JP2008208243A - Fluorine based polymer and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel polymer capable of being used as a surface modifier excellent in water/oil repellency and a slip property. <P>SOLUTION: An additional polymer of a monomer (a), i.e., a specific fluorine based silicone compound and an addition polymerizable monomer (b) containing a cross-linkable functional group and an addition polymerizable functional group, namely a polymer having a cross-linkable functional group in the non-cross-linked state is provided. Further, the polymer and the resin composition containing a cross-linkable functional group and a cross-linkable resin having a cross-linkable structure or its monomer are provided. Further, in the film formed by the resin composition, the resin film obtained by reacting/cross-linking the cross-linkable functional group and the cross-linkable structure is provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymer containing fluorine. Specifically, a polymer containing a fluorine-based silicon compound as a monomer, effective for imparting slipping property and antifouling property to the surface of a plasma display, a resin composition containing this polymer, and containing this resin composition The present invention relates to a surface treatment agent and a resin film comprising the surface treatment agent.

  Conventionally, various researches have been conducted on surface modifiers that form a film on the surface of various substrates to impart protection, water repellency, oil repellency, insulation, non-adhesiveness, antifouling properties, etc. of the substrate. Yes. As a method, for example, there is a method of improving water repellency by applying a coating material made of a fluororesin, a silicone resin or the like to a substrate.

  The types of chemicals that impart such physical properties can be broadly classified into fluorine-based, silicone-based, or composite systems thereof.

  As a fluorine-based drug, a water-repellent paint in which a fluoroalkyl group-containing radical polymerizable monomer is dispersed in a thermosetting matrix resin has been reported (for example, see Patent Document 1). The compatibility with other resins was low, and the adhesion to the substrate was insufficient.

  As a product using a silicone-based chemical, a plastic product in which a silicone resin is mixed has been proposed (see, for example, Patent Document 2). However, the compatibility between the silicone resin and other resins is also low, and the oil repellency is low. Was not enough.

  As a fluorine-based and silicone-based composite agent, a coating agent composition containing a silicone resin having a fluoroalkyl group has been reported (see, for example, Patent Document 3), but is soluble in a general organic solvent. However, there was a problem that a fluorine-based solvent had to be used.

Furthermore, a coating agent containing a polymer as a monomer of a compound containing fluorine and silicon is known (see, for example, Patent Document 4), but there remains room for study on the characteristics of the film to be formed. Yes.
JP-A-7-102187 Japanese Patent Laid-Open No. 4-103668 JP-A-9-151357 JP 11-236532 A

  The present invention is excellent in water and oil repellency and slipperiness, and also has non-adhesiveness, releasability, antifouling properties, abrasion resistance, corrosion resistance, electrical insulation properties, antireflection properties, flame retardancy and antistatic properties. It is an object of the present invention to provide a new polymer that can be used as a surface modifier or the like, which is expected to have excellent properties such as properties, chemical resistance, and weather resistance.

As a result of earnest research from the above viewpoint, the present inventors have found that an addition polymerizable monomer that is a fluorine-based silicon compound and an addition polymerizable monomer containing a crosslinkable functional group and an addition polymerizable monomer. Addition copolymer containing an addition-polymerizable monomer in the monomer and having no crosslinkable functional group selected as needed has excellent slip, water and oil repellency. It was found to be useful as a surface modifier.

  That is, the present invention relates to the polymers shown below.

[1] Monomer of monomer (a) which is a silicon compound represented by the following general formula (I) and addition polymerizable monomer (b) containing a crosslinkable functional group and an addition polymerizable functional group A polymer characterized in that it is an addition polymer as a body and has the crosslinkable functional group in an uncrosslinked state.

In the general formula (I), R _f is a linear or branched fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be substituted with oxygen; at least one hydrogen is fluorine or A fluoroaryl having 6 to 20 carbon atoms substituted with trifluoromethyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in aryl is substituted with fluorine or trifluoromethyl, and n is R represents an integer of 0 to 1,000, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen; And any methylene may be replaced by oxygen or cycloalkylene; substituted or unsubstituted aryl; and substituted or unsubstituted aryl Represents a group selected from a reel and an arylalkyl composed of an alkylene in which any hydrogen may be replaced by fluorine and any methylene may be replaced by oxygen or cycloalkylene, and A ¹ is an addition polymerization Represents a functional group.

[2] R _f in the general formula (I) is 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6 , 6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2, 2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-trifluoromethyl The polymer according to [1], which is phenyl.

[3]
R _f in the general formula (I) is tridecafluoro-1,1,2,2-tetrahydrooctyl or heptadecafluoro-1,1,2,2-tetrahydrodecyl [2] The polymer described in 1.

[4]
R ³ and R ⁴ in the general formula (I) are each independently methyl, phenyl or 3,3,3-trifluoropropyl, and R ¹ , R ² , R ⁵ , and R ⁶ are each independently The polymer according to any one of [1] to [3], which is methyl or phenyl, and A ¹ represents a radical polymerizable functional group.

[5] The polymer according to any one of [1] to [4], wherein A ¹ in the general formula (I) contains (meth) acryl or styryl.

[6] The polymer according to [5], wherein A ¹ in the general formula (I) is any ^one of the following general formulas (II), (III), or (IV).

In the general formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁷ represents hydrogen, linear or branched alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms. In the general formula (III), R ⁸ represents hydrogen, linear or branched alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and X ¹ has 2 to 20 carbon atoms. Represents alkylene, Y represents —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, or —OCH ₂ CH (CH ₃ ) —, p represents an integer of 0 to 3, and represents a general formula (IV in), Y ² represents an alkylene single bond or a methylene or C2-10.

[7] In general formula (II), Y ¹ is alkylene having 2 to 6 carbon atoms, R ⁷ is hydrogen or alkyl having 1 to 3 carbon atoms, and in general formula (III), X ¹ is —CH ₂ CH ₂ CH ₂ —, Y is —OCH ₂ CH ₂ —, p is 0 or 1, R ⁸ is hydrogen or alkyl having 1 to 3 carbons, and in general formula (IV), The polymer according to [6], wherein Y ² is a single bond or methylene or ethylene.

[8] The weight according to any one of [1] to [7], wherein the addition polymerizable functional group of the addition polymerizable monomer (b) is a radical polymerizable functional group. Coalescence.

[9] The crosslinkable functional group of the addition polymerizable monomer (b) is selected from hydroxyl, a monovalent functional group including a cyclic ether, alkyl halide, isocyanate, amino, and carboxyl. [9] The polymer described in [8].

[10] The polymer according to [9], wherein the crosslinkable functional group of the addition polymerizable monomer (b) is a monovalent functional group containing a cyclic ether.

[11] The polymer according to [10], wherein the monovalent functional group containing the cyclic ether is selected from glycidyl, oxetanyl, epoxycyclohexyl, and dioxolane.

[12] An addition polymerizable monomer (c) having an addition polymerizable functional group other than the monomer (a) and the addition polymerizable monomer (b) which is the silicon compound is further used as a monomer. The polymer according to any one of [1] to [11], wherein the polymer is an addition polymer.

[13] The polymer as described in [12], wherein the addition polymerizable functional group of the addition polymerizable monomer (c) is a radical polymerizable functional group.

[14] The polymer as described in [13], wherein the radical polymerizable functional group contains (meth) acryl or styryl.

[15] A monomer (a) which is a silicon compound represented by the following general formula (I), a monomer (b) containing a crosslinkable functional group and a radical polymerizable functional group, and a radical polymerizable functional group. A radical having a monomer (a) which is the silicon compound and a monomer (c) other than the monomer (b) and having the crosslinkable functional group in an uncrosslinked state A polymer comprising:
The crosslinkable functional group is selected from glycidyl, oxetanyl, epoxycyclohexyl, and dioxolane,
The polymer, wherein the radical polymerizable functional group of the monomer (c) contains (meth) acryl or styryl.

In the general formula (I), R _f represents tridecafluoro-1,1,2,2-tetrahydrooctyl or heptadecafluoro-1,1,2,2-tetrahydrodecyl, and n is 0 to 1, Represents an integer of 000, R ^{1 to} R ⁶ each independently represent methyl or phenyl, and A ¹ represents any ^one of the following general formulas (II), (III), or (IV).

In the general formula (II), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ⁷ represents hydrogen or linear or branched alkyl having 1 to 3 carbon atoms, and in general formula (III), X ¹ represents —CH ₂ CH ₂ CH ₂ —, Y represents —OCH ₂ CH ₂ —, p represents 0 or 1, R ⁸ represents hydrogen or alkyl having 1 to 3 carbon atoms, In (IV), Y ² represents a single bond or methylene or ethylene.

[16] A resin composition comprising the polymer according to any one of [1] to [15] and a resin or a monomer thereof.

[17] The resin composition according to [16], wherein the resin is a crosslinkable resin having a structure capable of crosslinking with the crosslinkable functional group in the polymer.

[18] The resin composition according to [17], wherein the crosslinkable resin is a thermosetting resin.

[19] The thermosetting resin or monomer thereof is a compound having hydroxyl, a monovalent functional group containing cyclic ether, alkyl halide, isocyanate, amino or carboxyl, [18] The resin composition described in 1.

[20] The resin composition according to [19], wherein the monovalent functional group containing the cyclic ether is selected from glycidyl, oxetanyl, epoxycyclohexyl, and dioxolane.

[21] A surface treatment agent containing the resin composition according to any one of [16] to [20].

[22] A resin film obtained from the surface treatment agent according to [21].

