphenylene ether, polyester, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, liquid crystal polymer, polyetheretherketone, polyimide, and polyamideimide.

[0056] <Cured film> The cured film of the present invention is formed by applying the composition to a substrate surface under conditions that allow the reactive groups to react to form a crosslinked structure. Examples of applicable substrates include inorganic substrates such as glass, ceramic, and metals (e.g., iron, stainless steel, and aluminum), and organic substrates such as plastics and wood. Examples of the substrate shape include plates, blocks, films, particles, and powders. The composition can be made into a photocurable or thermosetting material by selecting a curing agent, and can be cured by heating, active energy ray irradiation, or both. A cured film can be obtained by appropriately adjusting the wavelength of active energy ray irradiation, heating temperature, and heating time depending on the curing agent. An example of curing conditions is heating at 10 to 280°C for 2 minutes to 2 hours when the reactive group contains an epoxy group and an epoxy curing agent is used as the curing agent. The cured film thus formed is resistant to water and organic solvents and has water-repellent, oil-repellent, and water-slip properties. [Example]

[0057] The present invention will be described in more detail below. In the examples, "parts" and "%" are all by weight (parts by weight, % by weight) unless otherwise specified. The present invention is not limited to these examples.

[0058] <Monomers used> Monomer A: (A-1) Tri-branched organosiloxane synthesized in Synthesis Example 1 below (A-2) Bibranched organosiloxane synthesized in Synthesis Example 2 below Linear organosiloxane having addition polymerizable groups (comparison monomer for Monomer A): (A-3) Silaplane (registered trademark) FM-0721 (product name, manufactured by JNC Corporation) Monomer B: (B-1) Glycidyl methacrylate Monomer C: (C-1) Butyl methacrylate <Polymerization initiator used> V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., dimethyl-2,2'-azobisisobutyrate)

[0059] [Synthesis Example 1] Synthesis of 3-branched organosiloxane (A-1) A 500 mL four-neck flask equipped with a reflux condenser, thermometer, and septum cap was charged with 50.07 g of hexamethylcyclotrisiloxane and 225 mL of THF and sealed with nitrogen. The flask was placed in an oil bath maintained at 30°C and heated. When the liquid temperature reached 30°C, 18.8 mL of n-butyllithium (1.6 M hexane solution) was added to initiate polymerization. After 4 hours of reaction, 4.1 mL of triethylamine and 2.2 mL of 3-trichlorosilylpropyl methacrylate were added. After 17 hours of reaction, the reaction was terminated by adding 50 mL of distilled water and 50 mL of heptane. After completion of the reaction, the reaction mixture was transferred to a separatory funnel. The aqueous and organic layers were separated using the separatory funnel, and the aqueous layer was discarded. Next, 50 mL of 1N hydrochloric acid was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of saturated aqueous sodium bicarbonate solution was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of distilled water was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried over anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator, and the solvent was distilled off at 55°C and 1 kPa. The resulting oil (48.71 g) had GPC data (dimethylpolysiloxane standard): Mn = 4314, Mw / Mn = 1.25. The structure of the final product is shown in formula (1-1). TIFF2026018863000009.tif1874

[0060] [Synthesis Example 2] Synthesis of 2-branched organosiloxane (A-2) A 500 mL four-neck flask equipped with a reflux condenser, thermometer, and septum cap was charged with 50.10 g of hexamethylcyclotrisiloxane and 225 mL of toluene and sealed with nitrogen. The flask was placed in an oil bath maintained at 30°C and heated. When the liquid temperature reached 30°C, 12.8 mL of n-butyllithium (1.6 M hexane solution) was added to initiate polymerization. After 4 hours of reaction, 2.8 mL of triethylamine and 2.3 mL of 3-methacryloxypropylmethyldichlorosilane were added. After 17 hours of reaction, the reaction was terminated by adding 50 mL of distilled water and 50 mL of heptane. After completion of the reaction, the reaction mixture was transferred to a separatory funnel. The aqueous and organic layers were separated using the separatory funnel, and the aqueous layer was discarded. Next, 50 mL of 1N hydrochloric acid was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of saturated aqueous sodium bicarbonate solution was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of distilled water was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried over anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator, and the solvent was distilled off at 55°C and 1 kPa. The resulting oil (49.57 g) had GPC data (dimethylpolysiloxane standard): Mn = 4836, Mw / Mn = 1.20. The structure of the final product is shown in formula (1-2). TIFF2026018863000010.tif1874

[0061] [Example 1] Copolymerization of 3-branched organosiloxane with butyl methacrylate and glycidyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80°C and heated. Once the temperature reached 80°C, a mixture of (A-1) (0.10 g), butyl methacrylate (7.90 g), glycidyl methacrylate (2.00 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.04 g) obtained in Synthesis Example 1 was added to the flask via the dropping funnel over a 2-hour period. After 4 hours of reaction, the oil bath was removed and the mixture was cooled to room temperature. The resulting polymer solution (49.85 g) had GPC data (based on polymethyl methacrylate): Mn = 47641, Mw / Mn = 2.41.

