JP2009197071A - Fluoropolymer and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymer useful for a film etc. excellent in antifouling properties, non-adhesive performance, mold release characteristics, slip performance, abrasion resistance, corrosion resistance, electric insulation properties, antireflection performance, flame retardancy, antistatic properties, chemical resistance and weather resistance etc., and also having amphipatic properties and cleaning characteristics. <P>SOLUTION: This polymer comprises in the molecule a structural unit A derived from fluorosilsesquioxane having an addition-polymerizable functional group, a structural unit B derived from an addition-polymerizable monomer having a hydrophilic group, a structural unit C derived from an addition-polymerizable monomer and having a polymerizable unsaturated bond-containing group in a side chain, and optionally, a structural unit E derived from an addition-polymerizable monomer excepting the fluorosilsesquioxane having the addition-polymerizable functional group, the addition-polymerizable monomer having the hydrophilic group, and the addition-polymerizable monomer having a functional group capable of deriving the polymerizable unsaturated bond-containing group. Otherwise, this polymer comprises in the molecule the structural unit A, the structural unit B, the structural unit C, a structural unit D derived from an organopolysiloxane having an addition-polymerizable functional group, and optionally, a structural unit E' derived from an addition-polymerizable monomer excepting the fluorosilsesquioxane having the addition-polymerizable functional group, the addition-polymerizable monomer having the hydrophilic group, the addition-polymerizable monomer having a functional group capable of deriving the polymerizable unsaturated bond-containing group, and the organopolysiloxane having the addition-polymerizable functional group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a polymer containing fluorine. Furthermore, this invention relates to the surface modifier containing the resin composition containing a fluoropolymer.
Furthermore, this invention relates to the membrane | film | coat obtained by the surface modifier containing the resin composition containing a fluoropolymer.

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. Yes.
Specifically, the following methods can be mentioned as methods for imparting antifouling properties against dirt such as fingerprints and sebum.
1) A method in which a fluorine atom-containing alkylalkoxysilane compound and a hydrolyzate thereof are added to a curable resin composition to form a cured film to make the surface water- and oil-repellent (see, for example, Patent Document 1).
2) Applying a copolymer solution of a polydimethylsiloxane compound containing a (meth) acryloyl group and a polymerizable silane compound such as vinyltrimethoxysilane to a substrate as it is to form a film, A method for making the surface water- and oil-repellent (for example, see Patent Document 2).
3) By forming fine irregularities with silica fine particles on the surface of the base material and forming a film of a fluorine atom-containing alkylsilane compound on the surface layer, the water and oil repellency is further improved, the contact area is also reduced, and the dirt is further increased. A technique for making it difficult to attach (for example, see Patent Document 3)
However, in these conventional methods, dirt is still likely to adhere in applications where a finger touches repeatedly, such as a mobile phone or a touch panel, and because of water and oil repellency, the dirt is repelled, and the dirt is conspicuous. There was a problem that.
As a method other than the above,
4) A copolymer having water-repellent silicone and hydrophilic tertiary amine or quaternary ammonium in the side chain is applied to the substrate, and the surface is amphiphilic to impart antifogging and antifouling properties. Although a technique (for example, refer to Patent Document 4) is disclosed, the polymer copolymer solution is simply applied, and the adhesion to the substrate and durability are not sufficient.
Japanese Patent Laid-Open No. 10-104403 Japanese Patent Laid-Open No. 10-7986 Japanese Patent Laid-Open No. 10-310455 JP 2002-105434 A

  The present invention has been made to meet the above-described problems of the prior art, and is antifouling property, non-adhesiveness, release property, slipperiness, wear resistance, corrosion resistance, electrical insulation, antireflection property, It is an object of the present invention to provide a new polymer that is excellent in flame retardancy, antistatic properties, chemical resistance, weather resistance, and the like, and further has amphiphilic properties and cleaning properties, and is useful as an ultraviolet curable film.

As a result of intensive studies from the above viewpoint, the present inventors have derived from a structural unit derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule and an addition polymerizable monomer containing a hydrophilic group. And an addition copolymer comprising a structural unit derived from an addition polymerizable monomer and a structural unit having a group having a polymerizable unsaturated bond in the side chain as an essential component, or one in the molecule. A structural unit derived from fluorosilsesquioxane having two addition polymerizable functional groups, a structural unit derived from an addition polymerizable monomer containing a hydrophilic group, and a structural unit derived from an addition polymerizable monomer An addition copolymer comprising a structural unit having a group having a polymerizable unsaturated bond in the chain and a structural unit derived from an organopolysiloxane having an addition polymerizable functional group as an essential component has excellent amphipathic properties, Easily wash off the attached dirt And (cleaning) were useful as capable film.

  The present invention relates to a structural unit derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, a structural unit derived from an addition polymerizable monomer containing a hydrophilic group, and an addition polymerizable monomer. An addition copolymer, or a fluorosil having one addition-polymerizable functional group in the molecule, which is a structural unit derived from and having a structural unit having a group having a polymerizable unsaturated bond in the side chain as an essential component A structural unit derived from sesquioxane, a structural unit derived from an addition polymerizable monomer containing a hydrophilic group, and a structural unit derived from an addition polymerizable monomer and having a polymerizable unsaturated bond in the side chain And an addition copolymer comprising as an essential component a constitutional unit derived from an organopolysiloxane having an addition polymerizable functional group. Furthermore, the new use of the said fluoropolymer is provided. New uses include, for example, a fluorosilsesquioxane structural unit having one addition polymerizable functional group in the molecule, a structural unit derived from an addition polymerizable monomer containing a hydrophilic group, and a side chain. An addition copolymer having a structural unit of an addition polymerizable monomer having a group having a polymerizable unsaturated bond bonded thereto, or a fluorosilsesqui having one addition polymerizable functional group in the molecule. A structural unit derived from an oxan, a structural unit derived from an addition polymerizable monomer containing a hydrophilic group, and a structural unit of an addition polymerizable monomer in which a group having a polymerizable unsaturated bond is bonded to the side chain; For example, the structural unit derived from organopolysiloxane having an addition polymerizable functional group is an essential component, and an addition copolymer is used as a surface modifier. The polymer of the present invention can be radically cured by ultraviolet rays, and can be suitably used as an ultraviolet curable surface modifier.

式（１）において、Ｒ_f ¹〜Ｒ_f ⁷はそれぞれ独立して、任意のメチレンが酸素で置き換えられていてもよい、炭素数１〜２０のフルオロアルキル；少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数６〜２０のフルオロアリール；またはアリール中の少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数７〜２０のフルオロアリールアルキルを示し、Ａ¹は、付加重合性官能基を示す。
[４] 式（１）におけるＲ_f ¹〜Ｒ_f ⁷がそれぞれ独立して、３,３,３-トリフルオロプロピル、３,３,４,４,４-ペンタフルオロブチル、３,３,４,４,５,５,６,６,６-ノナフルオロヘキシル、トリデカフルオロ-１,１,２,２-テトラヒドロオクチル、ヘプタデカフルオロ-１,１,２,２-テトラヒドロデシル、ヘンイコサフルオロ-１,１,２,２-テトラヒドロドデシル、ペンタコサフルオロ-１,１,２,２-テトラヒドロテトラデシル、（３-ヘプタフルオロイソプロポキシ）プロピル、ペンタフルオロフェニルプロピル、ペンタフルオロフェニル、またはα,α,α-トリフルオロメチルフェニルを示すことを特徴とする、[３]に記載の重合体。
[５] 式（１）におけるＲ_f ¹〜Ｒ_f ⁷がそれぞれ独立して、３,３,３-トリフルオロプロピル、３,３,４,４,５,５,６,６,６-ノナフルオロヘキシル、またはトリデカフルオロ-１,１,２,２-テトラヒドロオクチルを示すことを特徴とする、[３]に記載の重合体。
[６] 式（１）におけるＡ¹がラジカル重合性官能基であることを特徴とする、[３]〜[５]のいずれかに記載の重合体。
[７] 式（１）におけるＡ¹が（メタ）アクリルまたはスチリルを含むことを特徴とする、[６]に記載の重合体。
[８] 式（１）におけるＡ¹が下記式（２）または（３）で示されるいずれかである、[７]に記載の重合体。

式（２）において、Ｙ¹が炭素数２〜１０のアルキレンを示し、Ｒ¹が水素、炭素数１〜５のアルキル、または炭素数６〜１０のアリールであり、式（３）において、Ｙ²が単結合または炭素数１〜１０のアルキレンを示す。
[９] 式（２）において、Ｙ¹が炭素数２〜６のアルキレンを示し、Ｒ¹が水素またはメチルを示し、式（３）においてＹ²が単結合または炭素数１あるいは２のアルキレンを示す、[８]に記載の重合体。
[１０] 親水性基を含む付加重合性単量体の親水性基が、ヒドロキシル、該ヒドロキシルの塩、カルボキシル、該カルボキシルの塩、スルホ、該スルホの塩、リン酸基、該リン酸基の塩、アミノ、該アミノの塩、アミド、四級アンモニウム塩またはオキシアルキレンである、[１]〜[９]のいずれかに記載の重合体。
[１１] 親水性基を含む付加重合性単量体の親水性基が、オキシアルキレン、またはアミ
ドである、[１]〜[９]のいずれかに記載の重合体。
[１２] 親水性基を含む付加重合性単量体が、ポリアルキレングリコールモノ（メタ）アクリレート、Ｎ−アルキル置換の（メタ）アクリルアミド、またはＮ，Ｎ−ジアルキル置換の（メタ）アクリルアミドである、[１]〜[９]のいずれかに記載の重合体。
[１３] 前記構成単位Ｃの重合性不飽和結合を有する基がラジカル重合性官能基である、[１]〜[１２]のいずれかに記載の重合体。
[１４] 前記構成単位Ｃの重合性不飽和結合を有する基が（メタ）アクリルまたはスチリルである、[１]〜[１３]のいずれかに記載の重合体。
[１５] 前記構成単位Ｄの付加重合性官能基を有するオルガノポリシロキサンが、下記式（４）で示されることを特徴とする、[２]〜[１４]のいずれかに記載の重合体。

式（４）において、ｎは１〜１，０００の整数であり；Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ独立して水素、炭素数が１〜３０であり、任意の水素がフッ素で置き換えられてもよく、そして任意の−ＣＨ₂−が−Ｏ−またはシクロアルキレンで置き換えられてもよいアルキル、置換もしくは非置換のアリール、および置換もしくは非置換のアリールと、任意の水素がフッ素で置き換えられてもよく任意の−ＣＨ₂−が−Ｏ−またはシクロアルキレンで置き換えられてもよいアルキレンとで構成されるアリールアルキルであり；Ａ²は付加重合性官能基である。
[１６] 式（４）におけるＲ²およびＲ³が、それぞれ独立して水素、フェニルまたは炭素数が１〜８で任意の水素がフッ素で置き換えられてもよいアルキルであり；Ｒ⁴およびＲ⁵が、それぞれ独立して炭素数が１〜２０であり任意の水素がフッ素で置き換えられてもよいアルキル、炭素数が６〜２０であり任意の水素がフッ素で置き換えられてもよいアリール、または炭素数が７〜２０であり任意の水素がフッ素で置き換えられてもよいアリールアルキルであり；Ｒ⁶が、炭素数が１〜２０であり任意の水素がフッ素で置き換えられてもよいアルキル、炭素数が６〜２０であり任意の水素がフッ素で置き換えられてもよいアリール、または炭素数が７〜２０であり任意の水素がフッ素で置き換えられてもよいアリールアルキルである[１５]に記載の重合体。
[１７] 式（４）におけるＲ²およびＲ³は、それぞれ独立してメチル、フェニルまたは３，３，３−トリフルオロプロピルであり；Ｒ⁴およびＲ⁵は、それぞれ独立してメチルまたはフェニルであり；Ｒ⁶はメチル、エチル、プロピル、ブチル、イソブチル、フェニル、３,３,３-トリフルオロプロピル、３,３,４,４,４-ペンタフルオロブチル、３,３,４,４,５,５,６,６,６-ノナフルオロヘキシル、トリデカフルオロ-１,１,２,２-テトラヒドロオクチル、ヘプタデカフルオロ-１,１,２,２-テトラヒドロデシル、ヘンイコサフルオロ-１,１,２,２-テトラヒドロドデシル、ペンタコサフルオロ-１,１,２,２-テトラヒドロテトラデシル、（３-ヘプタフルオロイソプロポキシ）プロピル、ペンタフルオロフェニルプロピル、ペンタフルオロフェニル、またはα,α,α-トリフルオロメチルフェニルである[１５]に記載の重合体。
[１８] 式（４）におけるＲ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ同時にメチルである[１５]に記載の重合体。
[１９] 式（４）におけるＡ²がラジカル重合性官能基であることを特徴とする、[１５]〜[１８]のいずれかに記載の重合体。
[２０] 式（２）におけるＡ²が（メタ）アクリルまたはスチリルを含むことを特徴とする、[１９]に記載の重合体。
[２１] 式（４）におけるＡ²が下記式（２）、（３）または（５）で示されるいずれかである[２０]に記載の重合体。