  The fluorine-based polymer of the present invention and the resin composition containing the polymer can be used for a coating film excellent in water / oil repellency and slipperiness.

  The polymer of the present invention comprises a monomer (a) that is a fluorine-based silicon compound represented by the above formula (I) (hereinafter also simply referred to as “monomer (a)”), a crosslinkable functional group, and An addition-polymerizable monomer (b) containing an addition-polymerizable functional group (hereinafter also simply referred to as “monomer (b)”) is an essential component, and any addition-polymerizable monomer selected as necessary. It can be obtained by addition copolymerization of the monomer (c) (hereinafter also simply referred to as “monomer (c)”).

<Monomer (a) which is a fluorine-based silicon compound>
A monomer (a) which is a fluorine-based silicon compound, which is a kind of raw material monomer of the polymer of the present invention, is represented by the following general formula (I) and has an addition polymerizable functional group.

The monomer (a) used in the present invention is the above general formula (I), wherein R _f is a linear or branched group having 1 to 20 carbon atoms in which arbitrary methylene may be substituted with oxygen Chain-like fluoroalkyl; fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen is substituted with fluorine or trifluoromethyl; or carbon in which at least one hydrogen in aryl is substituted with fluorine or trifluoromethyl The fluoroarylalkyl of number 7-20 is represented.

R _f preferably has fluorine at the tip, and includes trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3- Pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,5, 5-octafluoropentyl, nonafluoro-1,1,2,2-tetrahydrohexyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4 , 5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro- 1,1 2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, α-tri Specific examples thereof include 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6. , 6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2- Tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl , Pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-trifluoromethylphenyl is preferable from the viewpoint of liquid repellency and slipperiness in the film of the resin composition containing the polymer of the present invention. , Tridecafluoro-1,1,2,2-tetrahydrooctyl, or heptadecafluoro-1,1,2,2-tetrahydrodecyl is more preferable.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ in the general formula (I) are each independently hydrogen; the number of carbon atoms is 1 to 30, and arbitrary hydrogen is replaced with fluorine. And any methylene may be replaced by oxygen or cycloalkylene; substituted or unsubstituted aryl; and substituted or unsubstituted aryl and any hydrogen may be replaced by fluorine An arylalkyl composed of methylene and alkylene optionally substituted with oxygen or cycloalkylene;

R ¹ , R ² , R ⁵ , and R ⁶ in the general formula (I) are each independently alkyl having 1 to 20 carbon atoms, and arbitrary hydrogen may be replaced with fluorine; It is preferably aryl that may be replaced with any hydrogen by -20 and optionally substituted with fluorine, or arylalkyl that has 7 to 20 carbon atoms and optionally substituted with fluorine, each independently methyl Or it is more preferable that it is phenyl.

R ³ and R ⁴ in the general formula (I) are each independently preferably hydrogen, phenyl, or alkyl having 1 to 8 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, More preferably, it is independently methyl, phenyl or 3,3,3-trifluoropropyl.

Furthermore, in the monomer (a), R ^{1 to} R ⁶ in the general formula (I) are each preferably methyl.

A ¹ in the general formula (I) is an addition polymerizable functional group. A ¹ is a functional group for addition polymerization of the other monomer described later and the monomer (a). Addition polymerizable functional groups include vinyl,
Examples thereof include functional groups having an addition polymerizable double bond such as vinylene and vinylidene. A ¹ is preferably a radical polymerizable functional group, more preferably (meth) acrylic or styryl, and any one represented by the following general formula (II), (III) or (IV) Is more preferable.

In General Formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁷ represents hydrogen, linear or branched alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms. . In general formula (III), R ⁸ represents hydrogen, linear or branched alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and X ¹ is alkylene having 2 to 20 carbon atoms. Y represents —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, or —OCH ₂ CH (CH ₃ ) —, and p represents an integer of 0 to 3. Further, in the general formula (IV), Y ² represents a single bond, methylene, or alkylene having 2 to 10 carbon atoms.

In the present invention, in the general formula (II), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ⁷ represents hydrogen or alkyl having 1 to 3 carbon atoms, and particularly preferably represents methyl. In the formula (III), X ¹ represents —CH ₂ CH ₂ CH ₂ —, Y represents —OCH ₂ CH ₂ —, p represents 0 or 1, and R ⁸ represents hydrogen or 1 to 3 carbon atoms. In the general formula (IV), Y ² preferably represents a single bond or methylene or ethylene.

  Examples of such a preferable radical polymerizable functional group include methacryloxypropyl.

  N in the general formula (I) represents an integer of 0 to 1,000. n can be appropriately determined depending on, for example, the solubility of the polymer of the present invention in a solvent. n is preferably 0 to 500, and more preferably 0 to 200.

For example, as disclosed in Japanese Patent No. 2655683, the monomer (a) has an addition polymerizable functional group by polymerizing silanol having a fluorine-containing hydrocarbon group and hexamethylcyclotrisiloxane. It can be obtained by reacting chlorosilane to stop the polymerization. The monomer (a) is preferably represented by the following general formulas (I-1) and (I-2) (both n represents 0 to 500, and R ⁹ represents hydrogen or methyl). Compounds.

<Addition polymerizable monomer (b) having a crosslinkable functional group and an addition polymerizable functional group>
The addition polymerizable monomer (b) having a crosslinkable functional group and an addition polymerizable functional group is a compound containing a crosslinkable functional group and an addition polymerizable functional group. The addition polymerizable functional group of the monomer (b) is a functional group for addition polymerization of at least the monomer (b) and the monomer (a), and is a radical polymerizable functional group. Is preferred. The monomer (b) may have one or more addition polymerizable functional groups. The same addition polymerizable functional group and radical polymerizable functional group as in the monomer (a) can be applied to the addition polymerizable functional group and the radical polymerizable functional group of the monomer (b).

  In the polymer of the present invention, the crosslinkable functional group can be determined from a functional group capable of crosslinking with the other component when the composition of the polymer of the present invention and the other component are used. it can. The monomer (b) may have one or more crosslinkable functional groups. Examples of such crosslinkable functional groups include monovalent functional groups including epoxies such as glycidyl and epoxycyclohexyl and cyclic ethers such as oxetanyl, isocyanates, acid anhydrides, carboxyls, amines, alkyl halides, thiols, siloxys and hydroxyls. Etc., but preferably a monovalent functional group containing a cyclic ether. Such functional groups include epoxies such as glycidyl and epoxycyclohexyl, oxetanyl and dioxolane.

  As the monomer (b), a compound in which the crosslinkable functional group is introduced into an addition polymerizable monomer can be used. About the specific example of the said monomer (b), as a compound (addition polymerizable monomer in this invention) which comprises the part remove | excluding the said crosslinkable functional group from the said monomer (b), it is one or two. Examples include compounds having the above addition polymerizable double bonds, such as vinyl compounds, vinylidene compounds, and vinylene compounds. More specifically, (meth) acrylic acid derivatives and styrene derivatives, and additions described later. The compound etc. which are mentioned by the polymerizable monomer (c) are mentioned.

  Furthermore, examples of the above (meth) acrylic acid derivative include (meth) acrylic acid amide, (meth) acrylonitrile and the like in addition to (meth) acrylic acid and (meth) acrylic acid ester.

Specific examples of the monomer (b) include the aforementioned derivatives having the aforementioned crosslinkable functional group. For example, the monomer (b) which is a (meth) acrylic acid derivative having a monovalent functional group containing a cyclic ether as a crosslinkable functional group includes an epoxy-containing (meth) acrylate such as glycidyl (meth) acrylate; Cycloaliphatic epoxy-containing (meth) acrylates such as 4-epoxycyclohexylmethyl (meth) acrylate; Oxetanyl-containing (meth) acrylates such as 3-ethyl-3- (meth) acryloyloxymethyloxetane; 4- (meth) acryloyloxy And dioxolane-containing (meth) acrylates such as methyl-2-methyl-2-ethyl-1,3-dioxolane;

  As specific examples of the monomer (b), for example, the monomer (b) which is a styrene derivative having a crosslinkable functional group includes o-aminostyrene, p-styrene chlorosulfonic acid, styrenesulfonic acid and its Salt, vinylphenylmethyldithiocarbamate, 2- (2-bromopropionyloxy) styrene, 2- (2-bromoisobutyryloxy) styrene, 1- (2-((4-vinylphenyl) methoxy) -1-phenyl (Ethoxy) -2,2,6,6-tetramethylpiperidine and compounds represented by the following structural formulas.

As specific examples of the monomer (b), for example, the monomer (b) which is a (meth) acrylate having a crosslinkable functional group includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Hydroxyalkyl (meth) acrylates such as acrylate; 2- (meth) acryloyloxyethyl isocyanate; γ- (methacryloyloxypropyl) trimethoxysilane; (meth) acrylate-2-aminoethyl, 2- (2-bromopropionyloxy) ) Ethyl (meth) acrylate, 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate; 1- (meth) acryloxy-2-phenyl-2- (
2,2,6,6-tetramethyl-1-piperidinyloxy) ethane, 1- (4-((4- (meth) acryloxy) ethoxyethyl) phenylethoxy) piperidine, 1,2,2,6 6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate; and the like.

  The monomer (b) preferably includes 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and 3-ethyl-3- (meth) acryloyloxymethyloxetane.

<Arbitrary addition polymerizable monomer (c)>
In addition to the monomer (a) and the monomer (b), in order to control the compatibility with the resin, the leveling property, the content of the crosslinkable functional group in the copolymer, etc. An addition polymerizable monomer (c) other than the monomer (a) and the monomer (b) can also be used in combination at any ratio at which the effects of the present invention can be obtained.