[0062] [Example 2] Copolymerization of dibranched organosiloxane with butyl methacrylate and glycidyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80°C and heated. When the temperature reached 80°C, a mixture of (A-2) (0.10 g), butyl methacrylate (7.90 g), glycidyl methacrylate (2.00 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.04 g) obtained in Synthesis Example 2 was added to the flask via the dropping funnel over a 2-hour period. After the reaction was completed for 4 hours, the oil bath was removed and the flask was cooled to room temperature. The resulting polymer solution (47.40 g) had GPC data (based on polymethyl methacrylate): Mn = 41305, Mw / Mn = 2.04.

[0063] [Comparative Example 1] Copolymerization of linear organosiloxane with butyl methacrylate and glycidyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80 °C and heated. Once the temperature reached 80 °C, a mixture of (A-3) FM-0721 (0.10 g), butyl methacrylate (8.00 g), glycidyl methacrylate (2.00 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.04 g) was added to the flask via the dropping funnel over 2 hours. After 4 hours of reaction, the oil bath was removed and the mixture was cooled to room temperature. The resulting polymer solution (48.06 g) had GPC data (based on polymethyl methacrylate): Mn = 44892, Mw / Mn = 2.16.

[0064] [Comparative Example 2] Copolymerization of butyl methacrylate and glycidyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80 °C and heated. Once the temperature reached 80 °C, a mixture of butyl methacrylate (8.00 g), glycidyl methacrylate (2.00 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.04 g) was added to the flask via the dropping funnel over 2 hours. After 4 hours of reaction, the oil bath was removed and the flask was cooled to room temperature. The resulting polymer solution (48.06 g) had GPC data (based on polymethyl methacrylate): Mn = 40538, Mw / Mn = 2.11.

[0065] [Comparative Example 3] Copolymerization of 3-branched organosiloxane and butyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80°C and heated. Once the temperature reached 80°C, a mixture of (A-1) (0.30 g), butyl methacrylate (9.70 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.20 g) obtained in Synthesis Example 1 was added to the flask over 2 hours. After 4 hours of reaction, the oil bath was removed and the mixture was cooled to room temperature. The resulting polymer solution (49.62 g) had GPC data (based on polymethyl methacrylate): Mn = 13445, Mw / Mn = 2.41.

[0066] Comparative Example 4: Copolymerization of dibranched organosiloxane and butyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80°C and heated. Once the temperature reached 80°C, a mixture of (A-2) (0.30 g), butyl methacrylate (9.70 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.20 g) obtained in Synthesis Example 2 was added to the flask via the dropping funnel over a 2-hour period. After 4 hours of reaction, the oil bath was removed and the mixture was cooled to room temperature. The resulting polymer solution (49.94 g) had GPC data (based on polymethyl methacrylate): Mn = 14392, Mw / Mn = 2.36.

[0067] [Comparative Example 5] Copolymerization of linear organosiloxane and butyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80 °C and heated. Once the temperature reached 80 °C, a mixture of (A-3) FM-0721 (0.30 g), butyl methacrylate (9.70 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.20 g) was added to the flask via the dropping funnel over 2 hours. After 4 hours of reaction, the oil bath was removed and the flask was cooled to room temperature. The resulting polymer solution (48.81 g) had GPC data (based on polymethyl methacrylate): Mn = 14285, Mw / Mn = 2.36.

[0068] [Comparative Example 6] Homopolymerization of butyl methacrylate A 100 mL four-neck flask equipped with a reflux condenser, thermometer, dropping funnel, and ball stopper was charged with 24.00 g of 2-methoxy-1-methylethyl acetate and sealed with nitrogen. The flask was placed in an oil bath maintained at 80°C and heated. Once the temperature reached 80°C, a mixture of butyl methacrylate (10.00 g), 2-methoxy-1-methylethyl acetate (16.00 g), and V-601 (0.20 g) was added to the flask via the dropping funnel over 2 hours. After 4 hours of reaction, the oil bath was removed and the flask was cooled to room temperature. The resulting polymer solution (48.19 g) had GPC data (based on polymethyl methacrylate): Mn = 13596, Mw / Mn = 2.36.