式（２）において、Ｙ¹が炭素数２〜１０のアルキレンを示し、Ｒ¹が水素、炭素数１〜５のアルキル、または炭素数６〜１０のアリールであり、式（５）において、Ｒ⁷は水素、炭素数１〜５のアルキル、または炭素数６〜１０のアリールであり、Ｘ¹は炭素数が２〜２０のアルキレンであり、Ｙは−ＯＣＨ₂ＣＨ₂−、−ＯＣＨ（ＣＨ₃）ＣＨ₂−、または−ＯＣＨ₂ＣＨ（ＣＨ₃）−であり、ｐは０〜３の整数であり、式（３）において、Ｙ²が単結合または炭素数１〜１０のアルキレンを示す。
[２２] 式（２）において、Ｙ¹が炭素数２〜６のアルキレンを示し、Ｒ⁶が水素またはメチルを示し、式（５）において、Ｘ¹は−ＣＨ₂ＣＨ₂ＣＨ₂−を示し、Ｙは−ＯＣＨ₂ＣＨ₂−を示し、ｐは０または１を示し、Ｒ⁷が水素またはメチルを示し、式（３）においてＹ²が単結合または炭素数１あるいは２のアルキレンを示す、[２１]に記載の重合体。
[２３] [１]〜[２２]のいずれかに記載の重合体と、熱可塑性樹脂、熱硬化性樹脂および活性エネルギー線硬化性樹脂から選ばれる一種類以上の樹脂とを含む樹脂組成物。
[２４] さらに、重合性不飽和結合を有する基を含む重合体であって、[１]〜[２２]のいずれにも該当しない重合体を含む、[２３]に記載の樹脂組成物。
[２５] [１]〜[２２]のいずれかに記載の重合体または[２３]もしくは[２４]に記載の樹脂組成物を含有する表面改質剤。
[２６] [２５]に記載の表面改質剤により得られる両親媒性の皮膜。 That is, this invention relates to the polymer, resin composition, and film | membrane shown below.
[1] Structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, structural unit B derived from an addition polymerizable monomer containing a hydrophilic group, addition polymerizable monomer A structural unit C derived from a body and having a group having a polymerizable unsaturated bond in the side chain, and optionally a fluorosilsesquioxane having one addition polymerizable functional group in the molecule, a hydrophilic group And a polymer comprising a structural unit E derived from an addition polymerizable monomer other than the addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond.
[2] Structural unit A derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule, structural unit B derived from an addition-polymerizable monomer containing a hydrophilic group, addition-polymerizable monomer A structural unit C having a group having a polymerizable unsaturated bond in the side chain, a structural unit D derived from an organopolysiloxane having an addition polymerizable functional group, and, optionally, in the molecule Fluorosilsesquioxane having one addition polymerizable functional group, addition polymerizable monomer having a hydrophilic group, addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond, and A polymer comprising a structural unit E ′ derived from an addition polymerizable monomer other than an organopolysiloxane having an addition polymerizable functional group.
[3] The polymer according to [1] or [2], wherein the fluorosilsesquioxane having one addition polymerizable functional group in the molecule is represented by the following formula (1).

In Formula (1), R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoro A fluoroaryl having 6 to 20 carbon atoms replaced by methyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and A ¹ is An addition polymerizable functional group is shown.
[4] R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 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, henicosa Fluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α , α, α-trifluoromethylphenyl, The polymer according to [3].
[5] R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nona [3] The polymer according to [3], which represents fluorohexyl or tridecafluoro-1,1,2,2-tetrahydrooctyl.
[6] The polymer according to any one of [3] to [5], wherein A ¹ in the formula (1) is a radical polymerizable functional group.
[7] The polymer according to [6], wherein A ¹ in formula (1) contains (meth) acryl or styryl.
[8] The polymer according to [7], wherein A ¹ in the formula (1) is any one of the following formulas (2) or (3).

In Formula (2), Y ¹ represents alkylene having 2 to 10 carbons, R ¹ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons. In Formula (3), Y 1 ² represents a single bond or alkylene having 1 to 10 carbon atoms.
[9] In the formula (2), Y ¹ represents an alkylene having 2 to 6 carbon atoms, R ¹ represents hydrogen or methyl, and in the formula (3), Y ² represents a single bond or an alkylene having 1 or 2 carbon atoms. The polymer according to [8].
[10] The hydrophilic group of the addition-polymerizable monomer containing a hydrophilic group is hydroxyl, salt of hydroxyl, carboxyl, salt of carboxyl, sulfo, salt of sulfo, phosphate group, phosphate group The polymer according to any one of [1] to [9], which is a salt, amino, a salt of the amino, an amide, a quaternary ammonium salt, or oxyalkylene.
[11] The polymer according to any one of [1] to [9], wherein the hydrophilic group of the addition polymerizable monomer containing a hydrophilic group is oxyalkylene or amide.
[12] The addition polymerizable monomer containing a hydrophilic group is polyalkylene glycol mono (meth) acrylate, N-alkyl substituted (meth) acrylamide, or N, N-dialkyl substituted (meth) acrylamide. The polymer according to any one of [1] to [9].
[13] The polymer according to any one of [1] to [12], wherein the group having a polymerizable unsaturated bond of the structural unit C is a radically polymerizable functional group.
[14] The polymer according to any one of [1] to [13], wherein the group having a polymerizable unsaturated bond of the structural unit C is (meth) acryl or styryl.
[15] The polymer according to any one of [2] to [14], wherein the organopolysiloxane having an addition polymerizable functional group of the structural unit D is represented by the following formula (4).

In the formula (4), n is an integer of 1 to 1,000; R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a carbon number of 1 to 30, and any In which optionally hydrogen can be replaced by fluorine, and any —CH ₂ — can be replaced by —O— or cycloalkylene, substituted or unsubstituted aryl, and substituted or unsubstituted aryl, and Is an arylalkyl composed of alkylene in which hydrogen may be replaced by fluorine, and optional —CH ₂ — may be replaced by —O— or cycloalkylene; A ² is an addition-polymerizable functional group .
[16] R ² and R ³ in Formula (4) are each independently hydrogen, phenyl, or alkyl having 1 to 8 carbon atoms, and any hydrogen may be replaced by fluorine; R ⁴ and R ⁵ Are independently alkyl having 1 to 20 carbon atoms and arbitrary hydrogen may be replaced by fluorine, aryl having 6 to 20 carbon atoms and arbitrary hydrogen being replaced by fluorine, or carbon number be an arylalkyl be replaced by arbitrary hydrogen fluorine is 7 to 20; R ⁶ is alkyl may be any of hydrogen from 1 to 20 carbon atoms is replaced by fluorine, carbon atoms Is aryl having 6 to 20 and arbitrary hydrogen may be replaced with fluorine, or arylalkyl having 7 to 20 carbon atoms and optionally having hydrogen replaced with fluorine [15] Polymer.
[17] R ² and R ³ in formula (4) are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ⁴ and R ⁵ are each independently methyl or phenyl Yes; R ⁶ is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 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, - polymer according to trifluoromethylphenyl [15].
[18] The polymer according to [15], wherein R ² , R ³ , R ⁴ and R ⁵ in formula (4) are each simultaneously methyl.
[19] The polymer according to any one of [15] to [18], wherein A ² in the formula (4) is a radical polymerizable functional group.
[20] The polymer as described in [19], wherein A ² in the formula (2) contains (meth) acryl or styryl.
[21] The polymer according to [20], wherein A ² in the formula (4) is any one of the following formulas (2), (3), or (5).

In Formula (2), Y ¹ represents alkylene having 2 to 10 carbons, R ¹ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons. ⁷ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, X ¹ is alkylene having 2 to 20 carbon atoms, and Y is —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ — or —OCH ₂ CH (CH ₃ ) —, p is an integer of 0 to 3, and in formula (3), Y ² represents a single bond or an alkylene having 1 to 10 carbon atoms. .
[22] In formula (2), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ⁶ represents hydrogen or methyl, and in formula (5), X ¹ represents —CH ₂ CH ₂ CH ₂ —. , Y represents —OCH ₂ CH ₂ —, p represents 0 or 1, R ⁷ represents hydrogen or methyl, and Y ² represents a single bond or an alkylene having 1 or 2 carbon atoms in the formula (3). [21] The polymer according to [21].
[23] A resin composition comprising the polymer according to any one of [1] to [22] and one or more kinds of resins selected from a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin.
[24] The resin composition according to [23], further including a polymer containing a group having a polymerizable unsaturated bond, the polymer not corresponding to any of [1] to [22].
[25] A surface modifier containing the polymer according to any one of [1] to [22] or the resin composition according to [23] or [24].
[26] An amphiphilic film obtained by the surface modifier according to [25].

  In the polymer of the present invention, side chains of a hydrophilic part and a hydrophobic part coexist in the polymer and have excellent environmental responsiveness due to movement of the side chains. For example, in a hydrophobic environment in the air, the hydrophilic part in the polymer is buried inside, only the hydrophobic part is present on the interface, and when the environment changes to hydrophilic like water, the hydrophilic part in the polymer A part moves to an interface and a hydrophilic function expresses. As a result, even if dirt adheres to the surface, it can be expected that the dirt can be floated by the oil repellent function and the dirt can be washed away by the hydrophilic function. The fluorine-based polymer of the present invention and the resin composition containing the polymer have antifouling properties, non-adhesiveness, releasability, slipperiness, wear resistance, corrosion resistance, electrical insulation properties, and antireflection properties. It is also excellent in flame retardancy, antistatic properties, chemical resistance, weather resistance, and the like. For example, it can be used as an ultraviolet curable surface modifier by coating on the surface of various substrates.

In the present invention, addition polymerization means that addition polymerization is possible, addition polymerization monomer means a monomer capable of addition polymerization, and addition polymerizable functional group means addition polymerization. Means a functional group.
The polymer of the present invention contains the structural unit A, the structural unit B, and the structural unit C and the structural unit E as an optional component, or the structural unit A, the structural unit B, the structural unit C, and the structural unit D. And a structural unit E ′ as an optional component. In the polymer, the structural unit A is derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, and the structural unit B is hydrophilic. Derived from an addition polymerizable monomer containing a group, the structural unit C is a structural unit derived from an addition polymerizable monomer and derived from a monomer having a group having a polymerizable unsaturated bond in the side chain; The structural unit D is derived from an organopolysiloxane having an addition polymerizable functional group, and the structural unit E is an addition polymerization property other than the addition polymerizable monomer used as the structural unit A, the structural unit B, and the structural unit C. Derived from the monomer, the structural unit E ′ is Serial structural units A, structural units B, and from the addition polymerizable monomer other than the addition polymerizable monomer used as building blocks C, and the structural unit D. “Derived” means a polymerized residue when each monomer constitutes the polymer of the present invention. The molar fraction (%) of the structural unit A in the polymer is represented by a, the molar fraction (%) of the structural unit B in the polymer is represented by b, and the molar fraction of the structural unit C in the polymer ( %) Is represented by c, the molar fraction (%) of the structural unit D in the polymer is represented by d, the molar fraction (%) of the structural unit E in the polymer is represented by e, and the composition in the polymer The mole fraction (%) of the unit E ′ is represented by e ′, and 0 <a <100, 0 <b <100, 0 <c <100, 0 ≦ e <100, a + b + c + e = 100, or 0 <a, respectively. <100, 0 <b <100, 0 <c <100, 0 <d <100, 0 ≦ e ′ <100, a + b + c + d + e ′ = 100.
The polymer of the present invention comprises a fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, an addition polymerizable monomer (β) containing a hydrophilic group, and a polymerizable unsaturated bond. Obtained by polymerizing an addition-polymerizable monomer having a group having an addition-polymerizable group, or an addition-polymerizable monomer having a hydrophilic group and a fluorosilsesquioxane (α) having one addition-polymerizable functional group in the molecule. It is also possible to obtain by polymerizing a monomer (β), an organopolysiloxane (δ) having an addition polymerizable functional group, and an addition polymerizable monomer having a group having a polymerizable unsaturated bond. In order to introduce a group having a polymerizable unsaturated bond more efficiently, for example, polymerization is performed with an addition polymerizable monomer (α) having a fluorine atom and an addition polymerizable monomer (β) having a hydrophilic group. Addition with a functional group capable of introducing a group having a polymerizable unsaturated bond A copolymerizable monomer or an addition polymerizable monomer (α) having a fluorine atom, an addition polymerizable monomer (β) containing a hydrophilic group, and an organo having an addition polymerizable functional group Polysiloxane (δ) and an addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond are copolymerized to obtain a precursor polymer, and the precursor is obtained via this functional group. It is preferable to obtain by introducing a group having a polymerizable unsaturated bond into.