  The monomer (c) has one or two or more addition polymerizable functional groups such as addition polymerizable double bonds, and the monomer (b) is crosslinked in the polymer of the present invention. The compound which does not have the crosslinkable functional group which exists is mentioned. Examples of such a monomer (c) include (meth) acrylic acid and derivatives thereof, and styrene derivatives having one or two or more addition polymerizable double bonds and not having the crosslinkable functional group. Is mentioned. Such (meth) acrylic acid derivatives 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-ethylhexyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate and other alkyl (meth) acrylates; phenyl (meth) acrylate, toluyl (meth) acrylate Aryl (meth) acrylates such as rate; arylalkyl (meth) acrylates such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, etc. Alkoxyalkyl (meth) acrylates; ethylene oxide adducts of (meth) acrylic acid; and the like.

  The (meth) acrylic acid derivative having the above addition polymerizable double bond and having no crosslinkable functional group further includes trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth). Acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, diperfluoromethyl Methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, and 2-perfluoro Hexadecylethyl (meth) Fluoroalkyl (meth) acrylates such as acrylate and the like.

Furthermore, examples of the (meth) acrylic acid derivative having an addition polymerizable double bond and having no crosslinkable functional group include a (meth) acrylic acid derivative having a silsesquioxane skeleton. Specific examples of the (meth) acrylic acid derivative having such a silsesquioxane skeleton include 3- (3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^{3]. , 9} .1 ^5,15 .1 ^7,13 ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (
3,5,7,9,11,13,15-heptaisobutyl-pentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^{3, 9.1 5,15} .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5 1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaphenyl Pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1, ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3-[(3,5,7,9,11) , 13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] o Data siloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylates, 3 - [(3,5,7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 .1 ^7,13 ] ^{octasiloxane-} 1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaisooctylpentacyclo [ 9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11 , 13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3- [ (3, 5, 7, 9 , 11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate Can be mentioned.

  Examples of the styrene derivative having the above addition polymerizable double bond and having no crosslinkable functional group include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene.

Examples of the styrene derivative having the addition polymerizable double bond and not having the crosslinkable functional group further include styrene derivatives containing silsesquioxane. Examples of styrene derivatives containing such silsesquioxanes include 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^{3, 9} ． 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hept isobutyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hept isooctyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9.} 1 ^5,15 . 1 ^7,13 ] octasiloxane, and 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . Octasiloxane having a 4-vinylphenyl group (T ₈ type silsesquioxane), such as 1 ^7,13 ] octasiloxane; and 3- (3,5,7,9,11,13,15-heptaethyl Pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15) - hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11, 13,15- hepta isooctyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7, 9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] Kutaoctasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1. ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 .1 ^{5 , 15.1,7,13} ] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1. 1 ^3,9 .1 ^5,15 .1 ^7,13 ] ^{octasiloxane-} 1-yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisooctylpenta) cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane - - yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^{7 , 13} ] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene and 3-((3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethyl styrene, octasiloxane (T _8-inch silsesquioxane) having a 4-vinyl-phenylethyl group; include such .

  As the monomer (c), examples of the compound having two addition polymerizable double bonds include a diester of 1,3-butanediol and (meth) acrylic acid, 1,4-butanediol and (meth). Diester with acrylic acid, diester with 1,6-hexanediol and (meth) acrylic acid, diester with polyethylene glycol and (meth) acrylic acid, diester with diethylene glycol and (meth) acrylic acid, neopentyl glycol ( Diester of (meth) acrylic acid, diester of triethylene glycol and (meth) acrylic acid, diester of tripropylene glycol and (meth) acrylic acid, diester of hydroxypivalic acid ester neopentyl glycol and (meth) acrylic acid , Trimethylolpropane and (meth) acrylic Diester, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobisphenol A, bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxy Ethyl) 5,5-dimethylhydantoin, diester of 3-methylpentanediol and (meth) acrylic acid, diester of hydroxypivalic acid ester neopentyl glycol compound and (meth) acrylic acid, and bis [(meth) acryloyloxypropyl ] Di (meth) acrylate monomers such as tetramethyldisiloxane, and divinylbenzene.

  The monomer (c) having two addition polymerizable double bonds further has a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide. And a macromonomer having two addition polymerizable double bonds.

As the monomer (c), compounds having three or more addition polymerizable double bonds include, for example, a triester of trimethylolpropane and (meth) acrylic acid, a triester of pentaerythritol and (meth) acrylic acid. Esters, tetraesters of pentaerythritol and (meth) acrylic acid, pentaesters of dipentaerythritol and (meth) acrylic acid, triesters of tris (2-hydroxyethyl isocyanate) and (meth) acrylic acid, tris ( Diethylene glycol) trimerate and (meth) acrylic acid triester, 3,7,14-tris [(((meth) acryloyloxypropyl) dimethylsiloxy)]-1,3,5,7,9,11,14- hepta ethyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, 3,7,1 - tris [(((meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- hept isobutyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- hept isooctyl tricyclo [7.3.3.1 ^{5 , 11} ] heptasiloxane, 3,7,14-tris [(((meth) acryloyloxypropyl) dimethylsiloxy)]-1,3,5,7,9,11,14-heptacyclopentyltricyclo [7.3 .3.1 ^5,11] hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- Heputafu Nirutorishikuro [7.3.3.1 ^{5 and 11]} hept siloxane, octakis (3- (meth) acryloyloxy propyl dimethylsiloxy) octasilsesquioxane and octakis (3- (meth) acryloyloxy propyl) octa silsesquioxane Sun.

  The monomer (c) having three or more addition polymerizable double bonds further includes a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide. And a macromonomer having three or more polymerizable double bonds.

<Polymer of the present invention>
The polymer of the present invention essentially comprises the monomer (a) and the monomer (b), and may contain the monomer (c) selected as necessary. Is an addition copolymer. The polymer of the present invention may be an ordered copolymer such as block copolymer or a random copolymer, but is preferably a random copolymer. In addition, the polymer of the present invention may have a crosslinked structure that has already been subjected to crosslinking in the polymer, or may be a graft copolymer. The monomer (a), monomer (b) and monomer (c) may each be a single compound or two or more compounds.

  The polymer of the present invention comprises a structural unit derived from the monomer (a) (hereinafter referred to as structural unit (a)) and a structural unit derived from the monomer (b) (hereinafter referred to as structural unit (b)). It is preferable that a constituent unit derived from any monomer (c) that can be used as needed (hereinafter referred to as constituent unit (c)). In the polymer of the present invention, the molar ratio of the structural unit (a), the structural unit (b) and the structural unit (c) is arbitrary, and (a) :( b) = about 0.001: 99.999 to about 99.999: 0.001, (b) :( c) = about 0.001: 99.999 to about 99.999: 0.001, (a) :( c) = about 0.001: 99.999 ~ About 99.999: 0.001. As will be described later, when the polymer of the present invention is used as a surface modifier, (a) :( b) = about 1:99 to about 99: 1, (b) :( c) = about 1: 99 to about 99: 1, preferably (a) :( c) = about 1:99 to about 99: 1, (a) :( b) = about 1:99 to about 20:80, (b ): (C) = about 1:99 to about 20:80, more preferably (a) :( c) = about 1:99 to about 10:90.

  The weight average molecular weight of the polymer of the present invention varies depending on the content of the structural unit (a) and the like, but is about 1,000 to 1,000,000 as a guide. On the other hand, the molecular weight distribution (Mw / Mn) of the polymer of the present invention is about 1.01 to 2.5 as a guide.

  Further, the proportion of the structural unit (b) derived from the addition polymerizable monomer having a crosslinkable functional group contained in the polymer of the present invention is not particularly limited, and is blended when the polymer of the present invention is used as a coating agent. In order to achieve bonding with an epoxy resin that is a matrix resin, it is preferable that a crosslinkable functional group is included so as to obtain a preferable reactivity with the matrix resin or its monomer.

The polymer of the present invention has a structure in which the above-mentioned monomer (a), monomer (b) and monomer (c) are addition-polymerized, and the crosslinkable functional group of the monomer (b) At least a part of the structure is maintained as it is without being crosslinked. The polymer of the present invention can be obtained by addition polymerization of the monomer (a), the monomer (b) and the monomer (c) without causing the crosslinking functional group to undergo a crosslinking reaction. Alternatively, the polymer of the present invention is an addition polymerization of the monomer (b) in which the crosslinkable functional group is protected with a suitable protecting group, the monomer (a) and the monomer (c), It can be obtained by deprotecting the protecting group from the obtained addition copolymer. Alternatively, the polymer of the present invention is an addition copolymer obtained by addition polymerization of a monomer containing the monomer (a), and has a specific reactive group bonded to the main chain of the polymer. It can be obtained by reacting a compound with a compound that reacts with the reactive group to form the crosslinkable functional group. The manufacturing method of the polymer of this invention can be suitably selected according to the kind and reactivity of each functional group.

  More preferably, the polymer of the present invention uses the monomer (a), the monomer (b), and any monomer (c) that can be used as necessary as a monomer raw material. It can be obtained by addition polymerization.

  What is necessary is just to determine suitably the molar ratio of the said monomer (a), monomer (b), and monomer (c) contained in a monomer raw material according to the target polymer.

  In the case where a plurality of types of monomers are used as the monomer (b), the ratio of each monomer may be appropriately determined according to the characteristics of the target copolymer. In view of simplicity and versatility, radical copolymerization is preferred.