[0069] For the polymers obtained in Examples 1 and 2 and Comparative Examples 1 to 6, the monomer ratio, Mn, and Mw / Mn are shown in Table 1. [Table 1] TIFF2026018863000011.tif54150

[0070] The evaluation items and evaluation methods are shown below. <Film thickness> A portion of the cured film on the cured film substrate was scraped off with a cutter, and the resulting step height was measured using a contact step height gauge KLA Tencor P+16 (manufactured by KLA Tencor Corp.) The average value measured at three different points was taken as the film thickness. <Scratch resistance> The pencil hardness of the resulting cured film was measured using a pencil hardness tester according to JIS K5600-5-4. Scratch resistance was judged as ◯ if the pencil hardness was HB or higher, and × if the pencil hardness was less than HB. <Solvent resistance> A 1.3 μL droplet of diiodomethane was formed on the tip of the syringe needle, and then the syringe needle was moved to deposit the droplet on the surface of the cured film substrate. 60 seconds after deposition, the droplet was removed using a cleanroom rag. The droplet was then checked for the presence or absence of traces of droplets due to swelling or dissolution of the film. The film's solvent resistance was judged as "X" if there were traces, and "O" if there were no traces.

[0071] <Contact angle> A DropMaster 500 (Kyowa Interface Science Co., Ltd.) was used to measure the contact angle. Purified water and diiodomethane (Tokyo Chemical Industry Co., Ltd.) were used as probe liquids. A 1.8 μL droplet of distilled water or 1.3 μL of diiodomethane was formed at the tip of a syringe needle, and the syringe needle was moved to deposit the droplet on the surface of the cured film substrate. A still image of the droplet was taken 1 second after deposition. The image was taken at a preset time of 1000 ms after deposition in the DropMaster control program "FAMAS." Based on the still image, the contact angle was determined using the θ / 2 method, assuming the outline of the water droplet to be a perfect circle. Five measurements were taken on the same sample, and the average value was used as the contact angle. When comparing the same liquid, the higher the contact angle, the better the water repellency. When purified water was used as the probe liquid, a contact angle of 100° or more was marked as ◯, and an angle less than 100° was marked as ×. When diiodomethane was used as the probe liquid, a contact angle of 55° or more was marked as ◯, and an angle less than 55° was marked as ×.

[0072] <Sliding angle> A DropMaster 500 (Kyowa Interface Science Co., Ltd.) was used to measure the sliding angle. Purified water was used as the probe liquid. A 15 μL droplet was formed on the tip of a syringe needle, and then the syringe needle was moved to deposit the droplet on the surface of the cured film substrate. After deposition, the sample stage was tilted at a rate of 2 degrees per second, and still images of the droplet on the cured film substrate surface were taken every degree of tilt. The tilt angle of the sample stage when the contact point on the retreating side of the droplet moved 1 mm was defined as the sliding angle. If the contact point on the advancing side of the droplet could not move 1 mm at a tilt angle of 90 degrees, it was considered to have "not slid down." Five measurements were taken for the same sample, and the average value was defined as the sliding angle. The smaller the sliding angle, the better the water sliding property. If there was no sliding, it was marked with an X; if the sliding angle was 30° or more and less than 90°, it was marked with a △; if the sliding angle was 15° or more and less than 30°, it was marked with an ◯; and if the sliding angle was less than 15°, it was marked with an ◎.

[0073] <Sliding speed> A DropMaster 500 (Kyowa Interface Science Co., Ltd.) was used to measure the sliding speed. Purified water was used as the probe liquid. A 20 μL water droplet was formed using a syringe needle on the surface of a cured film substrate placed on a sample stage previously tilted at 35 degrees. Next, after the droplet was formed, the syringe needle was moved and the syringe needle was removed from the droplet, causing the droplet to slide down. If the contact line on the advancing side of the droplet had not moved 10 mm 10 seconds after the syringe needle was removed, it was considered to have "not slid down." The sliding speed (mm / s) was calculated from the time (seconds) for the droplet to slide down when both the advancing and retreating sides of the droplet had moved at least 10 mm. Five measurements were taken for the same sample, and the average value was used as the sliding speed. The faster the sliding speed, the better the water sliding ability. If there was no sliding, it was marked as ×; if the sliding speed was 1 mm / s or more but less than 40 mm / s, it was marked as △; if the sliding speed was 40 mm / s or more but less than 45 mm / s, it was marked as 〇; and if the sliding speed was 45 mm / s or more, it was marked as ◎. The smaller the sliding angle and the faster the sliding speed, the better the sliding performance.

