JP5228367B2 - Surface protection film - Google Patents

Description

  The present invention relates to a surface protective film used for protecting a surface by being attached to a flat panel display or the like.

  Conventionally, when a surface protective film having an adhesive layer provided on the surface of a base material layer is finished in a roll shape, the adhesive layer adheres to the base material layer and the like by winding, and thus blocking is difficult to peel off. A phenomenon may occur, and it may become impossible to feed out the surface protection film from the roll-shaped scroll. In order to prevent the malfunction due to the blocking phenomenon, the base material itself has a release property or the adhesive layer is protected with a release paper or the like, but the handling property is not good (for example, Patent Document 1). reference.). In the former case, there is a problem that the properties of the base material itself are limited. In the latter case, there are problems such as complicated processes.

  For this reason, in order to improve the problems caused by the blocking phenomenon, it has been studied to provide a release layer on the opposite surface of the adhesive layer with the base material layer interposed therebetween (for example, see Patent Document 2). Specifically, when a thermoplastic elastomer adhesive layer is provided by co-pushing, the adhesive layer is low-tackiness, so it is relatively easy to suppress the blocking phenomenon by selecting a general-purpose release agent. Is possible. However, when an adhesive layer is provided by coating a strong adhesive type adhesive, it takes a lot of time to select a release agent for preventing the blocking phenomenon, and it is very important to suppress the blocking phenomenon. Have difficulty.

JP-A-2-252777 JP 2003-41216 A

  For this reason, the problem of the present invention is that, even when a roll-shaped roll is provided, it has a release layer that exhibits stable release properties regardless of the material used for the adhesive layer. The object is to provide a surface protective film in which troubles due to the blocking phenomenon do not occur.

  As a result of searching for various mold release components from the above viewpoint, the present inventors have found that fluoropolymers containing fluorosilsesquioxane as an essential component are excellent in mold release properties. It has been found that the problem of the present invention can be solved by forming a release layer using coalescence, and the present invention has been completed.

［式（Ｉ）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。］
［３］ 前記式（Ｉ）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、前記［２］項記載の表面保護フィルム。
［４］ 前記式（Ｉ）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、または３,３,４,４,５,５,６,６,６-ノナフルオロヘキシルを示すことを特徴とする、前記［３］項記載の表面保護フィルム。
［５］ 前記式（Ｉ）におけるＡ¹が、ラジカル重合性官能基を示すことを特徴とする前記［２］〜［４］のいずれか一項記載の表面保護フィルム。
［６］ 前記式（Ｉ）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前記［２］〜［５］のいずれか一項記載の表面保護フィルム。
［７］ 前記式（Ｉ）におけるＡ¹が、下記式（II）または（III）で示されるいずれかであることを特徴とする前記［６］項記載の表面保護フィルム。

［式（II）において、Ｙ¹が炭素数２〜１０のアルキレンを示し、Ｘが水素または炭素数１〜３のアルキルを示し、
式（III）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。］
［８］ 前記式（II）において、Ｙ¹が炭素数２〜６のアルキレンを示し、Ｘが水素または炭素数１〜３のアルキルを示し、式（III）において、Ｙ²が単結合または炭素数１〜６のアルキレンを示す前記［７］項記載の表面保護フィルム。
［９］ 前記式（II）において、Ｙ¹がプロピレンを示し、Ｘは水素またはメチルを示し、式（III）において、Ｙ²が単結合またはエチレンを示す前記［７］項記載の表面保護フィルム。
［１０］ 前記付加重合性単量体（ｂ）が、（メタ）アクリル酸化合物またはスチレン化合物である、前記［１］〜［９］のいずれか一項記載の表面保護フィルム。
［１１］ 前記付加重合性単量体（ｂ）の少なくとも一部が、架橋性官能基を有する付加重合性単量体である、前記［１］〜［１０］のいずれか一項記載の表面保護フィルム。
［１２］ 前記表面保護フィルムの離型層に、エポキシ樹脂単量体を含む前記［１］〜［１１］のいずれか一項記載の表面保護フィルム。
［１３］ 接着層、基材層および離型層を有しており、基材層の片側の表面に接着層を有し、反対側の表面に離型層を有する表面保護フィルムであって、該基材層は、熱可塑性樹脂を含有する層であり、該接着層は、接着剤または粘着剤を含有する層であり、該離型層は、１つの付加重合性官能基を有するフルオロシルセスキオキサン（ａ）と、付加重合性官能基を有するオルガノポリシロキサン（ｃ）との付加共重合体、または、１つの付加重合性官能基を有するフルオロシルセスキオキサン（ａ）と、付加重合性官能基を有するオルガノポリシロキサン（ｃ）と、付加重合性単量体（ｂ）との付加共重合体を含有する層であることを特徴とする表面保護フィルム。
［１４］ 前記フルオロシルセスキオキサン（ａ）が、下記式（Ｉ）で示されることを特徴とする、前記［１３］項記載の表面保護フィルム。

［式（Ｉ）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。］
［１５］ 式（Ｉ）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前記［１４］項記載の表面保護フィルム。
［１６］ 式（Ｉ）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、または３,３,４,４,５,５,６,６,６-ノナフルオロヘキシルを示すことを特徴とする前記［１５］項記載の表面保護フィルム。
［１７］ オルガノポリシロキサン（ｃ）が下記式（IV）であることを特徴とする前記［
１３］〜［１６］のいずれか一項記載の表面保護フィルム。

［式（IV）において、ｎは１〜１，０００の整数であり；Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、およびＲ⁵は、それぞれ、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、から独立して選択される基であり；Ａ²は付加重合性官能基である。］
［１８］ 式（IV）におけるＲ¹およびＲ²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；Ｒ³およびＲ⁴が、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；Ｒ⁵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前記［１７］項記載の表面保護フィルム。
［１９］ 式（IV）におけるＲ¹およびＲ²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；Ｒ³およびＲ⁴は、それぞれ独立してメチルまたはフェニルであり；Ｒ⁵はメチル、エチル、プロピル、ブチル、イソブチル、またはフェニルである前記［１８］項記載の表面保護フィルム。
［２０］ Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ同時にメチルである前記［１９］項記載の表面保護フィルム。
［２１］ 式（Ｉ）におけるＡ¹および式（IV）におけるＡ²が付加重合性官能基であることを特徴とする前記［１４］〜［２０］のいずれか一項記載の表面保護フィルム。
［２２］ 式（Ｉ）におけるＡ¹および式（IV）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前記［２１］項記載の表面保護フィルム。
［２３］ 式（Ｉ）におけるＡ¹および式（IV）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前記［２２］項記載の表面保護フィルム。
［２４］ 式（Ｉ）におけるＡ¹が、下記式（Ｖ）または（VII）で示されるいずれかであり、式（IV）におけるＡ²が、下記式（Ｖ）、（VI）または（VII）で示されるいずれ
かである前記［２３］項記載の表面保護フィルム。

［式（Ｖ）において、Ｙ³が炭素数２〜１０のアルキレンを示し、Ｒ⁶が水素、または炭
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（VI）において、Ｒ⁷は水素、または炭素数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（VII）において、Ｙ⁴が単結合または炭素数１〜１０のアルキレンを示す。］
［２５］ 式（Ｖ）において、Ｙ³が炭素数２〜６のアルキレンを示し、Ｒ⁶が水素または炭素数１〜３のアルキルを示し、式（VI）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が水素または炭素数１〜３のアルキルを示し、式（VII）においてＹ⁴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、前記［２４］項記載の表面保護フィルム。
［２６］ 前記付加重合性単量体（ｂ）が架橋性官能基を有する付加重合性単量体及び架橋性官能基を有さない単量体から選ばれる少なくとも１種である前記［１３］〜［２５］のいずれか一項記載の表面保護フィルム。
［２７］ 前記付加重合性単量体（ｂ）が架橋性官能基を有する付加重合性単量体である前記［１３］〜［２５］のいずれか一項記載の表面保護フィルム。
［２８］ 前記架橋性官能基を有する付加重合性単量体がラジカル重合性官能基を有し、且つ同一分子内において１つ以上のヒドロキシル、グリシジル、オキセタニル、エポキシシクロヘキシル、ハロゲン化アルキル、ブロックドイソシアナト、イソシアナト、アミノまたはカルボキシルを有する化合物である前記［２７］項記載の表面保護フィルム。
［２９］ 前記架橋性官能基を有する付加重合性単量体におけるラジカル重合性官能基が（メタ）アクリルまたはスチリルである前記［２８］項記載の表面保護フィルム。
［３０］ 前記離型層に、熱可塑性樹脂および/または熱硬化性樹脂を含有する前記［１３］〜［２９］のいずれか一項記載の表面保護フィルム。
［３１］ 前記離型層に、熱硬化性樹脂を含有する前記［１３］〜［２９］のいずれか一項記載の表面保護フィルム。
［３２］ 熱硬化性樹脂がヒドロキシル、グリシジル、オキセタニル、エポキシシクロヘキシル、ハロゲン化アルキル、ブロックドイソシアナト、イソシアナト、アミノまたはカルボキシルを有する化合物である、前記［３１］項記載の表面保護フィルム。
［３３］ 熱硬化性樹脂がグリシジル、オキセタニル、またはエポキシシクロヘキシルを有する化合物である前記［３２］項記載の表面保護フィルム。 That is, this invention relates to the surface protection film shown below.
[1] A surface protective film having an adhesive layer, a base material layer, and a release layer, having an adhesive layer on one surface of the base material layer, and having a release layer on the opposite surface, The base material layer is a layer containing a thermoplastic resin, the adhesive layer is a layer containing an adhesive or a pressure-sensitive adhesive, and the release layer is
Addition polymer of fluorosilsesquioxane (a) having one addition polymerizable functional group, or fluorosilsesquioxane (a) having one addition polymerizable functional group, and addition polymerizable monomer (b And a surface protective film comprising an addition copolymer. [2] The surface protective film according to [1], wherein the fluorosilsesquioxane (a) is represented by the following formula (I).