Description of Structural Unit A <Fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule>
Fluorosilsesquioxane has a silsesquioxane skeleton in its molecular structure. Silsesquioxane is a general term for polysiloxanes represented by [(R—SiO _1.5 ) _n ] (where R is an optional substituent). The structure of the silsesquioxane is generally classified into a random structure, a ladder structure, and a cage structure according to the Si—O—Si skeleton. Furthermore, the cage structure is classified into T ₈ , T ₁₀ , T ₁₂ type and the like. Among them, the fluorosilsesquioxane used in the present invention preferably has a cage structure of T ₈ type [(R—SiO _1.5 ) ₈ ].

The fluorosilsesquioxane is characterized by having one addition polymerizable functional group. That is, one of R of silsesquioxane [(R—SiO _1.5 ) _n ] is an addition polymerizable functional group.
Examples of the above addition-polymerizable functional group include a group having a terminal olefin type or an internal olefin type radical polymerizable functional group; a group having a cationic polymerizable functional group such as vinyl ether or propenyl ether; and vinyl carboxyl or cyanoacryloyl And a group having an anion polymerizable functional group such as a radical polymerizable functional group.

The radical polymerizable functional group is not particularly limited as long as it is a radical polymerizable group. For example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N- Vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide, etc.
Groups containing meth) acrylic or styryl are preferred. Here, (meth) acryl is a general term for acrylic and methacrylic and means acrylic and / or methacrylic. The same shall apply hereinafter.

Examples of the radical polymerizable functional group having the (meth) acryl include a group represented by the following formula (2).
In formula (2), Y ¹ represents an alkylene having 2 to 10 carbon atoms, preferably an alkylene having 2 to 6 carbon atoms, and more preferably an alkylene (propylene) having 3 carbon atoms. R ¹ represents hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, preferably hydrogen or alkyl having 1 to 3 carbon atoms, particularly preferably hydrogen or methyl. Here, the alkyl having 1 to 5 carbon atoms may be either linear or branched.

Moreover, the group shown by the following formula | equation (3) is contained in the example of the radically polymerizable functional group which has said styryl. In formula (3), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms, preferably a single bond or alkylene having 1 to 6 carbon atoms, more preferably a single bond or alkylene having 1 or 2 carbon atoms. And particularly preferably a single bond or alkylene (ethylene) having 2 carbon atoms. Vinyl is bonded to any carbon of the benzene ring, preferably bonded to carbon in the para position with respect to Y ² .

Said fluorosilsesquioxane has at least one fluoroalkyl, fluoroarylalkyl or fluoroaryl. That is, at least one R of silsesquioxane (R—SiO _1.5 ) _n , preferably R other than the above addition polymerizable functional group, is fluoroalkyl, fluoroarylalkyl and / or fluoroaryl.

The fluoroalkyl may be either linear or branched. This fluoroalkyl has 1 to 20 carbon atoms, preferably 3 to 14 carbon atoms. Furthermore, any methylene of the fluoroalkyl may be replaced with oxygen. Here, methylene includes —CH ₂ —, —CFH—, or —CF ₂ —. That is, “any methylene may be replaced with oxygen” means that —CH ₂ —, —CFH—, or —CF ₂ — may be replaced with —O—. However, in the fluoroalkyl, two oxygens are not bonded (—O—O—). That is, the fluoroalkyl may have an ether bond. Also, in the preferred fluoroalkyl, the methylene adjacent to Si is not replaced with oxygen, and the terminal opposite to Si is CF ₃ . Furthermore, it is preferable that —CF ₂ — be replaced with oxygen rather than —CH ₂ — or —CFH— to be replaced with oxygen. Preferred specific examples of such fluoroalkyl 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-tetrahydrododecyl, henicosafluoro-1,1,2,2-tetrahydro Dodecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl and the like are included. Among them, perfluoroalkylethyl is preferably exemplified, but may be a group in which fluoroalkyl is bonded through —CH ₂ —CH ₂ —, or a group in which fluoroalkyl is bonded through —CH ₂ —. There may be.

  The fluoroarylalkyl is an alkyl containing an aryl containing fluorine, and preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. The fluorine contained is preferably one in which any one or more hydrogens in aryl are replaced with fluorine or trifluoromethyl. Examples of the aryl moiety include phenyl, naphthyl and the like, as well as heteroaryl, and examples of the alkyl moiety include methyl, ethyl, propyl and the like.

  The fluoroaryl is one in which any one or two or more hydrogens in the aryl are replaced with fluorine or trifluoromethyl, and the number of carbon atoms is preferably 6 to 20, more preferably Is 6. Examples of such aryl include phenyl, naphthyl and the like, as well as heteroaryl. Specific examples include fluorophenyl such as pentafluorophenyl and trifluoromethylphenyl.

  Of the above-mentioned fluoroalkyl, fluoroarylalkyl, or fluoroaryl contained in fluorosilsesquioxane, a preferred group is fluoroalkyl, more preferably perfluoroalkylethyl, and still more preferably 3,3,4- Trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl or tridecafluoro-1,1,2,2-tetrahydrooctyl.

As mentioned above, preferred fluorosilsesquioxanes have a T ₈ type structure, have one addition polymerizable functional group, and one or more fluoroalkyl, fluoroarylalkyl and / or fluoro It has aryl and is represented by the following structural formula (1).

In the above formula (1), A ¹ is an addition polysynthetic functional group, preferably the aforementioned radical polymerizable functional group, and R _f ^{1 to} R _f ⁷ are each independently the aforementioned fluoroalkyl, It is preferably fluoroarylalkyl or fluoroaryl. R _f ^{1 to} R _f ⁷ may be different groups or all may be the same group.
R _f ^{1 to} R _f ⁷ in formula (1) are each independently 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 preferred, and R _f ^{1 to} R _f ⁷ are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6. , 6-Nonafluorohexyl, or tridecafluoro-1,1,2,2- More preferably, it represents tetrahydrooctyl.

Explanation of Structural Unit B <Addition polymerizable monomer (β) containing hydrophilic group>
The addition polymerizable monomer containing a hydrophilic group may be a compound having a hydrophilic group and an addition polymerizable double bond in the molecule. Examples of such hydrophilic groups include hydroxyl, salt of hydroxyl, carboxyl, salt of carboxyl, sulfo, salt of sulfo, phosphate group, salt of phosphate group, amino, salt of amino, amide, A quaternary ammonium salt, oxyalkylene, etc. are mentioned. Preferred are vinyl compounds, vinylidene compounds, vinylene compounds, acrylic acid derivatives or styrene derivatives containing oxyalkylene or amide as a hydrophilic group. Here, the terminal hydroxyl group of oxyalkylene is preferably replaced with a group such as alkoxy, ester, or phenoxy.
Examples of such addition polymerizable monomers containing oxyalkylene include oxyalkylene-containing monomers such as polyalkylene glycol mono (meth) acrylates in which the terminal hydroxyl group is replaced with alkoxy, ester, or phenoxy. .
Specifically, methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono Monomers such as (meth) acrylate and phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate may be mentioned.
Examples of the addition polymerizable monomer containing an amide include N-alkyl-substituted (meth) acrylamide and N, N-dialkyl-substituted (meth) acrylamide.
Specifically, N-methyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-ethyl-N-aminoethyl Examples include monomers such as (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidone.

Explanation of Structural Unit C <Addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond>
As described above, the polymer of the present invention containing a group having a polymerizable unsaturated bond in the side chain can obtain a polymer having a functional group capable of introducing a group having a polymerizable unsaturated bond as a precursor. That is, the structural unit C is polymerized into a functional group capable of introducing a group having a polymerizable unsaturated bond of a structural unit derived from an addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond. It is a structural unit formed by introducing a group having a polymerizable unsaturated bond.
Here, examples of the functional group capable of introducing a group having a polymerizable unsaturated bond include a group having active hydrogen and a monovalent functional group containing a cyclic ether. Active hydrogen is hydrogen bonded to an atom (for example, nitrogen atom, sulfur atom, oxygen atom) having an electronegativity value exceeding that of carbon among hydrogen atoms existing in the molecule of the organic compound. That is. Therefore, a preferred precursor for obtaining the polymer of the present invention is a polymer containing a group having active hydrogen, and a fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, hydrophilic An addition polymerizable monomer (β) containing a functional group, an addition polymerizable monomer (ζ) containing a group having active hydrogen, and an addition polymerizable monomer containing a monovalent functional group containing a cyclic ether Fluorosilsesquioxane (α) having an addition-polymerizable functional group in the molecule, an addition-polymerizable monomer (β) containing a hydrophilic group, or an addition-polymerizable functional group as an essential component An addition polymerizable monomer containing an active hydrogen-containing group (ζ) and an addition polymerizable monomer containing a monovalent functional group containing a cyclic ether together with the organopolysiloxane (δ) are essential components of the present invention. A polymer precursor can be obtained.

Examples of the group having active hydrogen include —OH, —SH, —COOH, —NH, —NH ₂ , —CONH ₂ , —NHCONH—, —NHCOO—, Na ⁺ [CH (COOC ₂ H ₅ )], —CH. ₂ NO ₂ , OOH, —SiOH, —B (OH) ₂ , —PH ₃ , —SH and the like can be mentioned, carboxyl, amino and hydroxyl are preferable, and hydroxyl is more preferable. The addition polymerizable monomer (ζ) containing a group having active hydrogen may be a compound having a group having active hydrogen and an addition polymerizable double bond in the molecule, and includes a group having active hydrogen. Any of vinyl compounds, vinylidene compounds, and vinylene compounds may be used. An acrylic acid derivative or a styrene derivative containing a group having active hydrogen is preferable.

  Examples of the monovalent functional group containing a cyclic ether include groups such as glycidyl, epoxycyclohexyl, and oxetanyl.

Examples of the addition polymerizable monomer containing a group having active hydrogen include monomers disclosed in JP-A-9-208681, JP-A-2002-348344, and JP-A-2006-158961.
Specific examples include the following monomers.
Examples of the carboxyl-containing vinyl monomer include (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid. Examples include glycol monoether, citraconic acid, citraconic acid monoalkyl ester, (meth) acrylic acid hexadecane and cinnamic acid.
As the hydroxyl group-containing vinyl monomer, a hydroxyl-containing monofunctional vinyl monomer and a hydroxyl-containing polyfunctional vinyl monomer are used. As the hydroxyl-containing monofunctional vinyl monomer, a vinyl monomer having one vinyl is used. For example, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-butene-1- Ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether (2-propenoxyethanol), 16-hydroxyhexadecane methacrylate and soot Such as allyl ether, and the like. As the hydroxyl-containing polyfunctional vinyl monomer, a vinyl monomer having a plurality of vinyls is used. For example, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, diglycerin. Tri (meth) acrylate, sorbitan tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetraglycerin penta (meth) acrylate, glycerin di (meth) allyl ether, trimethylolpropane di (meth) allyl ether, pentaeryl Thritol tri (meth) allyl ether, diglycerin tri (meth) allyl ether, sorbitan tri (meth) allyl ether, dipentaerythritol penta (meth) allyl ether and Tet Glycerine penta (meth) allyl ether.
Examples of the amino-containing vinyl monomer include aminoethyl (meth) acrylate, aminoisopropyl (meth) acrylate, aminobutyl (meth) acrylate, aminohexyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, crotylamine, Examples include aminostyrene, methyl α-acetaminoacrylate, N-allylphenylenediamine, and 16-methacryloylhexadecanamine.