[0074] <Preparation of composition, fabrication and evaluation of cured film substrate> [Example 3] A composition was prepared by mixing 0.8 g of the polymerization liquid obtained in Example 1 and 0.16 g of trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Trading Co., Ltd.). The obtained composition was spin-coated onto a glass substrate at 1000 rpm for 10 seconds, and then heated at 200°C for 1 hour to cure the composition coating, producing a cured film substrate. The film thickness of the cured film was 2 μm. The glass substrate used was Eagle XG (trade name, manufactured by Corning Incorporated). The obtained cured film substrate was evaluated for scratch resistance, solvent resistance, contact angle, sliding angle, and sliding speed as described above.

[0075] [Example 4] The preparation of a composition, production of a cured film substrate, and evaluation were carried out in accordance with Example 3, except that the polymerization liquid obtained in Example 1 was replaced with the polymerization liquid obtained in Example 2. The thickness of the cured film was 2 μm. Comparative Example 7 The preparation of a composition, production of a cured film substrate, and evaluation were carried out in accordance with Example 3, except that the polymerization liquid obtained in Example 1 was replaced with the polymerization liquid obtained in Comparative Example 1. The thickness of the cured film was 2 μm. [Comparative Example 8] The preparation of a composition, production of a cured film substrate, and evaluation were carried out in accordance with Example 3, except that the polymerization liquid obtained in Example 1 was replaced with the polymerization liquid obtained in Comparative Example 2. The thickness of the cured film was 2 μm.

[0076] Comparative Example 9 A composition was prepared in accordance with Example 1, except that the polymerization liquid obtained in Example 1 was replaced with the polymerization liquid obtained in Comparative Example 3. The resulting composition was spin-coated onto a glass substrate at 1000 rpm for 10 seconds, and then dried at 150°C for 5 minutes to cure the composition coating, producing a cured film substrate. The cured film had a thickness of 2 μm. The glass substrate used was Eagle XG (trade name, manufactured by Corning Inc.). Using the resulting cured film substrate, scratch resistance and solvent resistance were evaluated in the same manner as in Example 3. Since scratches and droplet marks were observed in the evaluation of scratch resistance and solvent resistance, evaluation of contact angle, sliding angle, and sliding speed were not performed.

[0077] [Comparative Example 10] A composition was prepared and a cured film substrate was produced in accordance with Comparative Example 9, except that the polymerization liquid obtained in Comparative Example 3 was replaced with the polymerization liquid obtained in Comparative Example 4 to prepare a composition. The film thickness of the cured film was 2 μm. Using the obtained cured film substrate, the scratch resistance and solvent resistance were evaluated in the same manner as in Example 3. Since scratches and droplet marks were observed in the evaluation of scratch resistance and solvent resistance, the contact angle, sliding angle, and sliding speed were not evaluated. [Comparative Example 11] A composition was prepared and a cured film substrate was produced in accordance with Comparative Example 9, except that the polymerization liquid obtained in Comparative Example 3 was replaced with the polymerization liquid obtained in Comparative Example 5 to prepare a composition. The film thickness of the cured film was 2 μm. Using the obtained cured film substrate, the scratch resistance and solvent resistance were evaluated in the same manner as in Example 3. Since scratches and droplet marks were observed in the evaluation of scratch resistance and solvent resistance, the contact angle, sliding angle, and sliding speed were not evaluated. [Comparative Example 12] A composition was prepared and a cured film substrate was produced in accordance with Comparative Example 9, except that the polymerization liquid obtained in Comparative Example 3 was replaced with the polymerization liquid obtained in Comparative Example 6 to prepare a composition. The film thickness of the cured film was 2 μm. Using the obtained cured film substrate, the scratch resistance and solvent resistance were evaluated in the same manner as in Example 3. Since scratches and droplet marks were observed in the evaluation of scratch resistance and solvent resistance, the contact angle, sliding angle, and sliding speed were not evaluated.