[In Formula (I),
R _f ^{1 to} R _f ⁷ are each independently
1 to 20 carbon fluoroalkyls in which any methylene may be replaced by oxygen;
C6-C20 fluoroaryl in which at least one hydrogen is replaced with fluorine or trifluoromethyl; or C7-C20 fluoro in which at least one hydrogen in aryl is replaced with fluorine or trifluoromethyl Represents arylalkyl,
A ¹ represents an addition polymerizable functional group. ]
[3] R _f ^{1 to} R _f ⁷ in the formula (I) 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, heico Safluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or The surface protective film as described in the above item [2], which represents α, α, α-trifluoromethylphenyl.
[4] R _f ^{1 to} R _f ⁷ in the formula (I) are each independently 3,3,3-trifluoropropyl, or 3,3,4,4,5,5,6,6,6. -The surface protective film as described in the above item [3], which exhibits nonafluorohexyl.
[5] The surface protective film according to any one of [2] to [4], wherein A ¹ in the formula (I) represents a radical polymerizable functional group.
[6] The surface protective film according to any one of [2] to [5], wherein A ¹ in the formula (I) includes (meth) acryl or styryl.
[7] The surface protective film as described in the above item [6], wherein A ¹ in the formula (I) is represented by the following formula (II) or (III).

[In Formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, X represents hydrogen or alkyl having 1 to 3 carbon atoms,
In the formula (III), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms. ]
[8] In the formula (II), Y ¹ represents alkylene having 2 to 6 carbon atoms, X represents hydrogen or alkyl having 1 to 3 carbon atoms, and in formula (III), Y ² represents a single bond or carbon. The surface protection film of the said [7] item | term which shows alkylene of several 1-6.
[9] The surface protective film according to the above [7], wherein in the formula (II), Y ¹ represents propylene, X represents hydrogen or methyl, and in the formula (III), Y ² represents a single bond or ethylene. .
[10] The surface protective film according to any one of [1] to [9], wherein the addition polymerizable monomer (b) is a (meth) acrylic acid compound or a styrene compound.
[11] The surface according to any one of [1] to [10], wherein at least a part of the addition polymerizable monomer (b) is an addition polymerizable monomer having a crosslinkable functional group. Protective film.
[12] The surface protective film according to any one of [1] to [11], wherein the release layer of the surface protective film contains an epoxy resin monomer.
[13] A surface protective film having an adhesive layer, a base material layer, and a release layer, having an adhesive layer on one surface of the base material layer, and having a release layer on the opposite surface, The base material layer is a layer containing a thermoplastic resin, the adhesive layer is a layer containing an adhesive or a pressure-sensitive adhesive, and the release layer is a fluorosilic having one addition polymerizable functional group. Addition copolymer of sesquioxane (a) and organopolysiloxane (c) having addition polymerizable functional group, or fluorosilsesquioxane (a) having one addition polymerizable functional group and addition A surface protective film, which is a layer containing an addition copolymer of an organopolysiloxane (c) having a polymerizable functional group and an addition polymerizable monomer (b).
[14] The surface protective film according to [13], wherein the fluorosilsesquioxane (a) is represented by the following formula (I).

[In Formula (I),
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;
C6-C20 fluoroaryl in which at least one hydrogen is replaced with fluorine or trifluoromethyl; or C7-C20 fluoro in which at least one hydrogen in aryl is replaced with fluorine or trifluoromethyl an aryl alkyl, a ¹ represents an addition polymerizable functional group. ]
[15] R _f ^{1 to} R _f ⁷ in formula (I) 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 surface protective film as described in the above item [14],
[16] R _f ^{1 to} R _f ⁷ in formula (I) are each independently 3,3,3-trifluoropropyl, or 3,3,4,4,5,5,6,6,6- The surface protective film as described in the above item [15], which represents nonafluorohexyl.
[17] The organopolysiloxane (c) represented by the following formula (IV):
The surface protective film according to any one of [13] to [16].

[In the formula (IV), n is an integer of ^{1 to} 1,000; R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each hydrogen, 1 to 30 carbon atoms, 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 A group independently selected from arylalkyl composed of alkylene in which hydrogen may be replaced by fluorine or any —CH ₂ — may be replaced by —O— or cycloalkylene; A ² is an addition polymerizable functional group. ]
[18] R ¹ and R ² in formula (IV) are each independently hydrogen, phenyl, or alkyl having 1 to 8 carbon atoms, and any hydrogen may be replaced by fluorine; R ³ and R ⁴ Is 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 Is arylalkyl in which any hydrogen may be replaced with fluorine; R ⁵ is alkyl having 1 to 20 carbon atoms and any hydrogen may be replaced with fluorine, [17] The above item [17], wherein the aryl is 6 to 20 and any hydrogen may be replaced with fluorine, or arylalkyl that has 7 to 20 carbon atoms and any hydrogen may be replaced with fluorine. Surface protective film.
[19] R ¹ and R ² in formula (IV) are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ³ and R ⁴ are each independently methyl or phenyl Yes; The surface protective film according to [18], wherein R ⁵ is methyl, ethyl, propyl, butyl, isobutyl, or phenyl.
[20] The surface protective film according to [19], wherein R ¹ , R ² , R ³ and R ⁴ are each simultaneously methyl.
[21] The surface protective film according to any one of [14] to [20], wherein A ¹ in the formula (I) and A ² in the formula (IV) are addition polymerizable functional groups.
[22] The surface protective film as described in the above item [21], wherein A ¹ in the formula (I) and A ² in the formula (IV) are radical polymerizable functional groups.
[23] The surface protective film as described in the above item [22], wherein A ¹ in the formula (I) and A ² in the formula (IV) contain (meth) acryl or styryl.
[24] A ¹ in the formula (I) is any one of the following formulas (V) or (VII), and A ² in the formula (IV) is represented by the following formula (V), (VI) or (VII The surface protective film according to [23], which is any one of the following:

[In the formula (V), Y ³ represents alkylene having 2 to 10 carbon atoms, R ⁶ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbon atoms; , 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, 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 (VII), Y ⁴ is a single bond or a carbon number of 1 to 10 Represents alkylene. ]
[25] In formula (V), Y ³ represents alkylene having 2 to 6 carbon atoms, R ⁶ represents hydrogen or alkyl having 1 to 3 carbon atoms, and in formula (VI), 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 alkyl having 1 to 3 carbon atoms, and Y ⁴ is a single atom in formula (VII). The surface protective film according to the above [24], which represents a bond or alkylene having 1 or 2 carbon atoms.
[26] The above [13], wherein the addition polymerizable monomer (b) is at least one selected from an addition polymerizable monomer having a crosslinkable functional group and a monomer having no crosslinkable functional group. -The surface protection film as described in any one of [25].
[27] The surface protective film according to any one of [13] to [25], wherein the addition polymerizable monomer (b) is an addition polymerizable monomer having a crosslinkable functional group.
[28] The addition polymerizable monomer having a crosslinkable functional group has a radical polymerizable functional group, and one or more hydroxyl, glycidyl, oxetanyl, epoxycyclohexyl, halogenated alkyl, blocked in the same molecule. The surface protective film according to the above [27], which is a compound having isocyanato, isocyanato, amino or carboxyl.
[29] The surface protective film according to [28], wherein the radical polymerizable functional group in the addition polymerizable monomer having a crosslinkable functional group is (meth) acryl or styryl.
[30] The surface protective film according to any one of [13] to [29], wherein the release layer contains a thermoplastic resin and / or a thermosetting resin.
[31] The surface protective film according to any one of [13] to [29], wherein the release layer contains a thermosetting resin.
[32] The surface protective film according to [31] above, wherein the thermosetting resin is a compound having hydroxyl, glycidyl, oxetanyl, epoxycyclohexyl, alkyl halide, blocked isocyanato, isocyanato, amino or carboxyl.
[33] The surface protective film according to the above [32], wherein the thermosetting resin is a compound having glycidyl, oxetanyl, or epoxycyclohexyl.

  The surface protective film of the present invention has a release layer showing a stable release property with respect to an adhesive layer having various adhesive performances. Trouble caused by blocking phenomenon does not occur.