  In addition, an addition polymerizable monomer which is a (meth) acrylic acid derivative having a monovalent functional group containing a cyclic ether includes an epoxy-containing (meth) acrylate such as glycidyl (meth) acrylate; 3,4-epoxycyclohexyl Cycloaliphatic epoxy-containing (meth) acrylates such as methyl (meth) acrylate; Oxetanyl-containing (meth) acrylates such as 3-ethyl-3- (meth) acryloyloxymethyloxetane; 4- (meth) acryloyloxymethyl-2- And dioxolane-containing (meth) acrylates such as methyl-2-ethyl-1,3-dioxolane;

Description of Structural Unit D <Organopolysiloxane (δ) having addition polymerizable functional group>
Organopolysiloxane typified by polydimethylsiloxane (hereinafter sometimes referred to as silicone or polysiloxane) has two types having polymerizable functional groups at both ends and one end. , Functional groups such as amino, hydroxyl, methacryloxy, carboxyl, glycidyl, epoxycyclohexyl and oxetanyl. The organopolysiloxane at both ends can introduce a silicone component into the organic polymer main chain, and the organopolysiloxane at one end can graft the silicone component to the organic polymer side chain. The polymer thus obtained has unique characteristics as silicone, such as water repellency, mold release, slipperiness, low friction, antithrombogenicity, heat resistance, electrical properties, flexibility, oxygen permeability. It exhibits radiation resistance and is widely used in the electronic materials field, cosmetics and medical fields.

The organopolysiloxane (δ) having an addition polymerizable functional group, which is a raw material monomer of the polymer of the present invention, preferably has a molecular structure represented by the following formula (4).

In the organopolysiloxane used in the present invention, in the above formula (4), n is an integer of 1 to 1,000; R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen. Alkyl, substituted or unsubstituted aryl having 1 to 30 carbon atoms, in which any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene And an arylalkyl composed of substituted or unsubstituted aryl, and alkylene in which any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene A ² is an addition polymerizable functional group.

Furthermore, in the organopolysiloxane having an addition polymerizable functional group used in the present invention, R ² and R ³ in the above formula (4) are each independently hydrogen, phenyl, or any hydrogen having 1 to 8 carbon atoms. Is alkyl optionally substituted by fluorine;
R ⁴ and R ⁵ are independently alkyl having 1 to 20 carbon atoms and arbitrary hydrogen may be replaced with fluorine, and 6 to 20 carbon atoms and arbitrary hydrogen may be replaced with fluorine. Aryl, or arylalkyl having 7 to 20 carbon atoms in which any hydrogen may be replaced by fluorine;
R ⁶ is alkyl having 1 to 20 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, aryl having 6 to 20 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, or It is preferably an arylalkyl that is 7 to 20 and in which arbitrary hydrogen may be replaced by fluorine.

Further, in the organopolysiloxane used in the present invention, R ² and R ³ in the above formula (4) are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ⁴ and R ⁵ Each independently is methyl or phenyl; R ⁶ is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 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, pentafluoro Nirupuropiru, pentafluorophenyl, or alpha, alpha, is preferably a α- trifluoromethylphenyl.

Further, in the organopolysiloxane used in the present invention, in the above formula (4), R ² , R ³ , R ⁴ and R ⁵ are preferably each simultaneously methyl. Also preferably, A ² in the above formula (4) is a radical polymerizable functional group, more preferably the A ² contains a (meth) acrylic or styryl, A ² is represented by the following formula (2), (3 ) Or (5) is more preferred.

In formula (2), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ¹ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and in formula (5), R ⁷ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, X ¹ is alkylene having 2 to 20 carbon atoms, and Y is —OCH ₂ CH ₂ —, —OCH. (CH ₃ ) CH ₂ —, or —OCH ₂ CH (CH ₃ ) —, p is an integer of 0 to 3, and in Formula (3), Y ² is a single bond or an alkylene having 1 to 10 carbon atoms. Indicates. Here, the alkyl having 1 to 5 carbon atoms may be either linear or branched.

In the present invention, in the above formula (2), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ¹ represents hydrogen or methyl, and in formula (5), X ¹ represents —CH ₂ CH ₂ CH ₂ —. Y represents —OCH ₂ CH ₂ —, p represents 0 or 1, R ⁷ represents hydrogen or methyl, and Y ² represents a single bond or an alkylene having 1 or 2 carbon atoms in the formula (3). It is preferable to show. Examples of organopolysiloxanes preferably used in the present invention include Chisso Corporation Silaplane (registered trademark) FM0711, Chisso Corporation Silaplane (registered trademark) FM0721, Chisso Corporation Silaplane (registered trademark) FM0725, Chisso Corporation Silaplane (registered trademark) TM0701, Chisso Corporation Silaplane (registered trademark) TM0701T, and the like are included.

Explanation of Structural Unit E and Structural Unit E ′ <Arbitrary Addition Polymerizable Monomer (ε), (ε ′)>
In the polymer precursor of the present invention, in addition to the above addition polymerizable monomers (α), (β), (ζ) or (α), (β), (δ), (ζ), resin And other than the monomer (α), (β), (ζ) as necessary, in order to control the compatibility, leveling properties, and the content of groups having a polymerizable unsaturated bond in the copolymer. Addition polymerizable monomer (ε) or addition polymerizable monomer (ε ′) other than (α), (β), (δ), (ζ) can be used in an arbitrary ratio.
The addition polymerizable monomer (ε) or (ε ′) not having a group having active hydrogen has one addition polymerizable double bond and does not have a group having active hydrogen (meth) Examples thereof include an acrylic acid compound and a styrene compound having one addition polymerizable double bond and no group having active hydrogen. Specific examples of such (meth) acrylic acid compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 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 Alkyl (meth) acrylates such as (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; phenyl (meth) acrylate, toluyl (meth) ) Aryl (meth) acrylate such as acrylate; Arylalkyl (meth) acrylate such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate Such as alkoxyalkyl (meth) acrylates; ethylene oxide adducts of (meth) acrylic acid; and the like.
Further, examples of (meth) acrylic acid compounds having one addition polymerizable double bond and no active hydrogen group include (meth) acrylic acid compounds having a silsesquioxane skeleton. . Specific examples of the (meth) acrylic acid compound 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-hepta Isooctylpentacyclo [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 Rate, 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- Yl) propyl (meth) acrylate, 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] propyl (meth) acrylate, 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] propyl (meth) acrylate, 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-yloxy) dimethylsilyl] propyl (meth) acrylate Relate, 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-heptaphenylpentacyclo [9.5.1.1 ^3,9 .1 ^{5,15 .1,7,13} ] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate and the like.
Specific examples of the styrene compound having one addition polymerizable double bond and no active hydrogen-containing group include styrene, vinyl toluene, α-methyl styrene, p-chlorostyrene, and the like. .

Examples of the styrene compound having one addition polymerizable double bond and not having a group having active hydrogen further include a styrene compound 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-heptaisobutylpentacyclo [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-heptacyclopentylpentacyclo [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 with 4-vinylphenyl (T ₈ type silsesquioxane), such as 1 ^7,13 ] octasiloxane; and 3- (3,5,7,9,11,13,15-heptaethylpenta Cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15- Heptaisobutylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13) , 15-Heptaisooctylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9 , 11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octaoctasiloxane-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-heptaisooctylpentacyclo [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- hepta cyclopentyl point pen Tashi Chlo [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- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13], such octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 4-vinylphenyl Octasiloxane having ethyl (T ₈ type silsesquioxane); and the like.

Examples of the addition polymerizable monomers (ε) and (ε ′) include compounds having two addition polymerizable double bonds.
Examples of compounds having two addition polymerizable double bonds include 1,3-butanediol = di (meth) acrylate, 1,4-butanediol = di (meth) acrylate, 1,6-hexanediol = di (Meth) acrylate, polyethylene glycol = di (meth) acrylate, diethylene glycol = di (meth) acrylate, neopentyl glycol = di (meth) acrylate, triethylene glycol = di (meth) acrylate, tripropylene glycol = di (meth) Acrylate, hydroxypivalate ester neopentyl glycol = di (meth) acrylate, trimethylolpropane = di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobisphenol A Bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol = di (meth) acrylate, hydroxypivalate ester neopentyl glycol compound Di (meth) acrylate and di (meth) acrylate monomers such as bis [(meth) acryloyloxypropyl] tetramethyldisiloxane, and divinylbenzene.

Examples of the addition polymerizable monomers (ε) and (ε ′) include compounds having three or more addition polymerizable double bonds. Examples of compounds having three or more addition polymerizable double bonds include trimethylolpropane = tri (meth) acrylate, pentaerythritol = tri (meth) acrylate, pentaerythritol = tetra (meth) acrylate, dipentaerythritol = mono Hydroxypenta (meth) acrylate, tris (2-hydroxyethylisocyanate) = tri (meth) acrylate, tris (diethylene glycol) trimerate = tri (meth) acrylate, 3,7,14-tris [((((meth) acryloyloxypropyl) ) dimethylsiloxy)] - 1,3,5,7,9,11,14- hept ethyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, 3,7,14- tris [((( Meth) acryloyloxypropyl) 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-heptaisooctyltricyclo [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 ] heptasiloxane, 3,7,14-tris [(((meth) acryloyloxypropyl) dimethylsiloxy)] -1,3,5,7,9,11,14- heptaphenyl tricyclo [7.3.3.1 ^{5 and 11]} hept siloxane, octakis (3- (meth) acryloyloxy propyl dimethylsiloxy) octa silsesquioxane Oxan and O Takis (3- (meth) acryloyloxy propyl) octasilsesquioxane include.

  Examples of the addition polymerizable monomer (ε) and (ε ′) include a compound containing fluorine. The compound containing fluorine may be a compound having a fluorine atom group and an addition polymerizable double bond in the molecule, and may be any of a vinyl compound, a vinylidene compound, and a vinylene compound having a fluorine atom. An acrylic acid derivative or a styrene derivative having a fluorine atom is preferable.

Typical examples of the addition polymerizable monomer having a fluorine atom include fluoroalkyl (meth) acrylate, fluorostyrene and fluorine-containing polyether compounds.
Examples of such an addition polymerizable monomer having a fluorine atom include JP-A-10-251352, JP-A-2004-043671, JP-A-2004-155847, JP-A-2005-029743, JP-A-2006-117742, JP-A-2006-. 299016, and monomers disclosed in JP-A-2005-350560.
Specific examples include the following monomers.
Examples of the fluoroalkyl (meth) acrylate include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth) acrylate, 2,2,3, 3-tetrafluoro-t-pentyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,4,4,4-hexafluoro-t- Hexyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4,4-hexa Fluorobutyl (meth) acrylate, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluor Butyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,5-nonafluoro Pentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5 6,6,7,7,8,8-dodecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (Meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl (meth) acrylate, 3,3,4,4,5 5,6,6,7,7,8,8,9,9,10,10-hexadecafluorodecyl (meth) a Relate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) acrylate, 3,3,4 , 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-octadecafluoroundecyl (meth) acrylate, 3,3,4,4,5 5,6,6,7,7,8,8,9,9,10,10,11,11,11-nonadecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5 , 6,6
, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12-eicosafluorododecyl (meth) acrylate and the like.
Examples of fluorostyrene include fluoroalkyl styrene such as p-trifluoromethyl styrene, p-heptafluoropropyl styrene, and p-pentafluoroethyl styrene.
Specific examples of the fluorine-containing polyether compound include 1H, 1H-perfluoro-3,6-dioxaheptyl (meth) acrylate, 1H, 1H-perfluoro-3,6-dioxaoctyl (meth) acrylate, 1H , 1H-perfluoro-3,6-dioxadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9-trioxadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9 -Trioxaundecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9-trioxatridecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12-tetra Oxatridecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12-tetraoxatetradecanyl (me ) Acrylate, 1H, 1H-perfluoro-3,6,9,12-tetraoxahexadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxahexadecanyl (Meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxaheptadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15-penta Oxanonadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15,18-hexaoxaicosanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9 , 12,15,18-hexaoxadocosanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15,18,21-he Data oxa Trichoderma Sa sulfonyl (meth) acrylate, IH, 1H-perfluoro -3,6,9,12,15,18,21- hepta oxa penta Xhosa sulfonyl (meth) can be given acrylate.
Such an addition polymerizable monomer having a fluorine atom can also be synthesized by reacting a fluorine compound having a hydroxyl group with an acid halide having an addition polymerizable functional group.
Examples of such a fluorine compound having a hydroxyl group include (HO) C (CF ₃ ) ₂ CH ₃ , (HO) C (CF ₃ ) ₂ CH ₂ CH ₃ , (HO) C (CF ₃ ) ₂ CH ₂ O— A compound having CH ₂ —, (HO) C (CF ₃ ) ₂ CH ₂ CH ₂ O—CH _{3 and the} like can be mentioned.
It is also commercially available from Exfluor Research Corporation and can be purchased and used.
Further, the fluorine compound having a hydroxyl group can be synthesized and used, and a synthesis method is described in JP-A-10-147639.