  The addition polymerization can be performed using a polymerization initiator. Examples of the polymerization initiator used include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), Azo compounds such as dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di -Peroxides such as -t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyneodecanoate; and tetraethyl Radical polymerization initiators such as dithiocarbamates such as thiuram disulfide; It is included.

Furthermore, examples of the polymerization reaction include living radical polymerization and photopolymerization.
Living radical polymerization is represented by atom transfer radical polymerization; reversible addition-fragmentation chain transfer; iodine transfer polymerization; iniferter polymerization, and can be performed using a polymerization initiator or catalyst described in the following documents A to C. .
-Literature A: Mikiharu Tsunoike, Takeshi Endo, radical polymerization handbook, August 10, 1999 issue, NTS issue).
Reference B: HANDBOOK OF RADICAL POLYMERIZATION, K.K. Matyjaszewski, T .; P. Davis, Eds. , John Wiley and Sons, Canada 2002
Document C: Japanese Patent Application Laid-Open No. 2005-105265

Photopolymerization can be performed using the compound described in Document D as a photopolymerization initiator.
-Document D: Photopolymer social gathering edition, Photosensitive material list book, published on March 31, 1996 by Bunshin Publishing).

Specific examples of the photopolymerization initiator used are not particularly limited as long as they are compounds that generate radicals upon irradiation with ultraviolet rays or visible rays. Compounds used as 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-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2 Benzyl-2
-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3, 4,4'-tri (t-butylperoxycarbonyl) benzophenone, 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, -(4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, 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) 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, 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, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- 3- (1H -Pyrrol-1-yl) -phenyl) titanium, and the like. These compounds may be used alone or in combination of two or more. 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxy) Carbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone and the like are preferable.
The amount of the polymerization initiator used in the above addition polymerization may be about 0.01 to 10 mol% with respect to the total number of moles of monomers.

In the addition polymerization, a chain transfer agent may be used. The molecular weight can be appropriately controlled by using a chain transfer agent. Examples of chain transfer agents include thio-β-naphthol, thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptans such as mercaptopropionate), pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate, diethyl disulfide; etc., toluene, methyl isobutyrate, Carbon tetrachloride, isopropylbenzene, diethyl ketone, chloroform, ethylbenzene, butyl chloride, s-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene chloride , Methyl chloroform, t- butyl benzene, butyl alcohol, isobutyl alcohol, acetic acid, ethyl acetate, acetone, dioxane, tetrachloroethane, chlorobenzene, cyclohexane, t- butyl alcohol, benzene and the like. In particular, mercaptoacetic acid can lower the molecular weight of the polymer and make the molecular weight distribution uniform.
Chain transfer agents can be used alone or in admixture of two or more.

The specific production method of the polymer of the present invention may be the same as the production method of an ordinary addition polymer, for example, solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method, bulk-suspension method. A turbid polymerization method or a polymerization method using supercritical CO ₂ can be used. In the case of the solution polymerization method, in an appropriate solvent, the monomer (a), the monomer (b), an optional monomer (c) used as necessary, and a polymerization initiator, And a chain transfer agent or the like may be dissolved and subjected to an addition polymerization reaction by heating or irradiation with light.

Examples of the solvent 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 (salt chloride). Methylene, 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, propylene carbonate, etc.), amide solvents (N, N-dimethyl) Formamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbons Solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic Fluorine solvent (α, α, α-trifluorotoluene, hexafluorobenzene) and water are included. These may be used alone or in combination of two or more.
The amount of the solvent used is preferably such that the monomer concentration is about 10 to 80% by weight.

  The reaction temperature is not particularly limited and may be about 0 to 200 ° C as a guide, and preferably room temperature to about 150 ° C. The polymerization reaction can be performed under reduced pressure, normal pressure, or increased pressure, depending on the type of monomer and the type of solvent.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. This is because the generated radicals are inactivated by contact with oxygen to suppress the polymerization rate from decreasing, and a polymer having a molecular weight appropriately controlled is obtained. Further, the polymerization reaction is preferably carried out in a polymerization system from which dissolved oxygen is removed under reduced pressure (after removing dissolved oxygen under reduced pressure, the polymerization reaction may be carried out under reduced pressure as it is).

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

  When purifying the polymer of the present invention, a purification method by reprecipitation operation is preferred. This purification method is performed as follows. First, in the polymerization reaction solution containing the polymer and the unreacted monomer, a solvent that does not dissolve the polymer but dissolves the unreacted monomer, a so-called precipitant is added to this solution to remove only the polymer. Precipitate. A preferable use amount of the precipitating agent is, for example, 20 to 50 times based on the weight of the polymerization reaction solution.

A preferred precipitant is a solvent that is compatible with the solvent used in the polymerization, does not dissolve the polymer at all, dissolves only unreacted monomers, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitating agents are methanol, ethanol, 2-propanol, hexane, and heptane. These may be used alone or in combination of two or more. Moreover, when mixing and using, you may purchase and use Solmix AP-1, A-11, etc. which are marketed as a denatured alcohol from Nippon Alcohol Sales Co., Ltd. And in order to raise the removal efficiency of an unreacted monomer further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, only the polymer can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

<Application of polymer>
The polymer of the present invention can be used for any application, but can be molded by various molding processes (press molding, extrusion molding, injection molding, compression molding, etc.) in combination with other resins as necessary. It can be used as a product.

  In addition, the polymer of the present invention can be used as a surface treatment agent such as a surface modifier (so-called coating material) by combining other resins or resin monomers as necessary and dissolving or dispersing them in various solvents. It can also be used. In the present invention, a resin other than the polymer of the present invention may be referred to as “matrix resin”. As the matrix resin, a crosslinkable resin, a thermoplastic resin, a thermosetting resin, or the like can be used, and these can be properly used according to the purpose and application. The monomer forming the matrix resin may be referred to as “matrix resin monomer”. Resins other than the polymer of the present invention formed from the matrix resin monomer can also be used as the matrix resin. These resins may be used in combination as the matrix resin. In the case of the composite resin in which the polymer of the present invention and the matrix resin are cross-linked, the content of the matrix resin in the surface treatment agent of the present invention is preferably 90 to 99.99% by weight in total.

Use as a surface modifier
1) Applying a solution or dispersion containing the polymer of the present invention alone to a solid to form a coating film (film);
2) A solution or dispersion containing the polymer of the present invention and a matrix resin is applied to a solid, and the obtained coating film such as drying, curing reaction or crosslinking reaction is solidified, and the polymer of the present invention. And 3) a solution or dispersion containing the polymer of the present invention and a matrix resin monomer is applied to a solid, and the polymer of the present invention and the matrix resin are formed. Forming a coating film composed of the polymer of the present invention and a matrix resin by polymerizing the monomer.

The surface treating agent of the present invention is
4) A solution or dispersion liquid containing the polymer of the present invention and a crosslinkable resin (matrix resin) other than the polymer of the present invention having a structure capable of crosslinking with the crosslinkable functional group is applied to a solid. A coating film made of a composite resin obtained by crosslinking the polymer of the present invention and the matrix resin, and 5) the polymer of the present invention and the polymer of the present invention. The polymer of the present invention is obtained by coating a solid or a solution containing a crosslinkable functional group and a crosslinkable resin monomer having a crosslinkable structure (matrix resin monomer) capable of crosslinking reaction. It is more preferable to form a coating film made of a composite resin in which the polymer of the present invention and the matrix resin are crosslinked by polymerizing and crosslinking the matrix resin monomer.
In 4) and 5), a matrix resin and a matrix resin monomer may be used in combination.

For example, the formation of the coating film on the substrate is a solution (coating solution) containing the polymer of the present invention.
Can be performed by applying the resin composition to a substrate and drying it, and can also be performed by applying the resin composition of the present invention or a solution thereof to the substrate and drying it, and the matrix resin is a crosslinkable resin. In some cases, the resin composition of the present invention or a solution thereof can be applied to a substrate to crosslink the crosslinkable functional group. Further, when the matrix resin is a thermosetting resin, The resin composition or solution thereof can be applied to a substrate and the matrix resin can be cured by heating. The formed coating film has high water / oil repellency and low surface free energy. This high water repellency and oil repellency and low surface free energy are considered to be manifested due to the uneven distribution of fluorine atoms derived from the fluorinated silicon compound on the surface of the coating film to be formed.

  The matrix resin and the monomer thereof may be one kind or two or more kinds, respectively, may be a thermoplastic resin and a monomer thereof, or may be a crosslinkable resin and a monomer thereof. It may be a thermosetting resin and a monomer thereof, a resin having thermoplasticity and crosslinkability and a monomer thereof, or a resin having thermosetting property and crosslinkability. May be. In the present invention, a matrix resin and a matrix resin monomer may be used in combination.

  The crosslinkable resin as the matrix resin may have a structure capable of crosslinking with the crosslinkable functional group such as a functional group that reacts with the crosslinkable functional group or a structure in the main chain. The crosslinkable structure only needs to be present in the matrix resin in a sufficient number to crosslink at least one of the crosslinkable functional groups of the polymer of the present invention. Examples of the crosslinkable structure include one or more functional groups similar to the crosslinkable functional group of the monomer (b).

  As described above, the polymer of the present invention may be used alone as a surface modifier as in 1) above, but used as a surface modifier by mixing with other matrix resin as in 2) above. Alternatively, as in the above 3), it may be mixed with a monomer that forms a matrix resin and used as a surface modifier.

  As described in 2) above, when the polymer of the present invention is used by being mixed with another matrix resin, the original properties (mechanical properties, surface / interface properties, compatibility, etc.) of the resin can be modified.