  The surface protective film of the present invention has an adhesive layer, a base material layer and a release layer, has an adhesive layer on one surface of the base material layer, and has a release layer on the opposite surface. The base material layer is a layer containing a thermoplastic resin, the adhesive layer is a layer containing an adhesive or a pressure-sensitive adhesive, and the release layer has one addition polymerizable functional group. It is a layer containing an addition polymer of fluorosilsesquioxane (a) or an addition copolymer with another addition polymerizable monomer (b). Furthermore, in the present invention, the release layer is an addition copolymer of fluorosilsesquioxane (a) having one addition polymerizable functional group and organopolysiloxane (c) having an addition polymerizable functional group, Or addition copolymerization of fluorosilsesquioxane (a) having one addition polymerizable functional group, organopolysiloxane (c) having addition polymerizable functional group, and addition polymerizable monomer (b) It is a layer containing coalescence. The basic structure of the surface protective film of the present invention is a three-layer structure including an adhesive layer, a base material layer, and a release layer, but it may have a multilayer structure as necessary. For example, an intermediate layer such as an antistatic layer can be laminated between the adhesive layer and the base material layer.

  The base material layer constituting the surface protective film of the present invention is a layer formed of a material mainly composed of a thermoplastic resin, and is not particularly limited as long as it is a material that can be processed into a general film or sheet. The thermoplastic resin used in the present invention is not particularly limited, and polyolefin resin, ABS resin, polystyrene resin, AS resin, polyvinyl chloride resin, polyamide resin, polyethylene terephthalate resin, biodegradable resin (polylactic acid resin, succinate resin) Etc.). Of these, polyolefin resins are preferred from the viewpoints of economy, reduction of environmental burden, mechanical properties and processing properties of the thermoplastic resin composition. Examples of polyolefin resins include high-density polyethylene, linear low-density polyethylene, low-density polyethylene, and the like, propylene homopolymers, ethylene-propylene copolymers based on propylene, and ethylene-propylene based on propylene. -Polypropylene such as butene-1 copolymer, polybutene-1, polyhexene-1, polyoctene-1, poly-4-methylpentene-1, polymethylpentene, 1,2-polybutadiene, 1,4-polybutadiene, etc. can be used. . Further, these homopolymers contain a small amount of α-olefin such as ethylene, butene-1, hexene-1, octene-1, or 4-methylpentene-1 other than the monomers constituting the homopolymer as a copolymerization component. It may be contained. Two or more of the above polyolefin resins may be mixed and used. These may be not only polyolefin resins polymerized from ordinary Ziegler-Natta catalysts but also polyolefin resins polymerized from metallocene catalysts.

  The base material layer constituting the surface protective film of the present invention can be obtained by forming a film or sheet using a thermoplastic resin by a general inflation method, a T-die method, or the like. Moreover, it can also be set as a laminated film and a sheet-like material in one process by co-extruding these materials with the material of an adhesive layer.

  The thickness of the base material layer constituting the surface protective film of the present invention is not particularly limited, but is usually about 20 μm to 300 μm.

  The adhesive layer constituting the surface protective film of the present invention may be any material that is generally used for a member for the purpose of adhesion or adhesion, and if a thermoplastic material is used, it can be coextruded with the base material layer. Can be formed. Examples of materials that can be used as the pressure-sensitive adhesive in this case include styrene-based elastomers, urethane-based elastomers, ester-based elastomers, and olefin-based elastomers.

The adhesive layer constituting the surface protective film of the present invention can be formed by coating the base material layer with various adhesives. Examples of these materials include acrylic adhesives, methacrylic adhesives, silicon adhesives, epoxy adhesives, hot melt adhesives, polyurethane adhesives, and emulsion adhesives. Can be used properly. When the adhesive layer is formed by coating, the adhesive layer is generally stronger than the laminated film by coextrusion of the pressure sensitive adhesive. The phenomenon does not occur and the problem of feeding failure does not occur.

  The method for coating the adhesive on the surface of the substrate layer of the surface protective film of the present invention is not particularly limited, but spin coating, roll coating, slit coating, dipping, spray coating, gravure coating , Reverse coating method, 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. The substrate layer may be pretreated. Examples of 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 thickness of the adhesive layer constituting the surface protective film of the present invention is not particularly limited, but is usually about 1 μm to 50 μm.

  The release layer constituting the surface protective film of the present invention comprises an addition polymer of fluorosilsesquioxane (a) having one addition polymerizable functional group shown below, or another addition polymerizable monomer (b And a layer containing an addition copolymer. Furthermore, in the present invention, the release layer comprises an addition copolymer of fluorosilsesquioxane (a) having one addition polymerizable functional group shown below and organopolysiloxane (c) having an addition polymerizable functional group. Polymer, or fluorosilsesquioxane (a) having one addition polymerizable functional group, organopolysiloxane (c) having an addition polymerizable functional group, and addition polymerizable monomer (b) It is a layer containing an addition copolymer.

<Fluorosilsesquioxane (a)>
Fluorosilsesquioxane (a) having one addition polymerizable functional group (hereinafter referred to as “silsesquioxane”), which is a raw material monomer for the polymer used in the release layer constituting the surface protective film of the present invention. (A) ") also 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 (a) used in the present invention preferably has a cage structure of T ₈ type [(R—SiO _1.5 ) ₈ ].

Said fluorosilsesquioxane (a) is characterized by having one addition polymerizable functional group. That is, one of R in 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 Group having an anion-polymerizable functional group such as a radical-polymerizable functional group is preferable.

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 and the like are included, and among them, a group containing (meth) acryl or styryl is preferable. 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 (II). In formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms, more preferably alkylene (propylene) having 3 carbon atoms. X represents hydrogen or alkyl having 1 to 3 carbon atoms, preferably hydrogen or methyl.

Examples of the radical polymerizable functional group having styryl include groups represented by the following formula (III). In formula (III), 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 2 carbon atoms (ethylene). Vinyl is bonded to any carbon of the benzene ring, and preferably bonded to carbon in the para position with respect to Y ² .

The fluorosilsesquioxane (a) 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 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 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 by 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 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. Of these, perfluoroalkylethyl is preferably exemplified.

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 fluoroalkyl, fluoroarylalkyl, and fluoroaryl contained in the fluorosilsesquioxane (a), a preferred group is fluoroalkyl, more preferably perfluoroalkylethyl, and even more preferably 3.3. , 3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

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

In the above formula (I), A ¹ is preferably the aforementioned radical polymerizable functional group, and R _f ^{1 to} R _f ⁷ are each independently the above-described fluoroalkyl, fluoroarylalkyl, or fluoroaryl. Preferably there is. R _f ^{1 to} R _f ⁷ may be different groups or all may be the same group.

<Addition polymerizable monomer (b)>
Addition polymerizable monomers include those having a crosslinkable functional group and those having no crosslinkable functional group. The addition polymerizable monomer (b) having a crosslinkable functional group may be a compound having one or two or more addition polymerizable double bonds, such as a vinyl compound, a vinylidene compound, and a vinylene compound. More specifically, a (meth) acrylic acid compound or a styrene compound is exemplified.

  Examples of the (meth) acrylic acid compound include (meth) acrylic acid and (meth) acrylic acid ester, (meth) acrylic acid amide, (meth) acrylonitrile and the like.

  Examples of the (meth) acrylic acid compound of the addition polymerizable monomer (b) include (meth) acrylate having a crosslinkable functional group. Examples of such a crosslinkable functional group include epoxies such as glycidyl and epoxycyclohexyl, oxetanyl, isocyanato, acid anhydride, carboxyl, hydroxyl, etc., and preferably epoxies such as glycidyl and oxetanyl. Specific examples of the (meth) acrylate having the crosslinkable functional group include hydroxyalkyl (meth) acrylates such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; Epoxy-containing (meth) acrylates such as glycidyl (meth) acrylate; alicyclic epoxy-containing (meth) acrylates such as 3,4-epoxycyclohexylmethyl (meth) acrylate; 3-ethyl-3- (meth) acryloyloxymethyl oxetane Oxetanyl-containing (meth) acrylates such as 2- (meth) acryloyloxyethyl isocyanate; γ- (methacryloyloxypropyl) trimethoxysilane; (meth) acrylate-2-aminoethyl, 2- (2-bromopropionyloxy) ethyl (Meta) Acrelay 2- (2-bromoisobutyryloxy) ethyl (meth) acrylate; 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) Ethane, 1- (4-((4- (meth) acryloxy) ethoxyethyl) phenylethoxy) piperidine, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6, 6-pentamethyl-4-piperidyl (meth) acrylate;

Examples of the styrene compound having one addition polymerizable double bond include a styrene compound having a crosslinkable functional group. Specific examples of such crosslinkable functional groups include epoxies such as glycidyl, oxetanyl, halo, amino, isocyanato, acid anhydride, carboxyl, hydroxyl, thiol, siloxy and the like.
Examples of styrene compounds having a crosslinkable functional group include o-aminostyrene, p-styrene chlorosulfonic acid, styrene sulfonic acid and salts thereof, vinylphenylmethyldithiocarbamate, 2- (2-bromopropionyloxy) styrene, 2 -(2-bromoisobutyryloxy) styrene, 1- (2-((4-vinylphenyl) methoxy) -1-phenylethoxy) -2,2,6,6-tetramethylpiperidine and the following formula Are included.

  In addition to the addition-polymerizable monomer (b), the addition is carried out as necessary to control the mold release performance, compatibility with the epoxy resin, leveling properties, the amount of crosslinkable functional groups in the copolymer, etc. An addition polymerizable monomer other than the polymerizable monomer (b) can also be used in combination.