  The addition polymerizable monomers (ε) and (ε ′) may be used alone or in combination of two or more. When a plurality of types are used in combination, various composition ratios can be appropriately adjusted according to the specification of the target polymer.

<Precursor of polymer of the present invention>
The precursor for obtaining the polymer of the present invention is a fluorosilsesquioxane (α) -derived structural unit (structural unit A) having one addition polymerizable functional group in the molecule and an addition containing a hydrophilic group. A structural unit derived from a polymerizable monomer (β) (structural unit B) and a structural unit derived from an addition polymerizable monomer (ζ) containing a group having active hydrogen (structural unit F) are essential components. An addition copolymer, or a structural unit (structural unit A) derived from fluorosilsesquioxane (α) having one addition-polymerizable functional group in the molecule, and an addition-polymerizable monomer containing a hydrophilic group ( β) -derived structural unit (structural unit B), an addition-polymerizable monomer comprising an addition-polymerizable functional group-containing organopolysiloxane (δ) -derived structural unit (structural unit D), and an active hydrogen-containing group (Ζ) derived structural unit (structural unit F) as an essential component A copolymer, even ordered copolymers such as block copolymers, but may be a random copolymer, preferably a random copolymer. The polymer of the present invention may have a cross-linked structure or a graft copolymer.

When the polymer precursor of the present invention is composed of the structural unit A, the structural unit B, and the structural unit F, the moles of the structural unit A, the structural unit B, and the structural unit F in the polymer precursor of the present invention. The ratio is arbitrary and (a) :( b) = about 0.001: 99.999 to about 99.999: 0.001, (b) :( f) = about 0.001: 99.999 to about 99.999: 0.001, (a) :( f) = about 0.001: 99.999 to about 99.999: 0.001.
When the polymer precursor of the present invention is composed of the structural unit A, the structural unit B, the structural unit D, and the structural unit F, the structural unit A, the structural unit B, and the structural unit in the polymer of the present invention. The molar ratio of D and the structural unit F is arbitrary, and (a) :( b) = about 0.001: 99.999 to about 99.999: 0.001, (a) :( d) = about 0.00. 001: 99.999 to about 99.999: 0.001, (a) :( f) = about 0.001: 99.999 to about 99.999: 0.001, (b) :( d) = about 0.001: 99.999 to about 99.999: 0.001, (b): (f) = about 0.001: 99.999 to about 99.999: 0.001, (d): (f) = About 0.001: 99.999 to about 99.999: 0.001.
If the ratio of the structural unit C contained in the polymer of this invention is the range of said (f), it will not restrict | limit, The polymer of this invention is a coupling | bonding with the binder resin mix | blended when it is used as a coating agent. In order to improve the properties, it is only necessary to include a group having a polymerizable unsaturated bond to such an extent that preferable reactivity with the binder resin monomer is obtained.
As will be described later, when the copolymer of the present invention is used as a surface modifier, when the polymer of the present invention is composed of a structural unit A, a structural unit B, and a structural unit C, (a): (B) = about 1:99 to about 99: 1, (b) :( c) = about 1:99 to about 99: 1, (a) :( c) = about 1:99 to about 99: 1 Preferably there is. When the polymer of the present invention is composed of the structural unit A, the structural unit B, the structural unit C, and the structural unit D, (a) :( b) = about 1:99 to about 99: 1, (a ): (C) = about 1:99 to about 99: 1, (a) :( d) = about 1:99 to about 99: 1, (b) :( c) = about 1:99 to about 99: Preferably, (b) :( d) = about 1:99 to about 99: 1, (c) :( d) = about 1:99 to about 99: 1.
In the case where the polymer of the present invention further includes an arbitrary structural unit E or structural unit E ′, the structural unit A, the structural unit C (or the structural unit F) contained in the polymer of the present invention or a precursor thereof, and The molar ratios of the structural unit B or the structural unit A, the structural unit C (or the structural unit F), the structural unit B, and the structural unit D are the same.
The weight average molecular weight of the polymer of the present invention varies depending on the content of the structural unit (β) 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.
The polymer precursor of the present invention has a fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, an addition polymerizable monomer (β) containing a hydrophilic group, and active hydrogen. When a plurality of types of monomers are used as the addition polymerizable monomer (ζ) having a group, or any addition polymerizable monomer (ε) that can be used as necessary, or one in the molecule Fluorosilsesquioxane (α) having an addition polymerizable functional group, addition polymerizable monomer (β) having a hydrophilic group, addition polymerizable monomer (ζ) having a group having an active hydrogen, addition polymerization In the case where plural types of monomers are used as the organopolysiloxane (δ) having a functional functional group, or any addition polymerizable monomer (ε ′) that can be used as necessary, each monomer The ratio of these should be determined appropriately according to the properties of the target copolymer. That's fine. 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;
Furthermore, examples of the polymerization reaction include living radical polymerization and active energy ray polymerization.

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 described in the following references A to C.
・ Cited document A: supervised by Mikiharu Tsunoike, Takeshi Endo, radical polymerization handbook, issued August 10, 1999, issued by NTS).
・ Cited document B: HANDBOOK OF RADICAL POLYMERIZATION, K. Matyjaszewski, TP Davis, Eds., John Wiley and Sons, Canada 2002
・ Cited document C: JP-A-2005-105265
Active energy ray polymerization can be performed using the compound described in the cited document D as an active energy ray polymerization initiator.
・ Cited document D: Photopolymer social gathering, Photosensitive material list book, published on March 31, 1996 by Bunshin Publishing).

In the present invention, the active energy ray refers to an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams.
Specific examples of the active energy ray polymerization 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 active energy ray polymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 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-dimethyla Mino-1- (4-morpholinophenyl) -butanone-ethyl 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, 2- (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 is preferred.
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 the 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 -Mercaptopropionate), pentaerythritol tetra (3-mercaptoacetate) and other mercaptans; diphenyl disulfide, diethyl dithioglycolate, disulfides such as diethyl disulfide; and the like, 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, Four ethane chloride, 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, a dispersion polymerization method, a soap-free emulsion polymerization method, a seed emulsion polymerization method, a microemulsion polymerization method, a miniemulsion polymerization method, or a polymerization method using supercritical CO ₂ can be used.
In the case of the solution polymerization method, in a suitable solvent, fluorosilsesquioxane (α) having one addition polymerizable functional group in the molecule, addition polymerizable monomer (β) having a hydrophilic group, And an addition-polymerizable monomer (ζ) containing a group having active hydrogen and any addition-polymerizable monomer (ε) that can be used as necessary, or one addition-polymerizable in the molecule Fluorosilsesquioxane (α) having a functional group, an addition polymerizable monomer (β) containing a hydrophilic group, an addition polymerizable monomer (ζ) containing a group having an active hydrogen, and an addition polymerizable function An organopolysiloxane having a group (δ), an optional addition polymerizable monomer (ε ′) that can be used as necessary, a polymerization initiator, a chain transfer agent, etc. What is necessary is just to carry out addition polymerization reaction by irradiating active energy rays. .

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-dimethylformamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms) ), Perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol) ), An aromatic fluorine solvent (α, α, α-trifluorotoluene, hexafluorobenzene), and water. These may be used alone or in combination of two or more.
The amount of the solvent used may be an amount that makes the monomer concentration 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 being lowered, and a polymer having an appropriately controlled molecular weight 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, and may be used for forming a coating film as it is.
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 preferred amount of the precipitating agent is 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.

<Polymer of the present invention>
As described above, the group having a polymerizable unsaturated bond includes a precursor of the polymer of the present invention and a functional group (group having an active hydrogen) capable of introducing a group having a polymerizable unsaturated bond of the structural unit F. It can introduce | transduce by making the functional group and the compound which has group which has a polymerizable unsaturated bond in the same molecule react.
Examples of the compound having a functional group that reacts with a group having active hydrogen and a group having a polymerizable unsaturated bond in the same molecule include, for example, an isocyanate compound having a polymerizable unsaturated bond, and a polymerizable unsaturated bond. The acid halide which has, the carboxylic acid compound which has a polymerizable unsaturated bond, the carboxylic acid ester compound which has a polymerizable unsaturated bond, and an epoxy compound can be mentioned. The group having such a polymerizable unsaturated bond is preferably a radical polymerizable group, and examples thereof include (meth) acryl, allyl, and styryl.

式中、Ｒ⁸、Ｒ⁹は、水素またはメチルであり、Ｂは酸素、炭素数１〜３のアルキレン、または−ＯＲ¹⁰−である；Ｒ¹⁰は炭素数２〜１２のアルキレン、炭素数２〜１２のオキシアルキレン、炭素数６〜１２のアリーレンを表す。 As an isocyanate compound having (meth) acryl, a compound having the following structure can be used.

In the formula, R ⁸ and R ⁹ are hydrogen or methyl, B is oxygen, alkylene having 1 to 3 carbons, or —OR ¹⁰ —; R ¹⁰ is alkylene having 2 to 12 carbons, 2 carbons Represents -12 oxyalkylene and 6-12 carbon atoms arylene.

式中、Ｒ¹¹は炭素数１〜１０のアルキレンであり、Ｒ¹²は水素、またはメチルである。
好適に用いることのできる重合性不飽和結合を有するイソシアネート化合物の具体例は、２−イソシアナトエチルメタクリレート、２−イソシアナトエチルアクリレート、１，１−ビス（アクリロイルオキシメチル）エチルイソシアネート、４−（２−イソシアナト
イソプロピル）スチレンであり、好ましくは２−イソシアナトエチルメタクリレート、２−イソシアナトエチルアクリレート、１，１−ビス（アクリロイルオキシメチル）エチルイソシアネートである。 As the isocyanate compound having styryl, a compound having the following structure can be used.

In the formula, R ¹¹ is alkylene having 1 to 10 carbon atoms, and R ¹² is hydrogen or methyl.
Specific examples of the isocyanate compound having a polymerizable unsaturated bond that can be suitably used include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 4- ( 2-isocyanatoisopropyl) styrene, preferably 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate.

When the isocyanate compound having a polymerizable unsaturated bond is reacted with the group having active hydrogen, a urethanization catalyst can be used for the purpose of promoting the reaction.
Examples of the urethanization catalyst include organometallic urethanization catalysts and tertiary amine urethanization catalysts.

  Organometallic urethanization catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, naphthenic acid Mention may be made of organometallic urethanization catalysts such as cobalt.

Tertiary amine urethanization catalysts include triethylenediamine, N, N, N ′, N ′, N′-pentamethyldipropylenetriamine, N, N, N ′, N ′, N′-pentamethyldiethylenetriamine, N , N, N ′, N′-tetramethylhexamethylenediamine, bis (dimethylaminoethyl) ether, 2- (N, Ndimethylamino) -ethyl-3- (N, Ndimethylamino) propylether, N, N '-Dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, triethylamine, N, N-dimethylacetylamine, N, N-dimethyldodecylamine, N, N-dimethylhexadecylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N, N-dimethylbenze Amine, morpholine, N-methylmorpholine, N-ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4,4′-oxydiethylenedimorpholine, N, N′-dimethylpiperazine, N, N′-diethylpiperazine N, -methyl-N′-dimethylaminoethylpiperazine, 2,4,6-tri (dimethylaminomethyl) phenol, tetramethylguanidine, 3-dimethylamino-N, N-dimethylpropionamide, N, N, N ', N'-tetra (3-dimethylaminopropyl) methanediamine, N, N-dimethylaminoethanol, N, N, N', N'-tetramethyl-1,3-diamino-2-propanol, N, N , N′-trimethylaminoethylethanolamine, 1,4-bis (2-hydroxypropyl) -2-methylpiperazi 1- (2-hydroxypropyl) imidazole, 3,3-diamino-N-methylpropylamine, 1,8-diazobicyclo (5,4,0) -undecene-7, N-methyl-N-hydroxyethyl Examples include piperazine.
These can be used alone or in combination of two or more. The catalyst can be used in any amount with respect to the isocyanate, but is preferably 0.0001 to 1 mol%, more preferably 0.001 to 1 mol% based on the isocyanate.