  When used as a surface modifier, the matrix resin is preferably a thermosetting resin from the viewpoint of improving the mechanical strength and thermal characteristics of a resin film formed from the resin composition. When a thermosetting resin is used for the matrix resin, the crosslinking by the crosslinkable functional group and the curing of the thermosetting resin or the polymerization and curing of the monomer of the thermosetting resin may be performed separately. From the viewpoint of simplifying the production process, it is preferable that all of the crosslinking, curing, and polymerization / crosslinking are performed under the same conditions.

As matrix resins, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultrahigh molecular weight polyethylene, poly-4-methylpentene, Syndiotactic polystyrene, polyamide (nylon 6: DuPont brand name, nylon 6,6: DuPont brand name, nylon 6,10: DuPont brand name, nylon 6, T: DuPont brand name, nylon MXD6: DuPont company Product name, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene oxide, Fluorine resin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: Unitika Ltd. trade name, Vectra: Polyplastics Corp.) Product name, etc.), polyimide (Kapton: Toray Industries, Inc., AURUM: Mitsui Chemicals, Inc., etc.), polyetherimide, polyamideimide, phenol resin, alkyd resin, melamine resin, epoxy resin, urea Examples thereof include resins, bismaleimide resins, and silicone resins.

  These resins may be used alone or in combination of a plurality of resins.

  Further, as in the above 3), the polymer of the present invention may be used by mixing with a matrix resin monomer. In particular, when the polymer of the present invention having a crosslinkable functional group and a matrix resin monomer are mixed and used, the resin obtained by curing and the polymer of the present invention are cross-linked, resulting in mechanical properties, A composite resin excellent in surface / interface characteristics and compatibility can be obtained.

  Specifically, a solution containing a polymer of the present invention having a crosslinkable functional group, a monomer that forms a matrix resin, and a curing reaction initiator (for example, an acid generator) as required is applied to a substrate. Then, by drying and curing the coating film, a coating film (composite film) made of a composite resin with a matrix resin can be formed on the substrate.

  The formed composite film has high water / oil repellency and low surface free energy. This is presumably because fluorine atoms of the fluorine-based silicon compound contained in the polymer of the present invention are unevenly distributed on the surface layer of the composite film.

  Preferable examples of the matrix resin monomer include a monomer that forms an epoxy resin. The formed epoxy resin may be either an aliphatic epoxy resin or an aromatic epoxy resin. Accordingly, the matrix resin monomer can be, for example, a monomer that forms the epoxy resin shown below.

  Examples of epoxy resins formed include bisphenol A, bisphenol F, hydroquinone, resorcin, dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) dicyclopentane, 4,4′-dihydroxybenzophenone. Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4 -Hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (3 , 5-Dimethyl- -Hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4- Hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl-3,3 ′, 5,5′-tetramethylbiphenyl, bis (hydroxynaphthyl) methane, and 1,1′-binaphthol, 1,1′-bis ( Epoxy resins made from 3-t-butyl-6-methyl-4-hydroxyphenyl) butane and the like are included.

Furthermore, examples of the epoxy resin formed include phenol novolac epoxy resins that are glycidyl etherified products of reaction products with phenols such as phenol, o-cresol, catechol, and aldehydes such as formaldehyde; phenol, cresol, Polyglycidyl ether of polyphenols containing trityl skeleton obtained by condensation of phenols such as methyl-t-butylphenol and aromatic aldehydes such as hydroxybenzaldehyde; reaction product of polyphenols containing trityl skeleton and formaldehyde Polyglycidyl ethers of polyphenolic novolacs containing a trimethyl skeleton; reaction between phenols such as phenol, o-cresol, catechol, and xylylene dichloride, (hydroxymethyl) benzene, etc. Polyglycidyl ethers of polyaralkylphenol resins as products; phenols such as phenol, o-cresol and catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and unsaturated alicyclics such as dicyclopentadiene and limonene Alicyclic hydrocarbon-containing polyphenol resin-type epoxy resin or polynaphthol resin-type epoxy resin, which is a glycidyl ether of a reaction product with an aromatic hydrocarbon; alicyclic hydrocarbon-containing polyphenol resin or polynaphthol resin and formaldehyde Polyglycidyl ethers of cycloaliphatic hydrogen-containing polyphenol novolak resins or polynaphthol novolak resins that are reaction products of glycine with polyphenols obtained by condensation reaction of phenols with aromatic carbonyl compounds Ether compounds; phloroglycine, tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,3-bis [(4-hydroxyphenyl) methyl] benzene, 1 , 4-bis [(4-hydroxyphenyl) methyl] benzene and other trivalent or higher polyglycidyl ethers; glycidyl ether compounds derived from cyclic phenols such as calixarene; p-amino Phenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether 1,4-bis (4-aminopheno Ii) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4 -Aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis ( Methylamine), 1,3-cyclohexanebis (methylamine), amine-based epoxy resins derived from N, N-diglycidylaniline, etc .; p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid, etc. Glycidyl ester compounds derived from aromatic carboxylic acids of 5,5-dimethylhydantoin, etc. Hydantoin-based epoxy compounds derived from: 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexene dioxide, 3 Alicyclic epoxy resins such as 1,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; aliphatic epoxy resins obtained by oxidizing double bonds in unsaturated hydrocarbon compounds such as polybutadiene, etc. .

  The formed epoxy resin may be an alicyclic epoxy resin. Specific examples thereof include a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, or a cyclohexane oxide or cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. The resulting epoxy resin.

For example, 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) cyclohexane Meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methyl Cyclohexyl carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3
, 4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,2: 8,9 diepoxy limonene (Trade name: CEL3000, Daicel Chemical Co., Ltd.), epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (trade name: Epolide GT301, Daicel Chemical Co., Ltd.), epoxy Butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone (trade name: Epolide GT401, Daicel Chemical Industries), 1,2-epoxy of 2,2-bis (hydroxymethyl) -1-butanol -4 -(2-oxiranyl) cyclosexane adduct (trade name: EHPE3150, Daicel Chemical Co., Ltd.), 1,2-epoxy-4- (2-oxiranyl) cyclo of 2,2-bis (hydroxymethyl) -1-butanol A mixture of a sexane adduct and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (trade name: EHPE3150CE, Daicel Chemical Industries), 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400, Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M100, Daicel Chemical Co., Ltd.) and other epoxy resins and epoxidized polybutadiene (trade name: Epolide PB3 00, Daicel Chemical Co., Ltd.), epoxidized thermoplastic elastomer (trade name: EPOFRIEND include epoxy resins represented by Daicel Chemical Co., Ltd.) and the like.

  Further, the epoxy resin includes an epoxy resin obtained from a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof; an epoxy resin obtained from a polyglycidyl ester of an aliphatic long-chain polybasic acid; glycidyl acrylate or glycidyl methacrylate. Homopolymer synthesized by vinyl polymerization of glycidyl acrylate, or a copolymer synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers.

  The polyglycidyl ether includes 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol. Glycidyl ether of polyhydric alcohol such as diglycidyl ether of polyethylene glycol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol.

  The polyglycidyl ester is a polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, glycerin, and the like. And diglycidyl esters of family long chain dibasic acids.

  Further, the epoxy resin includes an epoxy resin obtained from a monoglycidyl ether of an aliphatic higher alcohol, phenol, cresol, butylphenol, or a polyether alcohol monoglycidyl ether obtained by adding an alkylene oxide thereto; Examples include epoxy resins obtained from glycidyl esters; epoxy resins obtained from epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene and the like.

  The matrix resin monomer to be combined with the polymer of the present invention may be any monomer that forms the above-described epoxy resin, but may be a compound shown below.

That is, examples of the matrix resin monomer include oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane, and 3,3-dichloromethyloxetane; trioxane such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; Cyclic ether compounds such as dioxolane and 1,3,6-trioxacyclooctane; cyclic lactone compounds such as β-propiolactone, γ-butyrolactone and ε-caprolactone; thiirane compounds such as ethylene sulfide; trimethylene sulfide, 3, Thietane compounds such as 3-dimethylthietane; Cyclic thioether compounds such as tetrahydrothiophene derivatives; Spiroorthoester compounds obtained by reaction of epoxy compounds with lactones; Spiroorthocarbonate compounds; Cyclic carbonates Compound; Vinyl ether compounds such as ethylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether; styrene, vinylcyclohexene, Ethylenically unsaturated compounds such as isobutylene and polybutadiene, amino groups, hydroxyl, glycidyl, oxetanyl, polydimethylsiloxane having epoxy cyclohexyl, polyalkylene oxide (polyethylene oxide, polypropylene oxide, block copolymer of polyethylene oxide and polypropylene oxide, etc. ), Fluorinated polyalkylene oxide (polyfluoroethylene oxide, polyfluoropropylene oxide, etc.), etc. In addition, and the like.

  As described above, the polymer of the present invention having a crosslinkable functional group can be used in combination with a monomer that forms a matrix resin (for example, an epoxy resin) and a curing reaction initiator (for example, an acid generator).

  There is no restriction | limiting in a hardening reaction initiator, For example, the compound which can discharge | release the substance which starts cationic polymerization by active energy ray irradiation or a thermal energy can be used. Examples of the curing reaction initiator include a carboxylic acid, an amine, an acid anhydride compound, an acid generator, and the like, and preferably a double salt that is an onium salt that releases a Lewis acid or a derivative thereof.