As the addition polymerizable monomer (b) having no crosslinkable functional group, a (meth) acrylic acid compound having one addition polymerizable double bond and no crosslinkable functional group and one addition Examples thereof include a styrene compound having a polymerizable double bond and having no crosslinkable functional group. 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, isobutyl (meth) Acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; phenyl (meth) acrylate, toluyl (me ) 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 Alkoxyalkyl (meth) acrylates such as; ethylene oxide adducts of (meth) acrylic acid; and the like.

  Specific examples of the (meth) acrylic acid compound having one addition polymerizable double bond and no crosslinkable functional group include trifluoromethylmethyl (meth) acrylate, 2-trifluoromethyl. Ethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, Diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, and 2-perfluorohexadecylethyl (meth) a Fluoroalkyl (meth) acrylates such as relations include.

Further, examples of the (meth) acrylic acid compound having one addition polymerizable double bond and having no crosslinkable functional group include a (meth) acrylic acid compound 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 having no crosslinkable functional 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 having no crosslinkable functional group further include a styrene compound containing silsesquioxane. Specific examples of the styrene compound containing silsesquioxane 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-heptaisooctylpentacyclo [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 having a 4-vinylphenyl group (T ₈ type silsesquioxane), such as 1 ^7,13 ] octasiloxane; and 3- (3,5,7,9,11,13,15-heptaethyl Pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15) -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- hepta isooctyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7, 9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3.5 , , 9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3 - ((3 , 5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl) ethyl styrene, 3 - ((3,5,7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane -1 -Yloxy) dimethylsilyl) 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-heptacyclopentylpentacyclo [ 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-hepta phenylpent-cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane l-yloxy) such as dimethylsilyl) ethylstyrene, 4-vinylphenyl ethyl Octasiloxane (T ₈ type silsesquioxane);

  Further, as the addition polymerizable monomer (b) other than the addition polymerizable monomer, a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide. And a macromonomer having one polymerizable double bond.

Examples of the addition polymerizable monomer (b) include a compound 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.
Further examples include macromonomers having a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide, and having two polymerizable double bonds. The

Examples of the addition polymerizable monomer (b) 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.
Further examples include macromonomers having a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide, and having three or more polymerizable double bonds. Is done.

  The addition polymerizable monomer (b) is preferably a (meth) acrylic acid compound, more preferably a (meth) acrylic acid ester, and still more preferably a lower alkyl (for example, carbon number) of (meth) acrylic acid. 1-3) Esters and esters having a crosslinkable functional group.

  By obtaining at least a part of the addition polymerizable monomer (b) as an addition polymerizable monomer having a crosslinkable functional group, a polymer used in the present invention into which the crosslinkable functional group is introduced is obtained. Can do. The polymer used in the present invention into which a crosslinkable functional group has been introduced is preferably contained in a release layer together with a matrix resin, as will be described later.

<Organopolysiloxane (c)>
Organopolysiloxane typified by polydimethylsiloxane (hereinafter sometimes referred to as silicone or polysiloxane) has specific properties such as water repellency, releasability, slipperiness, low friction, heat resistance and oxygen permeability. Therefore, it has a wide range of uses such as the electronic materials field, cosmetics and medical fields.
For example, by using an organopolysiloxane having a polymerizable functional group as a copolymerization component or polycondensation component of another organic polymer, the weather resistance, surface water repellency, lubricity, biocompatibility that are the characteristics of organopolysiloxane And gas permeability can be easily imparted. For the modification of organic polymers, organopolysiloxanes having various organic functional groups are known. For example, an organopolysiloxane having a carboxyl group, that is, a one-terminal carboxylic acid-modified organopolysiloxane is a fiber treatment agent, an emulsifier, a surface modifier for inorganic materials, and various resins such as epoxy resins, polyesters, alkyd resins, and urethane resins. It is useful as a modifier. In addition, organopolysiloxanes having various functional groups can be synthesized by introducing various new functional groups utilizing the reactivity of the carboxyl group. For example, the carboxyl group can be an amide or ester. As described above, the one-terminal carboxylic acid-modified organopolysiloxane is used for preparing various modified silicones. Japanese Patent Application Laid-Open No. 10-001537 discloses a modification of a polyester of a carboxylic acid-modified polysiloxane having both terminals, and Japanese Patent Publication No. 07-068424 discloses a cold resistance of an acrylic rubber composition obtained using a carboxylic acid-modified silicone. As well as improving the above, it is shown that the release property and roll processability of rubber obtained from the acrylic rubber composition are improved. Japanese Patent Application Laid-Open No. 09-059125 discloses a water-repellent cosmetic powder obtained by treating a powder with a carboxyl group-modified organopolysiloxane. In Japanese Patent Application Laid-Open No. 08-109263, a polysiloxane having a polyvalent metal salt is used as the both-end / side-chain carboxylic acid-modified polysiloxane, and its application as a gelling agent or cosmetic is shown. Furthermore, Japanese Patent Application Laid-Open No. 05-139997 discloses a percutaneous absorption enhancer that promotes permeation and absorption of a drug through the skin using a one-terminal carboxylic acid-modified silicone.
The organopolysiloxane having an addition polymerizable functional group, which is a raw material monomer for the polymer used in the present invention, preferably has a molecular structure represented by the following formula (IV).

The organopolysiloxane (c) used in the present invention is an integer of ^{1 to} 1,000 in the above formula (IV); R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each , 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 And an arylalkyl composed of a substituted or unsubstituted aryl and an alkylene in which any hydrogen may be replaced by fluorine or any —CH ₂ — may be replaced by —O— or cycloalkylene And A ² is preferably an addition-polymerizable functional group.

Furthermore, in the organopolysiloxane (c) used in the present invention, R ¹ and R ² in the above formula (IV) are each independently hydrogen, phenyl, or carbon atoms having 1 to 8 carbon atoms, and arbitrary hydrogen is replaced with fluorine. Alkyl which may be
R ³ and R ⁴ 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 ⁵ 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.

Furthermore, in the organopolysiloxane (c) used in the present invention, R ¹ and R ² in the above formula (IV) are each independently methyl, phenyl or 3,3,3-trifluoropropyl;
R ³ and R ⁴ are each independently methyl or phenyl;
R ⁵ is preferably methyl, ethyl, propyl, butyl, isobutyl, or phenyl.

Further, in the organopolysiloxane (c) used in the present invention, in the above formula (IV), R ¹ , R ² , R ³ and R ⁴ are preferably methyl at the same time. In the formula (IV), A ² is preferably an addition polymerizable functional group, A ² is preferably a radical polymerizable functional group, and A ² preferably contains (meth) acryl or styryl. , A ² is preferably any one of the following formulas (V), (VI) or (VII).

[In the formula (V), Y ³ represents alkylene having 2 to 10 carbon atoms, R ⁶ is hydrogen, alkyl having 1 to 5 carbon atoms, or aryl having 6 to 10 carbon atoms, and the alkyl is linear In the formula (VI), R ⁷ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons, and the alkyl is a straight chain 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 (VII), Y ⁴ represents a single bond or alkylene having 1 to 10 carbon atoms. ]

In the present invention, in the above formula (V), Y ³ represents alkylene having 2 to 6 carbon atoms, R ⁶ represents hydrogen or alkyl having 1 to 3 carbon atoms, and in formula (VI), 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 alkyl having 1 to 3 carbon atoms, and Y ⁴ in formula (VII) Preferably represents a single bond or alkylene having 1 or 2 carbon atoms.

  Examples of organopolysiloxanes preferably used in the present invention include Silaplane FM0711 (manufactured by Chisso Corporation), Silaplane FM0721 (manufactured by Chisso Corporation), Silaplane FM0725 (manufactured by Chisso Corporation), Silaplane TM0701 (Chisso Corporation) Company), Silaplane TM0701T (manufactured by Chisso Corporation) and the like.

<Addition polymer>
The polymer used in the present invention is an addition polymer of silsesquioxane (a) or an addition copolymer with another addition polymerizable monomer (b), and when it is a copolymer, The copolymer may be a block copolymer or the like, or may be a random copolymer, but is preferably a random copolymer. For addition copolymers of silsesquioxane (a) and organopolysiloxane (c), or addition copolymers with other addition polymerizable monomers (b), block copolymer, etc. Although it may be a random copolymer, it is preferably a random copolymer. In addition, the polymer used in the present invention may have a crosslinked structure or a graft copolymer.

The polymer used in the present invention contains at least a structural unit derived from silsesquioxane (a) (hereinafter referred to as structural unit (a)) and a structural unit derived from addition polymerizable monomer (b) (hereinafter referred to as The structural unit (b)) is preferably included.
In the polymer used in the present invention, the molar ratio of the structural unit (a) to the structural unit (b) is arbitrary, and if (a) :( b) = 100: 0 to 0.001: 99.999. Good. As will be described later, when the release layer contains the polymer used in the present invention, it is preferable that (a) :( b) = 50: 50 to 0.001: 99.999. In order to exhibit sufficient surface modification ability, it is necessary to include the structural unit (a) to some extent, but in order to obtain solubility in a solvent, the content of the structural unit (a) is within the above range. It is preferable to do.
The polymer used in the present invention contains at least a structural unit derived from silsesquioxane (a) and a structural unit derived from organopolysiloxane (c) (hereinafter referred to as structural unit (c)), and is addition polymerizable. It preferably contains a structural unit derived from the monomer (b). In the polymer used in the present invention, the molar ratio of the structural unit (a), the structural unit (c), and the structural unit (b) is arbitrary, and (a) :( b) = 0.001: 99.999- 99.999: 0.001, (b) :( c) = 0.001: 99.999-99.999: 0.001, (a) :( c) = 0.1: 99.9-99. 9: 0.1 may be sufficient. As will be described later, when the copolymer used in the present invention is used in the release layer, (a) :( b) = 30: 70 to 60:40, (b) :( c) = It is preferable that it is 85: 15-99: 1, (a) :( c) = 80: 20-95: 5.