  In order to obtain the polymer of this invention using the isocyanate compound which has the said polymerizable unsaturated bond, you may use a solvent as needed. The solvent used may be any group having an active hydrogen and an inert solvent for isocyanate. For example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, Ketone solvents such as methyl ethyl ketone and cyclohexanone, glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate and ethyl-3-ethoxypropionate, ether solvents such as tetrahydrofuran and dioxane, dimethylformamide, dimethyl Examples include polar solvents such as acetamide, N-methylpyrrolidone, and furfural, and these may be used alone or in combination of two or more. The amount of the solvent used may be an amount that makes the concentration of the polymer containing the group having active hydrogen about 10 to 80% by weight.

The reaction temperature is generally 0 to 120 ° C, preferably 20 to 100 ° C. If it is less than 0 ° C., the reaction becomes very slow, and if it exceeds 120 ° C., polymerization may be caused.
The molar ratio during the reaction is isocyanate: group having active hydrogen = 100: 1 to 0.01: 1, preferably 20: 1 to 0.1: 1.
In addition, a polymerization inhibitor may be present for the purpose of suppressing polymerization during the reaction between the isocyanate and the group having active hydrogen. As polymerization inhibitors, p-benzoquinone, naphthoquinone, phenanthraquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p- Benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-diacyloxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,5-t-butylhydroquinone, mono-t-butylhydroquinone or 2,5 -Di-t-amylhydroquinone etc. can be mentioned, and the amount used is 10 to 10,000 ppm with respect to the total amount of the precursor of the polymer of the present invention and the isocyanate compound having a polymerizable unsaturated bond, Preferably it is 50-1,000 ppm.

  On the other hand, examples of the acid halide having a polymerizable unsaturated bond include acrylic chloride, methacryl chloride, styrene carbonyl chloride, styrene sulfonyl chloride, 2-methacryloyloxyethyl succinyl chloride, and 2-methacryloyloxyethyl hexahydrophthalic acid. List chloride compounds such as luchloride and bromide compounds such as acrylic bromide, methacryl bromide, styrene carbonyl bromide, styrene sulfonyl bromide, 2-methacryloyloxyethyl succinyl bromide, and 2-methacryloyloxyethyl hexahydrophthalyl bromide. From the viewpoint of ultraviolet curing, acrylic acid and halides of methacrylic acid are preferred.

  In order to obtain the polymer of the present invention having a polymerizable unsaturated bond in the side chain using an acid halide having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a dehydrohalogenation reaction between an acid halide and a group having active hydrogen (preferably a hydroxyl group).

In this reaction, hydrogen halide is by-produced. In general, in order to remove this hydrogen halide from the reaction system, it is preferable to coexist a base as a hydrogen halide scavenger in the reaction system. The base as the hydrogen halide scavenger is not particularly limited, and a known one can be used. Examples of bases that are preferably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, tetramethylurea, sodium hydroxide, sodium carbonate, and the like. The amount of the base is preferably 1 mol or more per 1 mol of the carboxylic acid chloride.
In this reaction, it is generally preferable to use an organic solvent. Examples of solvents that can be suitably used as the solvent include aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, and ethylene chloride. Ethers such as diethyl ether, dioxane and tetrahydrofuran; N, N-dialkylformamides such as N, N-dimethylformamide and N, N-diethylformamide; dimethyl sulfoxide and the like.
The temperature in this reaction can be selected from a wide range. Generally, it can be selected from the range of -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C. While the reaction time varies depending on the type of raw material, it is usually 5 minutes to 24 hours, preferably 1 to 4 hours. Further, stirring is preferably performed during the reaction.
Usually, after the reaction, the reaction product can be separated by washing with water and drying, and then distilling off the solvent. It can also be used for the esterification reaction.

  Examples of the carboxylic acid compound having a polymerizable unsaturated bond include acrylic acid, methacrylic acid, and vinyl benzoic acid.

  In order to obtain the polymer of the present invention having a polymerizable unsaturated bond in the side chain using a carboxylic acid compound having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a dehydration condensation reaction between a carboxylic acid compound and a group having active hydrogen (preferably a hydroxyl group).

  Examples of the carboxylic acid ester compound having a polymerizable unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 1-butyl (meth) acrylate, and t-butyl (meth). Examples include acrylate and 2-ethylhexyl (meth) acrylate.

  In order to obtain the polymer of the present invention having a polymerizable unsaturated bond in the side chain using a carboxylic acid ester compound having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a transesterification reaction between a carboxylic acid ester compound and a group having active hydrogen (preferably a hydroxyl group).

  Examples of the epoxy compound having a polymerizable unsaturated bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like.

  In order to obtain the polymer of the present invention having a polymerizable unsaturated bond in the side chain using a compound having a polymerizable unsaturated bond, a known epoxy ring-opening reaction between a cyclic ether and a hydroxyl group can be used. .

  Further, a part of the isocyanate of a compound having a plurality of isocyanates such as isophorone diisocyanate is urethanated with a hydroxyl group-containing addition polymerizable monomer such as 2-hydroxyethyl acrylate to obtain an isocyanate compound having a polymerizable unsaturated bond, The polymer of the present invention having a polymerizable unsaturated bond in the side chain can be obtained by utilizing a urethanization reaction between the isocyanate compound and a group having active hydrogen (preferably a hydroxyl group).

<Application of polymer>
Although the polymer of this invention is used for arbitrary uses, if needed, it uses together the polymer containing group which has polymerizable unsaturated bonds other than the polymer of this invention, and other resin ( In the following, a binder resin) or a resin monomer (hereinafter referred to as a binder resin monomer) is combined, and if necessary, dissolved or dispersed in various solvents and used as a surface modifier (so-called coating agent). be able to.
The “polymer containing a group having a polymerizable unsaturated bond other than the polymer of the present invention” is an addition polymerizable compound containing alkyl as an optional component in addition to the structural unit C described in the description of the polymer of the present invention. You may contain the structural unit derived from a monomer. Here, any hydrogen in the alkyl may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene.
In addition, the “polymer containing a group having a polymerizable unsaturated bond other than the polymer of the present invention” contains, as an optional component, a structural unit derived from an addition polymerizable monomer containing a substituted or unsubstituted aryl. Or a substituted or unsubstituted aryl and an alkylene in which any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene. A structural unit derived from an addition polymerizable monomer containing arylalkyl may be contained.
In addition, the “polymer containing a group having a polymerizable unsaturated bond other than the polymer of the present invention” may contain a structural unit having a silsesquioxane skeleton as an optional component.
More specifically, the “polymer containing a group having a polymerizable unsaturated bond other than the polymer of the present invention” is the structural unit A, the structural unit E, or the structural unit E described in the description of the polymer of the present invention. 'May be included as an optional component.

In order to form a film on the surface of a substrate such as plastics, glass, metal, etc., and to exhibit functions such as cleaning properties, amphiphilic properties, mold release properties, and antifouling properties, 1) the polymer of the present invention alone 2) “polymer containing a group having a polymerizable unsaturated bond other than the polymer of the present invention” may be used in combination. 3) In combination with a binder resin and a binder resin monomer. May be used. In order to express these functions on the surface of the base material, it is important to make it closely contact with the base material, and in order to fix the polymer to the base material, it is preferable to use it in combination with a binder resin. 4) Binder resin by selecting a binder resin having a functional group capable of reacting with the polymer (hereinafter referred to as a reactive binder resin) and a component that crosslinks the polymer and the reactive binder resin by reaction. Thus, the polymer can be more firmly fixed to the substrate. In addition, in the case of applications that require characteristics such as heat resistance, light resistance, scratch resistance, and abrasion resistance, by selecting a binder resin having these characteristics, without impairing the original characteristics of the resin, The surface can be modified.
As described above, the polymer of the present invention may be used alone as a surface modifier as in 1), but as described in 2) above, “polymerizable unsaturated bonds other than the polymer of the present invention are formed. The polymer containing a group having a group "may be used in combination as a surface modifier, or may be used as a surface modifier by mixing with another binder resin as described in 3) above, as in 4) above. Further, it may be mixed with a binder resin monomer that can react with the polymer of the present invention (hereinafter also referred to as a reactive binder resin monomer) and used as a surface modifier.
When the “polymer containing a group having a polymerizable unsaturated bond other than the polymer of the present invention” is used in combination as in 2), for example, a polymer having a hydrophobic group can be added as appropriate. The hydrophilic / oil-repellent function exhibited by the polymer of the invention can be arbitrarily controlled, and the antifouling and cleaning functions can be further improved.
When the polymer of the present invention is used by mixing with another binder resin as in the above 3), the original properties (mechanical properties, surface / interface properties, compatibility, etc.) of the resin can be modified.

The binder resin may be any of a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin, and may be a plurality of types of resins.
Examples of the binder resin include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultrahigh molecular weight polyethylene, poly-4-methyl. Pentene, 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 brand name), 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 Ltd.) Product name, etc.), polyimide (Kapton: Toray Industries, Inc., AURUM: Mitsui Chemicals, Inc., etc.), polyetherimide, polyamideimide, phenol resin, alkyd resin, melamine resin, epoxy resin, urea Resins, bismaleimide resins, polyester urethane resins, polyether urethane resins and silicone resins are included.
These resins may be used alone, or a plurality of resins may be used in combination.

Further, as in 3) above, the polymer of the present invention may be used by mixing with a reactive binder resin monomer. In particular, when the polymer of the present invention having a polymerizable unsaturated bond in the side chain and a reactive binder resin monomer are mixed and used, the resin obtained by curing and the polymer of the present invention are cross-linked. As a result, a composite resin having excellent mechanical properties, surface / interface characteristics, and compatibility can be obtained.
Specifically, a solution containing the polymer of the present invention having a polymerizable unsaturated bond in the side chain, a reactive binder resin monomer, and, if necessary, a curing reaction initiator is applied to a substrate and applied. A film (composite film) made of a composite resin with a binder resin can be formed on the substrate by drying and curing the film.
The formed composite film has high water / oil repellency and low surface free energy.
Preferable examples of the reactive binder resin monomer include a monomer that forms a UV curable resin capable of radical curing by ultraviolet irradiation.

<Monomer forming UV curable resin>
Resins that can be radically cured by ultraviolet irradiation include radical polymerization of (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins, etc. A resin having an unsaturated bond can be exemplified.

  Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (Meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, the compound which has a silsesquioxane skeleton and has a (meth) acrylate in a functional group is also mentioned.

As said unsaturated polyester resin, the condensation product (unsaturated polyester) by esterification reaction of polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid as needed) was melt | dissolved in the polymerizable monomer. Things.
The unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, itaconic acid or the anhydride thereof is used as an acid component, and this is combined with ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane Polyhydric alcohols such as -1,4-dimethanol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are reacted as an alcohol component, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, Such as tetrahydrophthalic acid, adipic acid, sebacic acid Polymerizable not have an unsaturated bond or a polybasic acid anhydrides may include those prepared by adding as an acid component.

The polyester (meth) acrylate resin includes (1) an epoxy containing an α, β-unsaturated carboxylic acid ester in a terminal carboxyl polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol. (Meth) acrylate obtained by reacting a compound, (2) Saturated polybasic acid and / or obtained by reacting a terminal carboxyl polyester obtained from unsaturated polybasic acid and polyhydric alcohol with hydroxyl group-containing acrylate (meta And (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester having a terminal hydroxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol.
Examples of the saturated polybasic acid used as a raw material for polyester (meth) acrylate include polybasic compounds having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples include acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. Further, the polyhydric alcohol component is the same as the unsaturated polyester.

The epoxy (meth) acrylate resin that can be used in the present invention has a polymerizable unsaturated bond generated by a ring-opening reaction between a compound having glycidyl and a carboxyl of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. A compound obtained by dissolving a compound (vinyl ester) in a polymerizable monomer.
The vinyl ester is produced by a known method and includes epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.
Alternatively, various epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.) to impart flexibility.
Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolac glycidyl ethers and the like.

As the urethane (meth) acrylate resin, for example, after reacting a polyisocyanate and a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acryl compound and, if necessary, a hydroxyl group-containing allyl ether compound are reacted. And a radical-polymerizable unsaturated group-containing oligomer that can be obtained.
Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, Phenylmethane triisocyanate, Bannock D-750, Crisbon NK (trade name; manufactured by Dainippon Ink & Chemicals, Inc.), Desmodur L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Japan) Polyurethane Industry Co., Ltd.), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like.
Examples of the polyhydroxy compound include polyester polyol, polyether polyol, and the like. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, Trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol Tall
Examples include propylene oxide adducts, dipentaerythritol-tetrahydrofuran adducts, dipentaerythritol-ethylene oxide-propylene oxide adducts, and the like.
Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3- Butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3 -Cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol, etc. .
Although it does not specifically limit as said hydroxyl-containing (meth) acryl compound, A hydroxyl-containing (meth) acrylic acid ester is preferable, Specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanursannodi (meth) acrylate, pentaesitol tri (meth) ) Acrylate and the like.