[0078] <Discussion of evaluation results> The evaluation results for each example are shown in Table 2. [Table 2] TIFF2026018863000012.tif78153 The scratch resistance evaluation results show that Examples 3, 4, 7, and 8 have high pencil hardness and excellent scratch resistance compared to Comparative Examples 9 to 12, which do not use monomer B. Similarly, the solvent resistance evaluation results show that Examples 3, 4, 7, and 8 exhibit excellent solvent resistance compared to Comparative Examples 9 to 12. This is thought to be because the oxiranyl groups derived from monomer B form a crosslinked structure with trimellitic anhydride, increasing the molecular density. Looking at the contact angle, sliding angle, and sliding speed, Comparative Example 8, which did not use organosiloxane, was evaluated as poor, with a rating of ×. On the other hand, Examples 3, 4, and Comparative Example 7, which used organosiloxane, had contact angles and sliding angles of ◯ or higher, demonstrating that they were effective in water repellency, oil repellency, and water sliding. Among Examples 3, 4, and Comparative Example 7, which used organosiloxanes, Comparative Example 7, which used a linear siloxane, had a contact angle of ◯ and a sliding angle of ◯, similar to Example 4, but the sliding speed was △. In comparison, Example 4, which used a di-branched organosiloxane, had a sliding angle of ◯ and a sliding speed of ⊚, and Example 3, which used a tri-branched organosiloxane, had both a sliding angle and a sliding speed of ⊚, demonstrating that the polymers of the present invention, which use branched siloxanes, exhibit excellent water-slip properties. According to a composition using the polymer of the present invention, it is possible to obtain a cured film that is excellent in durability such as scratch resistance and solvent resistance, water repellency, and also in water sliding properties. [Industrial Applicability]

[0079] Because the present invention exhibits water repellency and water slip resistance, it can be applied to substrates that require water repellency and water droplet removal properties, and is effective for use in processes such as water-repellent coating films for substrates such as silicon wafers and glass, ship bottom paints, water-repellent films, water-repellent artificial leather, construction, and building products.

Claims

1. A polymer obtained by reacting raw material monomers including monomer A, which is a branched-chain organosiloxane having at least one addition-polymerizable functional group, and monomer B, which is an addition-polymerizable monomer having a reactive group.

2. The polymer according to claim 1 , wherein the raw material monomers further include an addition-polymerizable monomer C other than the monomer A and the monomer B.

3. The polymer according to claim 1 , wherein the monomer A is represented by the following formula (1): In formula (1), p is an integer from 10 to 700; a is 2 or 3; R １ , R ２ , R ３ , and R ４ are each independently hydrogen, alkyl, alkenyl, aryl, or arylalkyl; The alkyl has 1 to 30 carbon atoms, at least one hydrogen may be replaced by halogen, and at least one —CH ２ - may be replaced by one or more of -O- and cycloalkylene; The alkenyl has 2 to 3 carbon atoms; The aryl is a substituted or unsubstituted aryl having 6 to 20 carbon atoms; The arylalkyl is a substituted or unsubstituted aryl having 6 to 20 carbon atoms and a substituted or unsubstituted aryl having 1 to 30 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom, and at least one —CH ２ - is composed of alkylene optionally substituted with one or more of -O- and cycloalkylene; X １ is an addition polymerizable functional group.

4. In formula (1), R １ , R ２ , R ３ , and R ４ is each independently methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, chloromethyl, vinyl, allyl, phenyl, naphthyl, anthracenyl, pyrenyl, styryl, ethyleneoxy, or polyethyleneoxy.

5. In formula (1), R １ , R ２ , R ３ , and R ４ is each independently methyl, propyl, butyl, or phenyl.

6. The polymer according to claim 1 , wherein the monomer B is represented by the following formula (2): In formula (2), W is a monovalent organic group having any one reactive group selected from an alkenyl group, an alkoxycarbonyl group, an acyl group, a hydroxysilyl group, an alkoxysilyl group, a hydrosilyl group, an oxiranyl group, an oxetanyl group, a hydroxy group, a carboxy group, an isocyanato group, an isothiocyanato group, a mercapto group, an amino group, a formyl group, and an acid anhydride residue; X ２ is an addition polymerizable functional group.

7. X in formula (1) １ , and X in formula (2) ２ The polymer according to claim 3 or 6, wherein is a monovalent organic group containing a radically polymerizable functional group.

8. X in formula (1) １ , and X in formula (2) ２ and each independently represent a monovalent organic group represented by the following formula (3) or formula (4): In formula (3), R ６ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms; Y １ Ha-(OCH ２ CH ２ ) q -, -(OCHCH ３ CH ２ ) ｒ - or -(OCH ２ CH (CH ３ )) ｓ - and; q, r, and s are integers from 0 to 3; Z is a single bond or alkylene having 2 to 20 carbon atoms; In formula (4), Y ２ is a single bond or alkylene having 1 to 10 carbon atoms.

9. X in formula (1) １ , and X in formula (2) ２ The polymer according to claim 8 , wherein is a monovalent organic group having a (meth)acryloyloxy group.

10. A composition comprising the polymer of claim 1.

11. A composition comprising the polymer of claim 1 and a curing agent.

12. A cured film obtained from the composition according to claim 10 or 11.

Images