  Moreover, it is preferable that the fluorine atom content rate contained in the polymer used for this invention is 0.001 to 60 weight%.

  The weight average molecular weight of the polymer used in the present invention varies depending on the content of the structural unit (a) and the like, but is 1300 to 1 million as a guide. When the content of the structural unit (a) is high, the molecular weight tends to decrease. On the other hand, the molecular weight distribution (Mw / Mn) of the polymer used in the present invention is about 1.01 to 2.5 as a guide.

  The proportion of the structural unit derived from the addition polymerizable monomer having a crosslinkable functional group in the structural unit (b) contained in the polymer used in the present invention is not particularly limited, and the above-mentioned copolymer is applied. In order to achieve binding properties with the epoxy resin, which is a matrix resin to be blended when used as an agent, it only needs to contain a crosslinkable functional group to the extent that a favorable reactivity with the matrix resin monomer can be obtained. .

The polymer used in the present invention is obtained by subjecting fluorosilsesquioxane (a) and, if necessary, another addition polymerizable monomer (b) as monomer raw materials to addition polymerization. Can do.
What is necessary is just to determine suitably the molar ratio of the silsesquioxane (a) contained in a monomer raw material, and another addition polymerizable monomer (b) according to the target polymer. The proportion of the addition polymerizable monomer having a crosslinkable functional group contained in the other addition polymerizable monomer (b) may be appropriately selected according to the target polymer.
The polymer used in the present invention is a monomer raw material comprising fluorosilsesquioxane (a), organopolysiloxane (c), and, if necessary, another addition polymerizable monomer (b). As mentioned above, they can be obtained by addition polymerization. The molar ratio of the silsesquioxane (a), the organopolysiloxane (c) and the other addition polymerizable monomer (b) contained in the monomer raw material is appropriately determined according to the target polymer. That's fine. The ratio of the addition polymerizable monomer having a crosslinkable functional group or the addition polymerizable monomer having no crosslinkable functional group contained in the other addition polymerizable monomer (b) is also an object. What is necessary is just to select suitably according to a polymer. When a plurality of types of monomers are used as the addition polymerizable monomer (b) having a crosslinkable functional group, the ratio of each monomer is appropriately determined according to the characteristics of the target copolymer. That's fine. The proportion of the addition polymerizable monomer (b) having a crosslinkable functional group contained in the other addition polymerizable monomer (b) is also appropriately selected 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 photopolymerization.
Living radical polymerization is represented by atom transfer radical polymerization; reversible addition-fragmentation chain transfer; iodine transfer polymerization; iniferter polymerization, and can be performed using a polymerization initiator 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

Photopolymerization can be performed using the compound described in the cited document D as a photopolymerization initiator.・ Cited document D: Photopolymer social gathering, Photosensitive material list book, published on March 31, 1996 by Bunshin Publishing).
Specific examples of the photopolymerization initiator used are not particularly limited as long as they are compounds that generate radicals upon irradiation with ultraviolet rays or visible rays. Examples of the compound used as the photopolymerization initiator (D) include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- 4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 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-triazi 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'-teto Phenyl-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 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), mercaptans such as pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate, 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, tetrachloroethane, chlorobenzene, cyclohexane, t- butyl alcohol, benzene and the like. In particular, mercaptoacetic acid can lower the molecular weight of the polymer and make the molecular weight distribution uniform.
Chain transfer agents can be used alone or in admixture of two or more.

The specific production method of the polymer used in the present invention may be the same as the production method of the usual addition polymer, for example, solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method, bulk A suspension polymerization method or a polymerization method using supercritical CO ₂ can be used.
In the case of the solution polymerization method, dissolve fluorosilsesquioxane (a) and, if necessary, addition polymerizable monomer (b), a polymerization initiator, a chain transfer agent, etc. in an appropriate solvent. Then, the addition polymerization reaction may be performed by heating or irradiation with light. Alternatively, dissolve fluorosilsesquioxane (a), organopolysiloxane (c) and, if necessary, addition polymerizable monomer (b), polymerization initiator, chain transfer agent, etc. in an appropriate solvent. Then, the addition polymerization reaction may be performed by heating or irradiation with light.

Examples of the solvent used in the above polymerization reaction include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (salt chloride). Methylene, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, Propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethyl) Formamide, N, N-dimethylacetamide, etc.), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon solvents (abbreviations HFCs; HFCs having 2 or more carbon atoms can be used, and those having 2 to 6 carbon atoms can be used. HFCs can be preferably used.), Perfluorocarbon solvents (perfluoropentane, perfluorohexane, etc.), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane, etc.), oxygen-containing fluorine solvents (fluoroether, fluoro, etc.) Polyether, fluoroketone, fluoroalcohol, etc.), aromatic fluorine solvents (α, α, α-trifluorotoluene, hexafluorobenzene, etc.), water and the like. 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 10-80% by weight.
The reaction temperature is not particularly limited and may be 0 to 200 ° C. as a guide, and preferably room temperature to 150 ° C. The polymerization reaction can be performed under reduced pressure, normal pressure, or increased pressure depending on the type of monomer and the type of solvent.

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

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

<Preparation of release layer for surface protective film>
The polymer used in the present invention can be used for any other applications, but can be molded by various molding processes (press molding, extrusion molding, injection molding, compression molding, etc.) in combination with other resins as necessary. And the mold release layer of the surface protection film of this invention can be comprised.

The polymer used in the present invention can also be used as a release layer (so-called coating material) by combining other resins or resin monomers as necessary and dissolving or dispersing them in various solvents. . Use as a release layer
1) Forming a coating film by applying a solution or dispersion containing the polymer used in the present invention alone to a solid,
2) A solution or dispersion containing the polymer used in the present invention and another matrix resin is applied to a solid to form a coating film made of a composite resin with the matrix resin, and 3) the present invention The method includes applying a solution or dispersion containing a polymer to be used and a matrix resin monomer to a solid, and curing the matrix resin monomer to form a coating film made of a composite resin.

For example, a coating film can be formed on the substrate as a release layer by applying a solution (coating solution) containing the polymer used in the present invention to the substrate, drying, and curing as necessary. it can. The formed coating film has high water / oil repellency and low surface free energy.
This high water repellency and oil repellency and low surface free energy are considered to be manifested because the fluorine atoms on the fluorosilsesquioxane skeleton are unevenly distributed on the surface of the coating film to be formed.

Even in a release layer containing a polymer containing an organopolysiloxane, a coating film is formed as a release layer on the substrate in the same manner as described above by applying to a substrate, drying, and curing as necessary. be able to. The formed coating film has not only good releasability, but also water / oil repellency, antifouling property, non-adhesiveness, slipperiness, abrasion resistance, corrosion resistance, electrical insulation, antireflection property, flame resistance , Antistatic properties, chemical resistance, and weather resistance.
These characteristics are considered to be manifested because the organopolysiloxane present in the molecule of the same polymer is unevenly distributed on the surface of the coating film due to the excellent surface orientation of fluorosilsesquioxane.

  As described above, the polymer used in the present invention may be used alone as a release layer as in 1) above, but used as a release layer by mixing with other matrix resin as in 2) above. Alternatively, as in 3) above, the release layer may be formed by mixing with a monomer that forms a matrix resin (hereinafter also referred to as a matrix resin monomer).

As in 2) above, when the polymer used in the present invention is mixed with another matrix resin, the original properties (mechanical properties, surface / interface properties, compatibility, etc.) of the resin can be modified. it can.
Examples of matrix resins 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 product names), 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 Co., Ltd., Vectra: Polyplastics Co., Ltd.) ), Polyimide (Kapton: Toray Industries, Inc. trade name, AURUM: Mitsui Chemicals, Inc. trade name, etc.), polyetherimide, polyamideimide, phenol resin, alkyd resin, melamine resin, epoxy resin, urea resin, bismaleimide resin And silicone resin.
These resins may be used alone, or a plurality of resins may be used in combination.

Further, as in the above 3), the polymer used in the present invention may be used by mixing with a matrix resin monomer. In particular, when the polymer used in the present invention having a crosslinkable functional group and the matrix resin monomer are mixed and used, the resin obtained by curing and the polymer used in the present invention are cross-linked, and as a result In addition, a composite resin excellent in mechanical properties, surface / interface characteristics, and compatibility can be obtained.
Specifically, a solution containing a polymer having a crosslinkable functional group used in the present invention, a monomer for forming a matrix resin, and a curing reaction initiator (for example, an acid generator) as necessary is used as a substrate. The coating film (composite film) which consists of composite resin with a matrix resin can be formed on a board | substrate by apply | coating to and drying and hardening a coating film.
The formed composite film has high water / oil repellency and low surface free energy. This is presumably because fluorine atoms of fluorosilsesquioxane contained in the polymer used in the present invention are unevenly distributed on the surface layer of the composite film.