In addition, as the acrylate monomer, as disclosed in, for example, Japanese Patent No. 2655683, silanol having a fluorine-containing hydrocarbon group and hexamethylcyclotrisiloxane are polymerized to obtain chlorosilane having a polymerizable unsaturated group. Examples thereof include fluorine-based silicon compounds that can be obtained by reacting to stop polymerization. The fluorine-based silicon compound preferably includes compounds represented by the following formulas (I-1) and (I-2) (both n represents 0 to 500, and R ¹³ represents hydrogen or methyl). It is done.

<Surface treatment agent>
The surface treating agent of the present invention contains the polymer or resin composition of the present invention described above. From the viewpoint of adjusting the concentration of the polymer or resin composition of the present invention and various physical properties of the surface treatment agent, and from the viewpoint of curing the polymer or resin composition during subsequent film formation, Other components other than the polymer or resin composition of the invention may further be contained. Examples of such other components include a polymerization initiator and a solvent.
When the polymer of the present invention and the reactive binder resin monomer are mixed and used, a polymerization initiator can be used for the purpose of promoting curing. As such a polymerization initiator, heat,
Alternatively, an initiator that generates radicals with active energy rays may be used, and an active energy ray polymerization initiator that generates radicals with active energy rays is preferable.
As the active energy ray polymerization initiator, the active energy ray polymerization initiator described above can be used.
Further, the polymer of the present invention and the binder resin monomer may be dissolved in a solvent and used. Examples of solvents used include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene). Etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, benzo Nitriles), 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 may be about 1 to 50% by weight based on the total amount of the polymer of the present invention and the binder resin monomer.

  The surface treatment agent of the present invention includes an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiation assistant, as long as it does not adversely affect surface slipperiness, water repellency, and oil repellency due to the polymer or resin composition. Optional components such as leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers such as silica and alumina, and organic fillers Further, it may be contained.

  As the curing aid for improving the curability of the polymer or resin composition and improving the adhesion to the substrate, which is contained in the surface treatment agent of the present invention, for example, it has two or more thiols in one molecule. Compounds. More specifically, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, Methylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglyconate, trishydroxyethyltristhiopropionate, 1,4-bis (3-mercaptobuti Ryloxy) butane (trade name; Karenz MT BD1, manufactured by Showa Denko KK), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name; Karenz M PE1, Showa Denko KK), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name) ; Karenz MT NR1, manufactured by Showa Denko KK) and the like.

<Film and molded body>
The film of the present invention and the molded body having the film are obtained from the surface treatment agent of the present invention described above. More specifically, the film of the present invention is obtained by a step of forming a film of the surface treating agent of the present invention and a step of curing the film. The film can be formed by, for example, coating, and the film can be usually cured by one or more of drying, heating, and active energy ray irradiation.

The method for applying the solution containing the polymer 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, 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.
Examples of substrates to be applied are transparent glass substrates such as white plate glass, blue plate glass, silica coated blue plate glass; polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, triacetate, diacetate Synthetic resin sheet, film, etc .; cycloolefin resin including norbornene resin (trade name: Zeonoa, Zeonex, manufactured by Nippon Zeon Co., Ltd., trade name: Arton, manufactured by JSR Corporation), methacrylstyrene, polysulfone, alicyclic Transparent resin substrates used for optical applications such as acrylic resin and polyarylate; metal substrates such as aluminum plates, copper plates, nickel plates, stainless steel plates; other ceramic substrates, semiconductor substrates having photoelectric conversion elements; urethane rubber, styrene rubber, etc. Raising It is.
These substrates 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 phase. Reaction methods, vacuum deposition, etc. are included.
The applied solution can be dried in an environment of room temperature to about 200 ° C.
When an active energy ray polymerization initiator is used, it can be cured by irradiating a photoactive energy ray or an electron beam with an active energy ray source after coating and drying.
There are no particular restrictions on the active energy ray source, but depending on the nature of the active energy ray polymerization initiator used, for example, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, gas laser, solid state laser And an electron beam irradiation apparatus. Examples of the use of the film of the present invention include a release paper / release film film, a water / oil repellent film, an antifouling film, a sliding film, an antireflection film, and an insulating film.

  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 are calculated | required by GPC (gel permeation chromatography method) by using poly (methyl methacrylate) as a standard substance.

[Production Example 1]
Synthesis of γ-methacryloxypropylhepta (trifluoropropyl) -T ₈ -silsesquioxane To a 1 L 4-necked flask equipped with a reflux condenser, thermometer and dropping funnel was added trifluoropropyltrimethoxysilane ( 100 g), THF (500 mL), deionized water (10.5 g) and sodium hydroxide (7.9 g) were charged, and the mixture was heated by an oil bath from room temperature to a temperature at which THF was refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. The flask was then lifted from the oil bath and allowed to stand overnight at room temperature, then set in the oil bath again and concentrated by heating under constant pressure until a solid precipitated.
The precipitated product was collected by filtration using a pressure filter equipped with a membrane filter having a pore size of 0.5 μm. Next, the obtained solid was washed once with THF, and dried at 80 ° C. for 3 hours in a vacuum dryer to obtain 74 g of a colorless powdery solid.
The obtained solid matter (65 g), dichloromethane (491 g) and triethylamine (8.1 g) were charged into a 1 L four-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel, and the temperature was 3 ° C. in an ice bath. Until cooled. Then γ-methacryloxypropyltrichlorosilane (
21.2 g) was added, and after confirming that the exotherm had subsided, it was lifted from the ice bath and aged overnight at room temperature. After washing with deionized water three times, the dichloromethane layer was dehydrated with anhydrous magnesium sulfate, and magnesium sulfate was removed by filtration. The mixture was concentrated with a rotary evaporator until a viscous solid was precipitated, and 260 g of methanol was added and stirred until powdery. The powder was filtered using a pressure filter equipped with 5 μm filter paper, and dried in a vacuum dryer at 65 ° C. for 3 hours to obtain 41.5 g of a colorless powdery solid. The obtained solid was subjected to GPC and ¹ H-NMR measurement, and was found to be a compound (a-1) having a structure represented by the following formula.

[Example 1] Synthesis of polymer (A1) having fluorosilsesquioxane, oxyalkylene and acryloyl in the side chain <Synthesis of polymer having oxyalkylene and hydroxyl in the side chain>
In a 200 mL four-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel, 37.42 g of compound (a-1), 1.99 g of 2-hydroxyethyl methacrylate (HEMA), methoxypolyethylene glycol mono 30.59 g of methacrylate (PEG-MA; Blemmer PME-1000, manufactured by NOF Corporation) and 69.80 g of methyl ethyl ketone (MEK) were introduced and sealed with nitrogen. It was set in an oil bath maintained at 95 ° C. and refluxed, and deoxygenated for 10 minutes. Next, a solution prepared by dissolving 0.13 g of azobisisobutyronitrile (AIBN) and 0.07 g of mercaptoacetic acid (AcSH) in 1.76 g of MEK was introduced, and polymerization was started while maintaining the reflux temperature. After polymerizing for 3 hours, a solution in which 0.13 g of AIBN was dissolved in 1.44 g of MEK was introduced, and the polymerization was further continued for 5 hours to obtain a polymer having fluorosilsesquioxane, oxyalkylene and hydroxyl ( A polymerization solution containing a1) was obtained. The weight average molecular weight determined by GPC analysis of the polymerization solution was 14,000, and the molecular weight distribution was 1.1. The compositional mole fraction of the monomer component determined from ¹ H-NMR measurement was Compound (a-1): HEMA: PEG-MA = 37.8: 23.4: 38.8.

<Synthesis of polymer (A1) having fluorosilsesquioxane, oxyalkylene and acryloyl in the side chain>
53.70 g of a polymer solution (a1) containing a polymer having oxyalkylene and hydroxyl was introduced into a four-necked flask having an internal volume of 100 mL equipped with a reflux condenser, a thermometer, and a septum cap, and p-methoxyphenol was further introduced. (MEHQ) 0.0263 g and dibutyltin dilaurate (DBTDL) 0.0132 g were dissolved and introduced into 0.30 g of MEK, and sealed with nitrogen. It set to the oil bath maintained at 48 degreeC, and heated up. Next, when the liquid temperature reached 45 ° C., 1.18 g of acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was introduced to start the reaction. After reacting for 6 hours, the reaction was terminated by cooling to room temperature and introducing 1.20 g of MeOH to obtain a polymer solution containing a polymer (A1) having fluorosilsesquioxane, oxyalkylene and acryloyl. The weight average molecular weight determined by GPC analysis of the polymerization solution was 14,000, and the molecular weight distribution was 1.1.

[Example 2] Preparation of film 0.89 g of a polymer solution containing the polymer (A1) obtained in Example 1, and 7.60 g of polyfunctional urethane acrylate UA-306H (manufactured by Shin-Nakamura Chemical Co., Ltd.), Irgacure 184 (manufactured by Ciba Specialty Chemicals) 0.40 g was dissolved in 11.51 g of MEK to obtain a coating solution. The solid content concentration in the coating solution is 40% by weight.

  The obtained coating liquid was applied onto a polyethylene terephthalate film (thickness: 100 μm, brand name: Lumirror 100-U34, manufactured by Toray Industries, Inc.) using a coating rod (# 9, manufactured by RD Specialties). did. When the coating rod (# 9) is used, the wet film thickness (as described in the RD Specialties catalog) is 20 μm.

The obtained coating film was dried in a high-temperature chamber at 80 ° C. for 3 minutes, and using a conveyor-type UV irradiation apparatus attached with a high-pressure mercury lamp (H08-L41, rated 160 W / cm, manufactured by Iwasaki Electric Co., Ltd.) Ultraviolet rays were irradiated at an illuminance of 80 mW / cm ² and an exposure amount of 500 mJ / cm ² to obtain a transparent film having a theoretical film thickness of 8 μm. The exposure amount was measured with an illuminometer (UVPF-A1 / PD-365, manufactured by Iwasaki Electric Co., Ltd.). The theoretical film thickness was calculated from the wet film thickness when using the coating rod (# 9) and the resin solid content in the coating liquid according to the following formula.
Theoretical film thickness (μm) = (wet film thickness when a coating rod is used) × (solid content concentration in coating liquid (% by weight)) / 100

[Example 3] Synthesis of polymer (A2) having fluorosilsesquioxane, oxyalkylene, organopolysiloxane and acryloyl in the side chain Compound (a-1) in Example 1, 2-hydroxyethyl methacrylate (HEMA) In addition to methoxypolyethylene glycol monomethacrylate (PEG-MA; Bremer PME-1000, manufactured by NOF Corporation), one-end methacryloxy group-modified dimethyl silicone (FM-0721, molecular weight of about 6,300) was added. By performing the same operation as in Example 1, a polymer (A2) having fluorosilsesquioxane, oxyalkylene, organopolysiloxane and acryloyl can be obtained.

[Example 4] Preparation of coating In the same manner as in Example 2 except that the polymer (A2) obtained in Example 3 was used instead of the polymer (a1) in Example 2, antifouling properties and mold release were performed. A transparent film exhibiting properties, slipperiness, low friction, antithrombotic properties, heat resistance, electrical properties, flexibility, oxygen permeability, and radiation resistance can be obtained.

[Example 5] Synthesis of polymer (A3) having fluorosilsesquioxane, N-alkyl-substituted (meth) acrylamide, and acryloyl in the side chain N-methyl instead of methoxypolyethyleneglycol monomethacrylate in Example 1 A polymer (A3) having fluorosilsesquioxane, N-alkyl-substituted (meth) acrylamide, and acryloyl can be obtained by performing the same operation as in Example 1 except that methacrylamide is used.

[Example 6] Synthesis of polymer (A4) having fluorosilsesquioxane, N, N-dialkyl-substituted (meth) acrylamide, and acryloyl in the side chain N instead of methoxypolyethyleneglycol monomethacrylate in Example 1 , N-dimethyl (meth) acrylamide, except that fluorosilsesquioxane, N, N-dialkyl-substituted (meth) acrylamide, and a polymer having acryloyl (by using the same procedure as in Example 1) A4) can be obtained.