Representative examples of the curing reaction initiator include cation and anion salts represented by the following general formula.
[A] ^{m +} [B] ^m-

In the above general formula, the cation [A] ^{m +} is preferably an onium ion, for example, represented by the following general formula.
[(Α) _a Q] ^{m +}

α represents an organic group having 1 to 60 carbon atoms, which may contain any number of atoms other than carbon atoms. a represents an integer of 1 to 5. The a α's are independent and may be the same or different. Further, at least one α is preferably an organic group having an aromatic ring. Q represents an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{m +} is q, m = a−q (where N = N is treated as valence 0).

On the other hand, the anion [B] ^m− is preferably a halide complex, and is represented by the following general formula, for example.
[LX _b ] ^m-

L represents a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X represents a halogen atom. b represents an integer of 3 to 7. Further, when the valence of L in the anion [B] ^m− is p, m = b−p.

The anion [LX _b ] ^m− represented by the above general formula includes tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), hexafluoroarsenate (AsF _6). ), Hexachloroantimonate (SbCl ₆ ) and the like.

As the anion [B] ^m− , those represented by the following general formula can also be preferably used. L, X, and b are the same as described above.
[LX _b-1 (OH)] ^m−

The anion [B] ^m− further includes perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluenesulfonate anion, And trinitrobenzene sulfonic acid anion.

Among these onium salts, the curing reaction initiator in the present invention is more preferably an aromatic onium salt exemplified by the following (A) to (C). Among these, one of them can be used alone, or two or more can be mixed and used.
(I) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, and (b) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryl iodonium salts such as hexafluorophosphate and di (4-t-butylphenyl) iodonium hexafluorophosphate (c) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thio Phenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenyls Honium hexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4 , 4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis- Hexafluorophosphate, 4- [4 '-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4'-(benzoyl) phenylthio] phenyl-di- (4-fluoro Phenyl) sulfonium Kisa triarylsulfonium salts such as fluorophosphate

Further, the curing reaction initiator in the present invention may be a mixture of an iron-arene complex or an aluminum complex and silanols such as triphenylsilanol. The iron-arene complex includes (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron- Hexafluorophosphate and the like are included, and examples of the aluminum complex include tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and the like.

  Among these, from the viewpoint of practical use, the curing reaction initiator in the present invention is preferably an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  For example, when the matrix resin is an epoxy resin, the content of the curing reaction initiator (preferably an acid generator) is 10 to 500 mol of the epoxy group of the polymer of the present invention and the epoxy resin monomer. It is preferably 1 mole.

  As described above, the polymer of the present invention can be dissolved or dispersed in a solvent and used as a surface modifier. The concentration of the solid content (including the polymer of the present invention and other resins) contained in the surface modifier is not particularly limited, but may be 1 to 50% by weight.

  The solvent for dissolving or dispersing the polymer of the present invention is not particularly limited, but preferably contains 20% by weight or more of a compound having a boiling point of 50 ° C. to 200 ° C. The compound having a boiling point of 50 ° C. to 200 ° C. contained in the solvent may be one kind or a combination of two or more kinds.

  Compounds having a boiling point of 50 ° C. to 200 ° C. include water; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone; butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, oxyacetic acid Butyl, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate Aliphatic ethers such as dioxane; cyclic ethers such as dioxane; ketones such as cyclohexanone and cyclopentanone; aromatics such as toluene and xylene; cyclic esters; N, N-dimethylacetamide and the like.

  Further, the compound having a boiling point of 50 ° C. to 200 ° C. includes glycol or a derivative thereof. Examples of glycols include ethylene glycol, propylene glycol, 1,4-butanediol and the like.

  Glycol derivatives include glycol monoethers such as ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate , Glycol monoether acetates such as ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc. Glycol dimethyl ether; and the like.

  Among these, preferable examples of the solvent of the coating solution include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and ethyl lactate are included. Further, in view of safety to human body, preferable examples of the solvent include propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, and ethyl lactate.

  In addition, when the coating solution is applied to a substrate such as a substrate with a slit coater (which is preferably used for coating on a large substrate), propylene glycol monomethyl ether acetate is used in order to improve the coating uniformity. And a mixed solvent of methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether; a mixed solvent of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether is preferably used.

  The method for applying the solution containing the resin composition of the present invention to the substrate is not particularly limited, but spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating, There are a rod coating method, a bar coating method, a die coating method, a kiss coating method, a reverse kiss coating method, an air knife coating method, a curtain coating method, and the like.

  Examples of substrates to be applied include transparent glass substrates such as white plate glass, blue plate glass, and silica coated blue plate glass; synthetic resins such as polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, and polyimide. Sheets, films or substrates; metal substrates such as aluminum plates, copper plates, nickel plates, stainless steel plates; other ceramic substrates, semiconductor substrates having photoelectric conversion elements are included.

These base materials may be pretreated. Examples of the pretreatment include chemical treatment with a silane coupling agent, sandblast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas treatment. Phase reaction method, vacuum deposition, etc. are included.
The applied solution can be dried in an environment of room temperature to 200 ° C.

  The coating solution is produced by mixing and dissolving the polymer of the present invention and optional components in the solvent.

  Although there is no restriction | limiting in particular in the content rate of the polymer of this invention in the composite resin obtained, It is preferable that it is 0.01 to 10 weight%. This is for appropriately controlling the fluorine content in the composite resin. The fluorine concentration in the composite resin is 0.05 to 10% by weight, preferably 0.1 to 5% by weight.

The film made of the composite resin has high water repellency and oil repellency, and low surface free energy.
Next, a fluoropolymer composition for obtaining the resin film of the present invention, a surface treatment agent containing the fluoropolymer composition, and a coating film obtained from the surface treatment agent will be described.

  The surface treating agent of the present invention contains the polymer of the present invention, the matrix resin or a monomer thereof, and, if necessary, the aforementioned solvent. The surface treating agent of the present invention preferably contains 0.01 to 5% by weight of the polymer of the present invention as a fluorine atom derived from the monomer (a) in the polymer of the present invention. The aforementioned epoxy resin is preferably used for the matrix resin in the surface treatment agent of the present invention.

  The compounding ratio of the epoxy resin to be formed and the polymer of the present invention is not particularly limited, but it is preferable not to use the polymer of the present invention excessively from the viewpoint of cost efficiency. Therefore, the content concentration of the polymer of the present invention in the surface treatment agent of the present invention is preferably blended so as to be 0.01 to 5% by weight as fluorine atoms, and further 0.01 to 3% by weight as fluorine atoms. It is practical to blend so that

  The fluorine-based polymer composition for obtaining the coating film of the present invention, and the surface treatment agent containing the fluorine-based polymer composition, as long as they do not adversely affect the effects of the present invention, other additives, for example, Pigments, dyes, antioxidants, deterioration inhibitors, fillers, UV absorbers, antistatic agents and / or electromagnetic wave inhibitors may be included.

  The above-mentioned acid generator is preferably selected as the curing reaction initiator used in the surface treatment agent, and the content thereof is 10 to 500 mol of the epoxy group that the copolymer and the epoxy resin-forming raw material composition have, 1 mol is preferred.

  As the solvent that may be contained in the surface treating agent of the present invention, one or two or more of the aforementioned compounds having a boiling point of 50 ° C. to 200 ° C. and chlorofluorocarbon solvents can be used. Examples of the fluorocarbon solvents include hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbon solvents (perfluorocarbon solvents). Fluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroethers, fluoropolyethers, fluoroketones, fluoroalcohols), aromatic fluorine solvents ( α, α, α-trifluorotoluene, hexafluorobenzene) and the like.

  As described above, a chlorofluorocarbon organic solvent can be used as the solvent, but in view of environmental considerations, a nonfluorocarbon organic solvent is preferable. In general, for example, two or more kinds of mixed solvents selected from the group including MEK (2-butanone), CHN (cyclohexanone), MMP (methyl 3-methoxypropionate), and IPA (2-propanol) are suitable. Specifically, a mixed solvent of MEK, MMP, and IPA, or a mixed solvent of MEK, CHN, MMP, and IPA can be used. It is preferable to appropriately adjust the blending ratio of the epoxy resin, the copolymer, the leveling property, and the like as necessary.

  In the above mixed solvent, further in terms of improving coating uniformity, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate and the like are preferably blended. Among these, in consideration of safety to the human body, preferable examples of the solvent include propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, ethyl lactate and the like. Is preferred.

  In the present invention, the surface treatment agent includes, in addition to the polymer of the present invention, the matrix resin or monomer thereof, a curing initiator and a solvent, as necessary and within the range where the effects of the present invention can be obtained. Arbitrary components can be mixed and dissolved. The concentration of the non-volatile component of the surface treatment agent obtained as described above is not particularly limited, but is usually 1 to 50% by weight, and practically preferably about 5 to 20% by weight.

  The resin film of the present invention is obtained from the surface treatment agent of the present invention. More specifically, the film of the surface treatment agent of the present invention may be used, or the film may be solidified by drying, crosslinking, curing, or the like. The film of the surface treatment agent of the present invention can be formed by a known method in which a solution is applied to a substrate to form a solution film.

The method for applying the surface treatment agent to the substrate is not particularly limited, but spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating, rod coating. Method, bar coating method, die coating method, kiss coating method, reverse kiss coating method, air knife coating method, curtain coating method and the like.

  Crosslinking between the crosslinkable functional group and the matrix resin in the film of the surface treatment agent is performed when the surface treatment agent contains the polymer of the present invention and the matrix resin. It can be carried out by placing the film of the surface treatment agent under conditions for crosslinking with the crosslinkable structure therein. Such conditions include heating and light irradiation. In the present invention, it is preferable that the crosslinking is performed by heating under a firing condition of a resin film that is usually performed in the manufacture of a display element.