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

  Examples of the epoxy resin formed include bisphenol A, bisphenol F, hydroquinone, resorcin, dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) dicyclopentane, 4,4'-dihydroxybenzophenone. Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4 -Hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (3 , 5-Dimethyl-4-hydroxyphenyl) sulfone 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 4 , 4'-Dihydroxybiphenyl-3,3 ', 5,5'-tetramethylbiphenyl, bis (hydroxynaphthyl) methane, and 1,1'-binaphthol, 1,1'-bis (3-t-butyl- Epoxy resins made from 6-methyl-4-hydroxyphenyl) butane and the like are included.

Furthermore, examples of the epoxy resin to be formed include phenol novolac epoxy resins which are glycidyl etherified products of reaction products with phenols such as phenol, o-cresol and catechol, and aldehydes such as formaldehyde;
Polyglycidyl ether of polyphenols containing trityl skeleton obtained by condensation of phenols such as phenol, cresol, methyl-t-butylphenol and aromatic aldehydes such as hydroxybenzaldehyde;
A polyglycidyl ether of a polyphenol type novolak containing a trityl skeleton, which is a reaction product of a polyphenol containing a trityl skeleton and formaldehyde;
Polyglycidyl ethers of polyaralkylphenol resins which are reaction products of phenols such as phenol, o-cresol, catechol and the like with xylylene dichloride and (hydroxymethyl) benzene;
Fat that is a glycidyl ether of a reaction product of phenols such as phenol, o-cresol, catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene and unsaturated alicyclic hydrocarbons such as dicyclopentadiene and limonene Cyclic hydrocarbon-containing polyphenol resin type epoxy resin or polynaphthol resin type epoxy resin;
Polyglycidyl ethers of alicyclic hydrogen-containing polyphenol novolac resins or polynaphthol novolak resins which are reaction products of alicyclic hydrocarbon-containing polyphenol resins or polynaphthol resins and formaldehyde;
Glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds;
Phloroglysin, tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,3-bis [(4-hydroxyphenyl) methyl] benzene, 1,4-bis [(4-hydroxyphenyl) methyl] polyglycidyl ether of trivalent or higher phenols having benzene or the like as a basic skeleton;
Glycidyl ether compounds derived from cyclic phenols such as calixarene;
p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4 ' -Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis (methylamine), 1,3-cyclohexanebis Methylamine), N, amine-based epoxy resins derived from N- diglycidyl aniline;
glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid;
A hydantoin-based epoxy compound derived from 5,5-dimethylhydantoin or the like;
2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3, Alicyclic epoxy resins such as 4-epoxycyclohexanecarboxylate;
Examples include aliphatic epoxy resins obtained by oxidizing double bonds in unsaturated hydrocarbon compounds such as polybutadiene.

The formed epoxy resin may be an alicyclic epoxy resin. Specific examples thereof include a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, or a cyclohexane oxide or cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. The resulting epoxy resin.
For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Metadioxane, bis (3,4-epoxycyclohexylme Adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4- Epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, diepoxyhexahydrophthalic acid -2-ethylhexyl, 1,2: 8,9 diepoxy limonene (trade name: CEL3000, Daicel Chemical Co., Ltd.), epoxidized 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) Decorated ε-caprolactone (trade name: Epolide GT301, Daicel Chemical Co., Ltd.), epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone (trade name: Epolide GT401, Daicel Chemical Co., Ltd.), 2 1,2-Epoxy-4- (2-oxiranyl) cyclosoxane adduct of 2-bis (hydroxymethyl) -1-butanol (trade name: EHPE3150, Daicel Chemical Co., Ltd.), 2,2-bis (hydroxymethyl) ) -1-Butanol 1,2-epoxy-4- (2-oxiranyl) cyclosexane adduct and 3,4-epoxycyclohexanemethyl-3 ', 4'-epoxycyclohexanecarboxylate (trade name: EHPE3150CE) Daicel Chemical Co., Ltd.) 3,4-epoxycyclohexylmethyl acrylate ( Product name: Cyclomer A400, Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (Product name: Cyclomer M100, Daicel Chemical Co., Ltd.), Epoxidized polybutadiene (Product name: Epolide PB3600, Daicel Chemical Co., Ltd.) And epoxy resins represented by epoxidized thermoplastic elastomer (trade name: Epofriend, Daicel Chemical Co., Ltd.) and the like.

Further, examples of the epoxy resin include an epoxy resin obtained from a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof; an epoxy resin obtained from a polyglycidyl ester of an aliphatic long-chain polybasic acid; glycidyl acrylate or Homopolymers synthesized by vinyl polymerization of glycidyl methacrylate; glycidyl acrylate, or copolymers synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers are included.
Specific examples of the polyglycidyl ether include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, Examples thereof include glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol.
In addition, specific examples of the polyglycidyl ester include a polyether polyol polyglycidyl obtained by adding one or two or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, and glycerin. Ethers, diglycidyl esters of long aliphatic dibasic acids are included.

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

The matrix resin monomer to be combined with the polymer used in the present invention may be any monomer that forms the above-described epoxy resin, but may also be a compound shown below.
Oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane and 3,3-dichloromethyloxetane; trioxanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; 1,3-dioxolane and 1,3,6-trioxacyclo Cyclic ether compounds such as octane; cyclic lactone compounds such as β-propiolactone, γ-butyrolactone and ε-caprolactone; thiirane compounds such as ethylene sulfide; thietane compounds such as trimethylene sulfide and 3,3-dimethylthietane; tetrahydro Cyclic thioether compounds such as thiophene compounds; spiro ortho ester compounds obtained by reaction of epoxy compounds with lactones; spiro ortho carbonate compounds; cyclic carbonate compounds; ethylene glycol divinyl ether, alkyl Vinyl ether compounds such as vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether; ethylenic unsaturation such as styrene, vinylcyclohexene, isobutylene, polybutadiene Compound, amino group, hydroxyl, glycidyl, oxetanyl, polydimethylsiloxane having epoxycyclohexyl, polyalkylene oxide (polyethylene oxide, polypropylene oxide, block copolymer of polyethylene oxide and polypropylene oxide, etc.), fluorinated polyalkylene oxide (poly Fluoroethylene oxide, polyfluoropropylene oxide, etc.) may be used.

As described above, the polymer used in the present invention having a crosslinkable functional group may be used in combination with a monomer that forms a matrix resin (for example, an epoxy resin) and a curing reaction initiator (for example, an acid generator). it can.
There is no restriction | limiting in a hardening reaction initiator, What is necessary is just a compound which can discharge | release the substance which starts cationic polymerization by active energy ray irradiation or a thermal energy. Examples of the curing reaction initiator include a carboxylic acid, an amine, an acid anhydride compound, an acid generator, and the like, and preferably a double salt that is an onium salt that releases a Lewis acid or a compound thereof.

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

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

On the other hand, the anion [B] ^m− is preferably a halide complex, and is represented by the following formula, for example.
[LX _b ] ^m-
L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom. b is an integer of 3-7.
Further, when the valence of L in the anion [B] ^m− is p, m = b−p.
Specific examples of the anion [LX _b ] ^{m− represented by} the above general formula include tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), hexafluoroarsenate. (AsF ₆ ), hexachloroantimonate (SbCl ₆ ) and the like are included.

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

Examples of the anion [B] ^m- include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. Also included are ions, trinitrobenzenesulfonic acid anions, and the like.

Among such onium salts, the curing reaction initiator in the present invention is more preferably an aromatic onium salt exemplified by the following (A) to (C). Among these, one of them can be used alone, or two or more of them can be mixed and used.
(A) Phenyldiazonium hexafluorophosphate, aryldiazonium salts such as 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc. (b) Diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryl iodonium salts such as hexafluorophosphate and di (4-t-butylphenyl) iodonium hexafluorophosphate (c) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thio Phenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexa Fluorophosphate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4 ′ -Bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluorophosphate 4- [4 ′-(Benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium Triaryl sulfos such as hexafluorophosphate Ni salt

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

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

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

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

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

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

Furthermore, examples of the compound having a boiling point of 50 to 200 ° C. include glycol or a derivative thereof. Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, and the like.
Examples of glycol compounds include glycol monoethers such as ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; propylene glycol monomethyl ether acetate, propylene glycol mono Glycol monoacetates such as ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Le acetate; includes such diethylene glycol dimethyl ether, diethylene glycol diethyl ether, glycol dimethyl ether and diethylene glycol methyl ethyl ether.

Among these, preferable examples of the solvent of the coating solution include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and ethyl lactate are included. Further, in view of safety to human body, preferable examples of the solvent include propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, and ethyl lactate.
In addition, when the coating solution is applied to a substrate or the like with a slit coater (preferably used for coating on a large substrate), propylene glycol monomethyl ether acetate and It is preferable to use a mixed solvent of diethylene glycol methyl ethyl ether; a mixed solvent of methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether; a mixed solvent of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether.

  The method for applying the solution containing the polymer used in the present invention to the surface of the base material layer is not particularly limited, but spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, Examples include reverse coating, rod coating, bar coating, die coating, kiss coating, reverse kiss coating, air knife coating, and curtain coating. These substrate layers 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 method, vacuum deposition and the like are included. The applied solution can be dried in an environment of room temperature to 200 ° C.