[Comparative Example 1] Synthesis of polymer (B1) having fluorosilsesquioxane, methyl and acryloyl in the side chain <Synthesis of polymer having fluorosilsesquioxane, methyl and hydroxyl in the side chain>
In a 100 mL three-necked flask equipped with a reflux condenser, thermometer and dropping funnel, 30.84 g of compound (a-1), 1.65 g of 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA) ) And 2.48g of methyl ethyl ketone (MEK) were introduced and sealed with nitrogen. It was set in an oil bath maintained at 95 ° C. and refluxed, and deoxygenated for 10 minutes. Next, a solution in which 0.10 g of azobisisobutyronitrile (AIBN) and 0.06 g of mercaptoacetic acid (AcSH) were dissolved in 1.45 g of MEK was introduced, and polymerization was started while maintaining the reflux temperature. After polymerization for 3 hours, a solution in which 0.10 g of AIBN was dissolved in 1.19 g of MEK was introduced, and the polymerization was further continued for 5 hours to obtain a polymer having a fluorosilsesquioxane, methyl and hydroxyl (b1 ) Was obtained. The weight average molecular weight determined by GPC analysis of the polymerization solution was 38,000, and the molecular weight distribution was 1.6. The compositional mole fraction of the monomer component determined from ¹ H-NMR measurement was Compound (a-1): HEMA: MMA = 41.9: 27.3: 30.8.

<Synthesis of polymer (B1) having fluorosilsesquioxane, methyl and acryloyl in side chain>
52.75 g of a polymer solution (a1) containing a polymer having oxyalkylene and hydroxyl was introduced into a four-necked flask with an internal volume of 100 mL equipped with a reflux condenser, a thermometer and a septum cap, and p-methoxyphenol was further introduced. (MEHQ) 0.0267 g and dibutyltin dilaurate (DBTDL) 0.0217 g were dissolved in 0.20 g of MEK and introduced, and sealed with nitrogen. It set to the oil bath maintained at 48 degreeC, and heated up. Next, when the liquid temperature reached 45 ° C., 1.94 g of acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was introduced, and the reaction was started. After reacting for 6 hours, the reaction was terminated by cooling to room temperature and introducing 1.32 g of MeOH to obtain a polymer solution containing a polymer (B1) having fluorosilsesquioxane, methyl and acryloyl. The weight average molecular weight determined by GPC analysis of the polymerization solution was 38,000, and the molecular weight distribution was 1.6.

[Comparative Example 2] Preparation of Film A film thickness of about 8 μm was obtained in the same manner as in Example 2 except that the polymer (B1) obtained in Comparative Example 1 was used instead of the polymer (A1) in Example 2. A transparent film was obtained.

[Test 1]
The physical property values of the films obtained in Example 2 and Comparative Example 2 were measured by the following methods.

1) Contact angle and surface free energy measurement About the obtained film, FACE contact angle meter (image processing type) CA-X type (manufactured by Kyowa Interface Science Co., Ltd.) is used as probe liquid and distilled water (nitrogen / phosphorus measurement). , Manufactured by Kanto Chemical Co., Ltd.), and hexadecane (99%, manufactured by Aldrich) were measured, and the surface free energy was calculated according to Kaelble-Uy theory.

2) Dynamic contact angle measurement Advancing contact angle and receding based on the expansion / contraction method using distilled water (for measuring nitrogen and phosphorus, manufactured by Kanto Chemical Co., Inc.) as the probe liquid using the same apparatus as 1) The contact angle was measured and the hysteresis was calculated.

3) Contamination resistance test Using an oil-based signature pen (Magic Ink (registered trademark), red, M500-T2, Teranishi Chemical Co., Ltd.), draw a 1.5mm x 100mm line on the coating film to repel the magic. confirmed. Moreover, the coating film after drawing the line with the magic was washed with distilled water, and the coating film after washing was evaluated according to the following evaluation criteria.
++: Magic line can be washed away +: Magic line can be washed off almost

(Consideration of evaluation results such as test examples)
From Table 1, when Example 2 and Comparative Example 2 are compared, the film of Example 2 obtained using a polymer having hydrophilic oxyalkylene has no polymer having hydrophilic oxyalkylene. The hysteresis, which is the difference between the advancing contact angle and the receding contact angle, was larger than that of the film of Comparative Example 2 obtained using The magnitude of hysteresis indicates the environmental responsiveness of the test sample, that is, the mobility of the segment on the surface in a hydrophilic / hydrophobic environment. In Example 2, the hydrophilic oxyalkylene exhibits excellent environmental responsiveness. did.
In Example 2, the magic ink was repelled and the cleaning property was improved in terms of stain resistance. This is because not only the function of the fluorosilsesquioxane compound but also the excellent features of the hydrophilic oxyalkylene present in the same molecule were effectively expressed by the excellent blooming characteristics of the fluorosilsesquioxane compound. Is suggested.

  Specific applications of the polymer and surface modifier of the present invention include, for example, prevention of toner sticking and charge enhancement, addition of a non-adhesive function to a fixing roller, a mag roller, a rubber roller, etc., and sliding on a peeling nail. Surface modifiers for electronic copier members, such as for the addition of dynamic functions, automotive topcoats for antifouling purposes, surface modifiers for hard coats, antifouling treatment agents for optical applications used in lenses, etc. Antifogging treatment agent, antifouling treatment agent for building materials such as wall materials and flooring materials, mold release treatment agent for nanoimprinting, resist material modifier, water repellent and waterproof treatment agent for printed circuit boards Protective film used in displays, antifouling treatment for protective film, antifouling of touch panel, surface modifier for preventing fingerprint adhesion, mold release for imparting release function to films such as polyester It is possible to utilize such sense agents can result in diversity in the properties and uses.

Claims (26)

  Structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, structural unit B derived from an addition polymerizable monomer containing a hydrophilic group, derived from an addition polymerizable monomer Constitutional unit C having a group having a polymerizable unsaturated bond in the side chain, and optionally addition of fluorosilsesquioxane having one addition polymerizable functional group in the molecule, hydrophilic group A polymer comprising a structural unit E derived from an addition polymerizable monomer other than the addition polymerizable monomer having a functional group capable of introducing a polymerizable monomer and a group having a polymerizable unsaturated bond.   Structural unit A derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, structural unit B derived from an addition polymerizable monomer containing a hydrophilic group, derived from an addition polymerizable monomer A structural unit C having a group having a polymerizable unsaturated bond in the side chain, a structural unit D derived from an organopolysiloxane having an addition polymerizable functional group, and, optionally, one addition in the molecule Fluorosilsesquioxane having a polymerizable functional group, an addition polymerizable monomer having a hydrophilic group, an addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond, and addition polymerizability A polymer comprising a structural unit E ′ derived from an addition polymerizable monomer other than an organopolysiloxane having a functional group. The polymer according to claim 1 or 2, wherein the fluorosilsesquioxane having one addition polymerizable functional group in the molecule is represented by the following formula (1).

In Formula (1), R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoro A fluoroaryl having 6 to 20 carbon atoms replaced by methyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and A ¹ is An addition polymerizable functional group is shown. R _f ^{1 to} R _f ⁷ in formula (1) are each independently 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, 4. A polymer according to claim 3, characterized in that it represents α-trifluoromethylphenyl. R _f ^{1 to} R _f ⁷ in formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, Or polymer according to claim 3, characterized in that it represents tridecafluoro-1,1,2,2-tetrahydrooctyl. The polymer according to any one of claims 3 to 5, wherein A ¹ in the formula (1) is a radical polymerizable functional group. The polymer according to claim 6, wherein A ¹ in the formula (1) contains (meth) acryl or styryl. The polymer according to claim 7, wherein A ¹ in the formula (1) is any one represented by the following formula (2) or (3).

In Formula (2), Y ¹ represents alkylene having 2 to 10 carbons, R ¹ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons. In Formula (3), Y 1 ² represents a single bond or alkylene having 1 to 10 carbon atoms. In formula (2), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ¹ represents hydrogen or methyl, and Y ² in formula (3) represents a single bond or alkylene having 1 or 2 carbon atoms, Item 9. The polymer according to Item 8.   The hydrophilic group of the addition polymerizable monomer containing a hydrophilic group is hydroxyl, salt of hydroxyl, carboxyl, salt of carboxyl, sulfo, salt of sulfo, phosphate group, salt of phosphate group, amino The polymer according to any one of claims 1 to 9, which is a salt of amino, amide, quaternary ammonium salt or oxyalkylene.   The polymer according to any one of claims 1 to 9, wherein the hydrophilic group of the addition polymerizable monomer containing a hydrophilic group is oxyalkylene or amide.   The addition polymerizable monomer containing a hydrophilic group is polyalkylene glycol mono (meth) acrylate, N-alkyl-substituted (meth) acrylamide, or N, N-dialkyl-substituted (meth) acrylamide. The polymer as described in any one of -9.   The polymer according to any one of claims 1 to 12, wherein the group having a polymerizable unsaturated bond of the structural unit C is a radically polymerizable functional group.   The polymer according to any one of claims 1 to 13, wherein the group having a polymerizable unsaturated bond of the structural unit C is (meth) acryl or styryl. The polymer according to any one of claims 2 to 14, wherein the organopolysiloxane having an addition polymerizable functional group of the structural unit D is represented by the following formula (4).

In the formula (4), n is an integer of 1 to 1,000; R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Are each independently hydrogen, alkyl having 1 to 30 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene , Substituted or unsubstituted aryl, and substituted or unsubstituted aryl and alkylene in which any hydrogen may be replaced by fluorine and any —CH ₂ — may be replaced by —O— or cycloalkylene A configured arylalkyl; A ² is an addition polymerizable functional group. R ² and R ³ in formula (4) are each independently hydrogen, phenyl or alkyl having 1 to 8 carbon atoms, and any hydrogen may be replaced by fluorine; R ⁴ and R ⁵ are each Independently alkyl having 1 to 20 carbon atoms and arbitrary hydrogen may be replaced with fluorine, aryl having 6 to 20 carbon atoms and arbitrary hydrogen being replaced with fluorine, or 7 carbon atoms R ⁶ is alkyl having 1 to 20 carbon atoms and arbitrary hydrogen may be replaced with fluorine, and R ⁶ is alkyl having ⁶ to 20 carbon atoms. 16. The aryl which is 20 and arbitrary hydrogen may be replaced with fluorine, or arylalkyl which has 7 to 20 carbon atoms and may optionally be replaced with fluorine. Polymer. R ² and R ³ in formula (4) are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ⁴ and R ⁵ are each independently methyl or phenyl; R ⁶ is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 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-tri The polymer of claim 15 which is Le Oro methylphenyl. The polymer according to claim 15, wherein R ² , R ³ , R ⁴ and R ⁵ in the formula (4) are each simultaneously methyl. The polymer according to any one of claims 15 to 18, wherein A ² in the formula (4) is a radical polymerizable functional group. The polymer according to claim 19, wherein A ² in the formula (2) contains (meth) acryl or styryl. The polymer according to claim 20, wherein A ² in the formula (4) is any one of the following formulas (2), (3), or (5).

In Formula (2), Y ¹ represents alkylene having 2 to 10 carbons, R ¹ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons. ⁷ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, X ¹ is alkylene having 2 to 20 carbon atoms, and Y is —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ — or —OCH ₂ CH (CH ₃ ) —, p is an integer of 0 to 3, and in formula (3), Y ² represents a single bond or an alkylene having 1 to 10 carbon atoms. . In Formula (2), Y ¹ represents alkylene having 2 to 6 carbon atoms, R ⁶ represents hydrogen or methyl, and in Formula (5), X ¹ represents —CH ₂ CH ₂ CH ₂ —, and Y represents -OCH ₂ CH ₂ - indicates, p is 0 or 1, R ⁷ represents hydrogen or methyl, represents an alkylene Y ² is a single bond or a C 1 or 2 in the formula (3), according to claim 21 The polymer described in 1.   The resin composition containing the polymer as described in any one of Claims 1-22, and 1 or more types of resin chosen from a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin.   Furthermore, it is a polymer containing the group which has a polymerizable unsaturated bond, Comprising: The resin composition of Claim 23 containing the polymer which does not correspond to any of Claims 1-22.   A surface modifier containing the polymer according to any one of claims 1 to 22 or the resin composition according to claim 23 or 24.   An amphiphilic film obtained by the surface modifier according to claim 25.