  When the surface treatment agent contains the polymer of the present invention and the monomer of the matrix resin, the film is placed under conditions for polymerizing the monomer of the matrix resin in addition to the above-mentioned crosslinking conditions. Thus, the resin film of the present invention is formed. The monomer of the matrix resin can be polymerized under conditions such as heating and light irradiation. In the resin film of the present invention, it is preferable from the viewpoint of simplification of the production process that the conditions for the crosslinking and the conditions for polymerizing the monomer of the matrix resin are the same.

  The coating amount of the surface treatment agent is usually preferably 0.1 to 20 μm as the thickness of the coating film after firing, and more preferably about 0.3 to 3 μm practically.

  The firing conditions after the application of the surface treatment agent (release agent solution) can be set in consideration of the curing conditions of the matrix resin and the heat resistance of the substrate. For example, when the matrix resin is the epoxy resin, the firing temperature is usually preferably 120 to 200 ° C, and more preferably 130 to 180 ° C practically. The firing time is adjusted depending on the thickness of the resin film, the type of the base material, the thickness of the base material, and the firing temperature. Usually, when a plastic film is used as the base material, it is preferably 15 to 600 seconds. . More specifically, for example, when a polyethylene terephthalate film having a baking temperature of 150 ° C., a resin film thickness of 1 μm, and a substrate thickness of 75 μm is used, 45 to 600 seconds is sufficient.

  The resin film of the present invention can express various properties only by itself or by adding known appropriate additives, and can be used in various applications that require such properties. In addition to water and oil repellency and slipperiness, these properties include antifouling properties, non-adhesiveness, release properties, wear resistance, corrosion resistance, electrical insulation, antireflection properties, flame resistance, Antistatic properties, chemical resistance, weather resistance, etc. can be mentioned. Applications of the resin film of the present invention include a coating film for peeling, a water / oil repellent coating film, an antifouling coating film, a sliding coating film, and an antireflection coating. Examples thereof include a coating film and an insulating coating film.

  In addition, since the resin film of the present invention seems to have a structure derived from the monomer (a) in the vicinity of the surface of the resin film, the treatment for adjusting the orientation of molecules in the resin film is performed, At least some of the characteristics are improved. Examples of such treatment include rubbing alignment treatment in which rubbing cloth rubs in one direction.

  Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the scope of the present invention is not limited by these descriptions. In addition, the data of the weight average molecular weight in a present Example were calculated | required by GPC (gel permeation chromatography method) by using poly (methyl methacrylate) as a standard substance.

[Example 1]
Synthesis of polymer (A1) <Polymerization>
A fluorine-based silicon compound represented by the following general formula (I-3) (with a molecular weight of about 6) was placed in a three-necked flask with an internal volume of 50 mL equipped with a reflux condenser, thermometer, dropping funnel and septum cap with a syringe for argon bubbling. , 000) (a-1) 3.78 g, methyl methacrylate (MMA) 5.46 g, 3,4-epoxycyclohexylmethyl methacrylate (M100) 1.26 g, 2-butanone (MEK) 19.43 g introduced. And sealed with nitrogen. A three-necked flask was set in an oil bath maintained at 95 ° C., the contents were refluxed, and deoxygenated for 10 minutes. Next, a solution prepared by dissolving 0.0421 g of 2,2′-azobisisobutyronitrile (AIBN) and 0.0236 g of mercaptoacetic acid (AcSH) in 0.5916 g of MEK was introduced into a three-necked flask, and the reflux temperature was increased. The polymerization was started while keeping After polymerization for 3 hours, a solution in which 0.0421 g of AIBN was dissolved in 0.3790 g of MEK was introduced into the three-necked flask, and the polymerization was further continued for 2 hours. After completion of the polymerization, 15 mL of denatured alcohol (Solmix AP-1, manufactured by Nippon Alcohol Sales Co., Ltd.) was added to the polymerization solution, and then poured into 300 mL of Solmix AP-1 to precipitate a polymer. The supernatant was removed and dried under reduced pressure (80 ° C., 5 hours) to obtain 10 g of the polymer (A1). The weight average molecular weight determined by GPC analysis of the obtained polymer was 45,000, and the molecular weight distribution was 2.08. The compositional molar fraction of the monomer components determined from the ¹ H-NMR measurement of the polymer (A1) is a compound (a-1): MMA: M100 = 0.8: 87.7: 11.5.

[Comparative Example 1]
Synthesis of polymer (B1) <Polymerization>
Instead of the fluorine-based silicon compound (a-1), one-terminal methacryloxypropyl group-modified dimethyl silicone represented by the following general formula (V) (FM-0721, manufactured by Chisso Corporation, molecular weight of about 6,000) (b- Using 1), 10 g of polymer (B1) was obtained by the same operation as in Example 1. The weight average molecular weight determined by GPC analysis of the obtained polymer was 37,000, and the molecular weight distribution was 1.73. The compositional molar fraction of the monomer components determined from the ¹ H-NMR measurement of the polymer (B1) the compound (b-1): MMA: M100 = 0.8: 88.4: 10.8.

[Example 2]
Preparation of Coating Solution and Coating Film 1.01 g of the obtained polymer (A1) and EHPE3150CE (1,2-epoxy-4- (2-oxiranyl) of 2,2-bis (hydroxymethyl) -1-butanol A mixture of cyclohexane adduct and (3′4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate, epoxy equivalent: 151 g / mol, manufactured by Daicel Chemical Industries, Ltd. (9.07 g) was mixed with a mixed solvent (2-butanone). / Cyclohexanone / 3-methyl 3-methoxypropionate / 2-propanol = weight ratio 50/20/15/15) was dissolved in 90.71 g. Furthermore, 0.082 g (epoxy group / cation polymerization initiator = 379/1 (molar ratio), epoxy amount: 60.1 mmol) of cationic polymerization initiator Sun-Aid SI-60 (manufactured by Sanshin Chemical Industry Co., Ltd.) as a curing agent. In addition, a coating solution was obtained.

  The fluorine concentration in the resin solid content of the obtained coating liquid was 0.16% by weight, and the silicon compound concentration in the resin solid content was 3.0% by weight. “Fluorine concentration in resin solid content” and “silicon compound concentration in resin solid content” are the weight of fluorine and silicon compound contained in polymer (A1) with respect to the total weight of polymer (A1) and EHPE3150CE. It was calculated from the ratio of the weight of fluorine in the polymer (A1), the ratio of the weight of the silicon compound in the polymer (A1), and the weight ratio of the polymer (A1) to EHPE3150CE.

  The obtained coating solution was applied onto a polyethylene terephthalate film (thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.) using a coating rod (# 4, manufactured by RD Specialties). did. The obtained coating film was cured and dried at 150 ° C. for 10 minutes in a high temperature chamber to obtain a transparent coating film having a thickness of about 0.9 μm.

[Example 3]
Preparation of Coating Liquid and Coating Film A coating liquid was prepared in the same manner as in Example 2 except that the polymer (A1) was changed to 0.60 g and EHPE3150CE was changed to 9.48 g, to obtain a coating film. The fluorine concentration in the obtained resin solid was 0.10% by weight, and the silicon compound concentration in the resin solid was 1.8% by weight.

[Example 4]
Preparation of coating liquid and coating film A coating liquid was prepared in the same manner as in Example 2 except that 0.25 g of the polymer (A1) and 9.83 g of EHPE3150CE were changed to obtain a coating film. The fluorine concentration in the obtained resin solid was 0.04% by weight, and the silicon compound concentration in the resin solid was 0.8% by weight.

[Comparative Example 2]
Preparation of Coating Solution and Coating Film A coating solution was prepared in the same manner as in Example 2 except that the polymer (A1) was changed to the polymer (B1), and a coating solution was obtained. The silicon compound concentration in the resin solid content of the obtained coating liquid was 3.0% by weight.

  Using the obtained coating liquid, a coating film was produced in the same manner as in Example 2, and a transparent coating film having a thickness of about 0.9 μm was obtained.

[Comparative Example 3]
Preparation of Coating Liquid and Coating Film A coating liquid was prepared in the same manner as in Comparative Example 2 except that the polymer (B1) was changed to 0.60 g and EHPE3150CE was changed to 9.48 g, to obtain a coating film. The silicon compound concentration in the obtained resin solid was 1.8% by weight.

[Comparative Example 4]
Preparation of Coating Solution and Coating Film A coating solution was prepared in the same manner as in Comparative Example 2 except that the polymer (B1) was changed to 0.25 g and EHPE3150CE was changed to 9.83 g to obtain a coating film. The silicon compound concentration in the obtained resin solid was 0.8% by weight.

[Example 5]
Rubbing orientation treatment of coating film Surface property tester HEIDON Type: 14FW (made by Shinto Kagaku Co., Ltd.) ASTM rubbing cloth (Yokawa Chemical Co., Ltd. Rayon: YA-18-R) moving direction and texture direction These were wound so as to coincide with each other, and the surface of the coating film obtained in Example 2 was moved 20 times in the same direction at a moving speed of 300 mm / min with a vertical load of 200 g, and a rubbing alignment treatment was performed. A coating film was obtained.

[Example 6]
Rubbing orientation treatment of the coating film A coating film obtained by subjecting the coating film obtained in Example 3 to rubbing orientation treatment in the same manner as in Example 5 was obtained.

[Example 7]
Rubbing alignment treatment of coating film A coating film obtained by subjecting the coating film obtained in Example 4 to rubbing alignment treatment in the same manner as in Example 5 was obtained.