  The coating solution is produced by mixing and dissolving the polymer used in the present invention and, if necessary, optional components in the solvent.

Although there is no restriction | limiting in particular in the content rate of the polymer used for this invention in the composite resin (solid content) obtained, It is preferable that it is 0.01 to 10 weight%. This is for appropriately controlling the fluorine content in the composite resin. The fluorine concentration in the composite resin is 0.05 to 10% by weight, preferably 0.1 to 5% by weight.
The coating film made of the composite resin has high water repellency and oil repellency, and low surface free energy.

Next, by coating, a fluorine-based polymer composition preferably used for producing a release layer constituting the surface protective film of the present invention, a surface modifier containing the fluorine-based polymer composition, and the surface modifier The mold release layer obtained will be described.
The surface modifier used in the present invention is a crosslinkability blended with fluorosilsesquioxane (a), organopolysiloxane (c), if necessary, with respect to the raw material composition forming the epoxy resin. It can be obtained by blending a coating solution containing 0.01 to 5% by weight of a copolymer with an addition polymerizable monomer (b) having a functional group as a fluorine atom.

  As an epoxy resin formed from the composition which forms the said epoxy-type resin, any of an aliphatic epoxy resin and an aromatic epoxy resin may be sufficient. The main monomers forming such an epoxy resin include bisphenol A, bisphenol F, hydroquinone, resorcin, dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) dicyclopentane, 4,4 ′. -Dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, Bis (3,5-dimethyl-4-hydroxyphenyl) Luphon, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane 4,4'-dihydroxybiphenyl-3,3 ', 5,5'-tetramethylbiphenyl, bis (hydroxynaphthyl) methane, and 1,1'-binaphthol, 1,1'-bis (3-t-butyl -6-methyl-4-hydroxyphenyl) butane and the like.

Furthermore, examples of the epoxy resin to be formed include phenol novolac epoxy resins which are glycidyl etherified products of reaction products with phenols such as phenol, о-cresol and catechol, and aldehydes such as formaldehyde;
Polyglycidyl ether of polyphenols containing trityl skeleton obtained by condensation of phenols such as phenol, cresol, methyl-t-butylphenol and aromatic aldehydes such as hydroxybenzaldehyde;
A polyglycidyl ether of a polyphenol type novolak containing a trityl skeleton, which is a reaction product of a polyphenol containing a trityl skeleton and formaldehyde;
Polyglycidyl ethers of polyaralkylphenol resins which are reaction products of phenols such as phenol, o-cresol, catechol and the like with xylylene dichloride and (hydroxymethyl) benzene;
Fat that is a glycidyl ether of a reaction product of phenols such as phenol, o-cresol, catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene and unsaturated alicyclic hydrocarbons such as dicyclopentadiene and limonene Cyclic hydrocarbon-containing polyphenol resin type epoxy resin or polynaphthol resin type epoxy resin;
Polyglycidyl ethers of alicyclic hydrogen-containing polyphenol novolac resins or polynaphthol novolak resins which are reaction products of alicyclic hydrocarbon-containing polyphenol resins or polynaphthol resins and formaldehyde;
Glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds;
Phloroglysin, tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,3-bis [(4-hydroxyphenyl) methyl] benzene, 1,4-bis [(4-hydroxyphenyl) methyl] polyglycidyl ether of trivalent or higher phenols having benzene or the like as a basic skeleton;
Glycidyl ether compounds derived from cyclic phenols such as calixarene;
p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4 ' -Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis (methylamine), 1,3-cyclohexanebis Methylamine), N, amine-based epoxy resins derived from N- diglycidyl aniline;
glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid;
A hydantoin-based epoxy compound derived from 5,5-dimethylhydantoin or the like;
2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3, Alicyclic epoxy resins such as 4-epoxycyclohexanecarboxylate;
Examples include aliphatic epoxy resins obtained by oxidizing double bonds in unsaturated hydrocarbon compounds such as polybutadiene.

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

For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy 1-methylcyclohexyl-3,4-epoxy 1-methylcyclohexanecarboxylate, 6 -Methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy 3-methylcyclohexylmethyl-3,4-epoxy 3-methylcyclohexanecarboxylate, 3,4 -Epoxy 5-methylcyclohexylmethyl-3,4-epoxy 5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3 , 4-Epoxycyclohexylmethyl Adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy6-methylcyclohexylmethyl) adipate, 3,4-epoxy6-methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), Dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate An epoxy resin obtained from the above.

  Furthermore, examples of the epoxy resin formed include epoxy resins obtained from polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof; epoxy resins obtained from polyglycidyl esters of aliphatic long-chain polybasic acids; glycidyl Homopolymers synthesized by vinyl polymerization of acrylate or glycidyl methacrylate; glycidyl acrylate or copolymers synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers are included.

  Specific examples of the polyglycidyl ether include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol. Examples include glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.

  In addition, specific examples of the polyglycidyl ester include a polyether polyol polyglycidyl obtained by adding one or two or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, and glycerin. Ethers, diglycidyl esters of long aliphatic dibasic acids are included.

  Further examples of the epoxy resin formed include epoxy resins obtained from monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, or polyether alcohols obtained by adding alkylene oxides to these. Epoxy resins obtained from glycidyl esters of higher fatty acids; epoxy resins obtained from epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene and the like.

  The mixing ratio of the epoxy resin to be formed and the copolymer is not particularly limited, but the use of an excessive copolymer is not preferable in terms of cost efficiency. Accordingly, it is preferable that the content of the copolymer in the coating film is blended so as to be 0.01 to 5% by weight as fluorine atoms, and further blended so as to be 0.01 to 3% by weight as fluorine atoms. Is practical.

  The fluoropolymer composition preferably used for preparing the coating film constituting the release layer of the surface protective film of the present invention, the surface modifier containing the fluoropolymer composition, the effect of the present invention Other additives such as pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents and / or anti-electromagnetic wave agents may be included within a range that does not adversely affect the above.

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

  The coating liquid preferably used for producing the coating film constituting the release layer of the surface protective film of the present invention is prepared by dissolving and / or dispersing the raw material composition and copolymer forming the epoxy resin in a solvent. Can be obtained. Although it does not restrict | limit especially as this solvent, It is preferable to contain the compound which has a boiling point of 50-200 degreeC 20weight% or more. The compound having a boiling point of 50 to 200 ° C. contained in the solvent may be one kind or a combination of two or more kinds.

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

Furthermore, examples of the compound having a boiling point of 50 to 200 ° C. include glycol or a derivative thereof. Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, and the like.
Examples of the glycol compounds include glycol monoethers such as ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Noether acetate; glycol dimethyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225, etc.), hydrofluorocarbon solvents (abbreviations HFCs; HFCs having 2 or more carbon atoms) And HFCs having 2 to 6 carbon atoms can be preferably used.), Perfluorocarbon solvents (perfluoropentane, perfluorohexane, etc.), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane, etc.), Oxygen-containing fluorinated solvents (fluoroethers, fluoropolyethers, fluoroketones, fluoroalcohols, etc.), aromatic fluorinated solvents ( , Alpha, alpha-trifluorotoluene, include hexafluorobenzene and the like) and the like.

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

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

  In addition to the raw material composition for forming an epoxy resin, a copolymer, a curing initiator, and a solvent, the coating liquid preferably used in the present invention is mixed with optional components as necessary and within a range not inhibiting the present invention.・ Can be dissolved. The concentration of the non-volatile component (solid content) of the coating liquid obtained as described above is not particularly limited, but is usually 1 to 50% by weight, and practically preferably about 5 to 20% by weight. .

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

  The coating amount of the coating solution is usually set so that the thickness of the coating film after firing is 0.1 to 20 μm. The practical thickness of the coating film after firing is about 0.3 to 3 μm.

  The baking conditions after application of the coating solution are set in consideration of the curing conditions of the epoxy resin and the heat resistance of the substrate, and the baking temperature is usually 50 to 200 ° C., practically 100 to 180 ° C. The The firing time is adjusted depending on the set thickness of the coating film after firing, the type of base material, the thickness of the base material, and the firing temperature, and is usually 15 to 120 seconds when a plastic film is used. For example, when a baking temperature is 160 ° C., and a polyethylene terephthalate film having a thickness of 1 μm and a substrate thickness of 75 μm is used as the substrate, a baking time of 45 to 60 seconds is sufficient.

  The release layer constituting the surface protective film of the present invention can be easily formed by forming the coating film on the surface opposite to the surface on which the adhesive layer of the base material layer of the present invention is formed. is there.

  The thickness of the release layer constituting the surface protective film of the present invention is not particularly limited, but is usually about 1 nm to 1500 μm.

  The release layer constituting the surface protective film of the present invention has good adhesion to the substrate layer due to the characteristics of the polymer or polymer composition, and the release layer surface is used for the adhesive layer. Since any of the possible adhesives exhibits good releasability, blocking phenomenon does not occur even when the surface protective film of the present invention is finished into a roll-shaped roll, and can be easily drawn out.

  The surface protective film of the present invention can be obtained by using the apparatus exemplified in Japanese Patent Application Laid-Open No. 15-41216 in which a coater is provided downstream of the T-die method co-pressing or single-layer extrusion apparatus. It can also be manufactured in one step without going through a body film.

<Example>
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.