[Comparative Example 5]
Rubbing alignment treatment of the coating film The rubbing alignment treatment was performed in the same manner as in Example 5 except that the coating film obtained in Example 2 was changed to the coating film obtained in Comparative Example 2, and the rubbing alignment treatment was performed. A coating film was obtained.

[Comparative Example 6]
Coating film rubbing alignment treatment A coating film obtained by subjecting the coating film obtained in Comparative Example 3 to rubbing alignment treatment in the same manner as in Comparative Example 5 was obtained.

[Comparative Example 7]
Rubbing orientation treatment of coating film A coating film obtained by subjecting the coating film obtained in Comparative Example 4 to rubbing orientation treatment in the same manner as in Comparative Example 5 was obtained.

[test]
The physical property values of the coating films of Examples 2 to 7 and Comparative Examples 2 to 7 in the present invention were measured by the following methods.

1) Contact angle and surface free energy measurement Distilled water (for nitrogen / phosphorus measurement, manufactured by Kanto Chemical Co., Inc.) and methylene iodide (99%, manufactured by Aldrich) were used as probe liquids, and the FACE contact angle was used for the measuring device. Using a meter (image processing type) CA-X type (manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angle in the coating film is measured and obtained under conditions where the dropping amount is about 1.8 μL and the measurement temperature is 20 ° C. The surface free energy was calculated from the contact angle value according to the Kaelble-Uy theory.

2) Friction resistance test (ASTM flat indenter)
Using a surface property tester HEIDON Type: 14FW (manufactured by Shinto Kagaku Co., Ltd.), measurement was performed according to ASTM D1894.

  Table 1 shows the physical property values of the coating films obtained.

(Consideration of evaluation results of examples)
When comparing Examples 2 to 7 and Comparative Examples 2 to 7 with contact angles, Examples 2 to 7 into which fluorine-based silicon compounds were introduced had higher contact angles of pure water and methylene iodide, and surface free energy was higher. It has led to a decline. It can be seen that the water- and oil-repellent properties, particularly the oil-repellent properties are manifested by the fluorine-containing effect.

  Moreover, when Example 5-7 and Comparative Examples 5-7 are compared by a dynamic friction coefficient, the direction of Examples 5-7 is given by giving a rubbing orientation process and expressing the function of a fluorine-type silicon compound more effectively. However, it can be seen that the dynamic friction coefficient is reduced and the slip property (slip property) is improved.

  Furthermore, when Example 2-4 and Example 5-7 are compared by a dynamic friction coefficient, the dynamic friction coefficient of Examples 5-7 is lower than the dynamic friction coefficient of Examples 2-4. Such a tendency is not observed when Comparative Examples 2 to 4 and Comparative Examples 5 to 7 are compared by the dynamic friction coefficient, and thus seems to be a unique effect by containing the fluorine-based silicon compound in the present invention. . Therefore, it can be seen that the film of the present invention can further improve the slip property by performing a rubbing treatment.

  The polymer and surface treatment agent of the present invention are effective in improving water repellency / oil repellency, slip property (slip property), and specific applications include, for example, an antifouling treatment agent for a protective film used in a display, It can be used as a surface modifier for preventing stains on the display surface and touch panel, preventing fingerprint adhesion, etc., and can diversify various properties and applications.

Claims (22)

A monomer (a) which is a silicon compound represented by the following general formula (I) and an addition polymerizable monomer (b) containing a crosslinkable functional group and an addition polymerizable functional group are used as monomers. A polymer which is an addition polymer and has the crosslinkable functional group in an uncrosslinked state.

(In general formula (I),
R _f is a C1-C20 linear or branched fluoroalkyl optionally substituted with any methylene with oxygen; at least one hydrogen substituted with fluorine or trifluoromethyl, A fluoroaryl having 6 to 20 carbon atoms; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is substituted with fluorine or trifluoromethyl;
n represents an integer of 0 to 1,000,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen; having 1 to 30 carbon atoms, any hydrogen may be replaced with fluorine, and any Alkyl in which methylene may be replaced by oxygen or cycloalkylene; substituted or unsubstituted aryl; and substituted or unsubstituted aryl, and any hydrogen may be replaced by fluorine, and any methylene is replaced by oxygen or cycloalkylene An arylalkyl composed of optionally substituted alkylene; and a group selected from
A ¹ represents an addition polymerizable functional group. ) R _f in the general formula (I) is 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydro Dodecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α, α-trifluoromethylphenyl The polymer according to claim 1. 3. _Rf in the general formula (I) is tridecafluoro-1,1,2,2-tetrahydrooctyl or heptadecafluoro-1,1,2,2-tetrahydrodecyl. The polymer described in 1. R ³ and R ⁴ in the general formula (I) are each independently methyl, phenyl or 3,3,3-trifluoropropyl,
R ¹ , R ² , R ⁵ , and R ⁶ are each independently methyl or phenyl;
The polymer according to claim 1, wherein A ¹ represents a radical polymerizable functional group. A ¹ in general formula (I) contains (meth) acryl or styryl, The polymer as described in any one of Claims 1-4 characterized by the above-mentioned. The polymer according to claim 5, wherein A ¹ in the general formula (I) is any ^one of the following general formulas (II), (III), and (IV).

(In General Formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁷ represents hydrogen, linear or branched alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms. Represent,
In the general formula (III), R ⁸ represents hydrogen, linear or branched alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and X ¹ represents alkylene having 2 to 20 carbon atoms. Y represents —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, or —OCH ₂ CH (CH ₃ ) —, p represents an integer of 0 to 3,
In the general formula (IV), Y ² represents a single bond, methylene, or alkylene having 2 to 10 carbon atoms. ) In the general formula (II), Y ¹ is alkylene having 2 to 6 carbon atoms, R ⁷ is hydrogen or alkyl having 1 to 3 carbon atoms,
In the general formula (III), X ¹ is —CH ₂ CH ₂ CH ₂ —, Y is —OCH ₂ CH ₂ —, p is 0 or 1, and R ⁸ is hydrogen or 1 to 3 carbon atoms. The alkyl of
The polymer according to claim 6, wherein in the general formula (IV), Y ² is a single bond or methylene or ethylene.   The polymer according to any one of claims 1 to 7, wherein the addition polymerizable functional group of the addition polymerizable monomer (b) is a radical polymerizable functional group.   The crosslinkable functional group of the addition polymerizable monomer (b) is selected from hydroxyl, a monovalent functional group including a cyclic ether, alkyl halide, isocyanate, amino and carboxyl. 9. The polymer according to 8.   The polymer according to claim 9, wherein the crosslinkable functional group of the addition polymerizable monomer (b) is a monovalent functional group containing a cyclic ether.   11. The polymer according to claim 10, wherein the monovalent functional group containing the cyclic ether is selected from glycidyl, oxetanyl, epoxycyclohexyl, and dioxolane.   Addition weight further comprising an addition polymerizable monomer (c) other than the monomer (a) and the addition polymerizable monomer (b), which are silicon compounds, having an addition polymerizable functional group. The polymer according to any one of claims 1 to 11, wherein the polymer is a coalescence. The polymer according to claim 12, wherein the addition polymerizable functional group of the addition polymerizable monomer (c) is a radical polymerizable functional group.   14. The polymer according to claim 13, wherein the radical polymerizable functional group contains (meth) acryl or styryl. The monomer (a) which is a silicon compound represented by the following general formula (I), the monomer (b) containing a crosslinkable functional group and a radical polymerizable functional group, and a radical polymerizable functional group, A radical polymer having a monomer (a) which is a silicon compound and a monomer (c) other than the monomer (b) and having the crosslinkable functional group in an uncrosslinked state. There,
The crosslinkable functional group is selected from glycidyl, oxetanyl, epoxycyclohexyl, and dioxolane,
The polymer, wherein the radical polymerizable functional group of the monomer (c) contains (meth) acryl or styryl.

(In the general formula (I), R _f represents tridecafluoro-1,1,2,2-tetrahydrooctyl or heptadecafluoro-1,1,2,2-tetrahydrodecyl, and n is 0 to 1, 000 represents an integer of 000, R ^{1 to} R ⁶ each independently represent methyl or phenyl, and A ¹ represents any ^one of the following general formulas (II), (III), or (IV).

(In the general formula (II), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ⁷ represents hydrogen or linear or branched alkyl having 1 to 3 carbon atoms,
In the general formula (III), X ¹ represents —CH ₂ CH ₂ CH ₂ —, Y represents —OCH ₂ CH ₂ —, p represents 0 or 1, and R ⁸ represents hydrogen or 1 to 3 carbon atoms. Represents alkyl,
In the general formula (IV), Y ² represents a single bond or methylene or ethylene. )   The resin composition containing the polymer as described in any one of Claims 1-15, and resin or its monomer.   The resin composition according to claim 16, wherein the resin is a crosslinkable resin having a structure capable of crosslinking with the crosslinkable functional group in the polymer.   The resin composition according to claim 17, wherein the crosslinkable resin is a thermosetting resin.   The thermosetting resin or a monomer thereof is a compound having a monovalent functional group including hydroxyl, cyclic ether, alkyl halide, isocyanate, amino, or carboxyl, according to claim 18. Resin composition.   The resin composition according to claim 19, wherein the monovalent functional group containing the cyclic ether is selected from glycidyl, oxetanyl, epoxycyclohexyl, and dioxolane.   The surface treating agent containing the resin composition as described in any one of Claims 16-20.   A resin film obtained from the surface treatment agent according to claim 21.