[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 at room temperature overnight, 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 in a vacuum dryer at 80 ° C. for 3 hours to obtain 74 g of a colorless powdery solid.

The obtained solid (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 3 ° C. in an ice bath. Until cooled. Next, 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 ion-exchanged 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 measurements, and was found to be a compound (a-1) having a structure represented by the following formula.

<Example 1>
Preparation of Polymerizable Composition A heat-resistant glass ampoule was charged with compound (a-1) as fluorosilsesquioxane (a), methyl methacrylate as addition polymerizable monomer (b), and 2,2′- as a polymerization initiator. Azobisisobutyronitrile and α, α, α-trifluorotoluene as a solvent used in the polymerization reaction were introduced and cooled quickly using liquid nitrogen. Thereafter, freeze vacuum deaeration (pressure: 1.0 Pa) was performed three times in a vacuum apparatus equipped with an oil rotary pump, and the ampule was quickly sealed using a hand burner while maintaining the vacuum state.
The molar ratio of compound (a-1) and methyl methacrylate sealed in ampoule is (a-1): methacrylate = 10: 90; the amount of α, α, α-trifluorotoluene is compound (a-1) The amount of 2,2′-azobisisobutyronitrile was 0.005 mol% with respect to the total number of moles of compound (a-1) and methyl methacrylate. .

Polymerization The sealed heat-resistant glass ampoule was set in a constant temperature shaking bath at 60 ° C. and polymerized for 5 hours to obtain a viscous solution. After completion of the polymerization, n-heptane was added as a reprecipitation solvent to precipitate the polymer. The supernatant was removed and dried under reduced pressure (80 ° C., 3 hours) to obtain a polymer (A1). The weight average molecular weight of the polymer (A1) determined by GPC analysis was 182,800, and Mw / Mn was 1.68. Also the polymer (A1), the composition molar ratio of the monomer component as determined by ¹ H-NMR measurement, the compound (a-1): Methyl methacrylate = 6.9: was 93.1.

Preparation of Release Layer Coating Liquid The obtained polymer (A1) was dissolved in 2-butanone to obtain a coating liquid (C-1) having a polymer concentration of 5% by weight.

<Example 2>
Preparation and polymerization of polymerizable composition Compound as fluorosilsesquioxane (a) in a 200 mL four-necked flask equipped with a reflux condenser, thermometer, dropping funnel and septum cap with syringe for argon bubbling (A-1) (15.3 g), methyl methacrylate (13.6 g) as the addition polymerizable monomer (b), glycidyl methacrylate (1.1 g) as the matrix resin monomer, and a solvent used in the polymerization reaction α, α, α-trifluorotoluene (69.7 g) was added, and while sealing with argon, argon was blown from a syringe to perform deoxygenation.
After sufficient deoxygenation, 2,2′-azobisisobutyronitrile (0.2556 g) as a polymerization initiator and mercaptoacetic acid (0.0288 g) as a chain transfer agent were placed in an oil bath at 60 ° C. The polymerization was performed. After polymerization for 8 hours, the polymer composition was poured into 2 L of n-heptane to precipitate a polymer. The supernatant was removed and dried under reduced pressure (80 ° C., 3 hours) to obtain 26.2 g of a polymer (A2).
The weight average molecular weight of the polymer (A2) determined by GPC analysis was 91,900, and Mw / Mn was 1.62. Also the polymer (A2), the composition molar ratio of the monomer component as determined by ¹ H-NMR measurement, the compound (a-1): Methyl methacrylate: glycidyl methacrylate = 7.1: 88.0: 4.9 Met. Further, the fluorine concentration of the polymer (A2) determined by ¹ H-NMR measurement was 15.57% by weight.

Preparation of release layer coating liquid 0.24 g of polymer (A2) and EHPE3150CE (1,2-epoxy-4- (2-oxiranyl) cyclohexane addition of 2,2-bis (hydroxymethyl) -1-butanol Mixture of (3'4'-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate, epoxy equivalent: 151 g / mol, manufactured by Daicel Chemical Industries, Ltd.) 3.76 g of mixed solvent (2-butanone / cyclohexanone) / 2-propanol = weight ratio 50/30/20) was dissolved in 36.0 g. Furthermore, 0.03 g of a cationic polymerization initiator (epoxy group / cationic polymerization initiator = 398/1 (molar ratio), epoxy amount: 25.0 mmol) was added as a curing agent to obtain a coating liquid (C-2).

<Example 3>
Polyethylene terephthalate is used as the material for the base layer, and styrene elastomer (JSR Corporation: Dynalon) is used as the material for the adhesive layer. Then, a laminated film of polyethylene terephthalate / styrene elastomer was obtained.
Next, the coating liquid (C-1) obtained in Example 1 was coated with polyethylene terephthalate / polyethylene terephthalate of a polyethylene terephthalate / styrene elastomer using a coating rod (# 4, manufactured by RD Specialties). It was applied to the layer surface. When the coating rod (# 4) is used, the wet film thickness is 9 μm. The obtained coating film was cured and dried to obtain a release layer having a film thickness of about 0.45 μm to obtain the surface protective film of the present invention.

<Example 4>
In Example 3, the same operation as in Example 3 was performed except that the coating liquid (C-2) obtained in Example 2 was used instead of the coating liquid (C-1) obtained in Example 1. A surface protective film of the present invention was obtained.

<Example 5>
Polyethylene terephthalate was used as a material for the base material layer and melt-extruded by the T-die method to obtain a 100 μm single layer film. One side of the film is coated with an acrylic adhesive (acrylic polymer / epoxy crosslinking agent having an average molecular weight of 600,000) obtained by ordinary solution polymerization so that the thickness after drying is 20 μm, and then polyethylene terephthalate / acrylic A two-layer film of an adhesive was obtained.
Next, the coating liquid (C-1) obtained in Example 1 was coated with polyethylene terephthalate / polyethylene terephthalate of a polyethylene terephthalate / styrene elastomer using a coating rod (# 4, manufactured by RD Specialties). It was applied to the layer surface. When the coating rod (# 4) is used, the wet film thickness is 9 μm. The obtained coating film was cured and dried to obtain a release layer having a film thickness of about 0.45 μm to obtain the surface protective film of the present invention.

<Example 6>
In Example 5, the same operation as in Example 5 was performed except that the coating liquid (C-2) obtained in Example 2 was used instead of the coating liquid (C-1) obtained in Example 1. A surface protective film of the present invention was obtained.

<Example 7>
The surface protective film obtained in Example 3 was slit into a width of 500 mm using a slitter winder and wound up to obtain a roll-shaped article of the surface protective film. The obtained roll-shaped article was rewound using a rewinder at a speed of 400 m / min.

<Example 8>
The surface protective film obtained in Example 4 was slit into a width of 500 mm using a slitter winder and wound up to obtain a roll-shaped article of the surface protective film. The obtained roll-shaped article was rewound using a rewinder at a speed of 400 m / min.

<Example 9>
The surface protective film obtained in Example 5 was slit into a width of 500 mm using a slitter winder and wound up to obtain a roll-shaped article of the surface protective film. The obtained roll-shaped article was rewound using a rewinder at a speed of 400 m / min.

<Example 10>
The surface protective film obtained in Example 6 was slit into a width of 500 mm using a slitter winder and wound up to obtain a roll-shaped article of the surface protective film. The obtained roll-shaped article was rewound using a rewinder at a speed of 400 m / min.

<Comparative Example 1>
The laminated film of polyethylene terephthalate / styrene elastomer obtained in Example 3 was slit into a width of 500 mm using a slitter winder without coating, to obtain a roll-shaped article of a surface protective film. The obtained roll-shaped article was rewound at a speed of 400 m / min using a rewinder.

<Comparative example 2>
The two-layer film of polyethylene terephthalate / acrylic adhesive obtained in Example 5 was slit into a 500 mm width using a slitter winder without coating, to obtain a roll-shaped article of a surface protective film. The obtained roll-shaped article was rewound at a speed of 400 m / min using a rewinder.

  As described above, when the surface protective film was rolled back, the surface protective films of Examples 7 to 10 having the configuration of the present invention were able to be fed out satisfactorily.

Cross-sectional view of the surface protective film of the present invention

Explanation of symbols

1 Release layer 2 Base material layer 3 Adhesive layer

Claims (32)

A surface protective film having an adhesive layer, a base material layer, and a release layer, having an adhesive layer on one surface of the base material layer, and having a release layer on the opposite surface, The layer is a layer containing a thermoplastic resin, the adhesive layer is a layer containing an adhesive or a pressure-sensitive adhesive, and the release layer is
Addition polymers of fluorosilsesquioxane represented by the following formula (I) (a), or a fluorosilsesquioxane represented by the following formula (I) (a), the addition polymerizable monomer and (b) A surface protective film characterized by being a layer containing the above addition copolymer.

[In Formula (I),
R _f ^{1 to} R _f ⁷ are each independently
1 to 20 carbon fluoroalkyls in which any methylene may be replaced by oxygen;
C6-C20 fluoroaryl in which at least one hydrogen is replaced with fluorine or trifluoromethyl; or C7-C20 fluoro in which at least one hydrogen in aryl is replaced with fluorine or trifluoromethyl Represents arylalkyl,
A ¹ represents an addition polymerizable functional group. ] R _f ^{1 to} R _f ⁷ in the formula (I) 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 , alpha-characterized in that it presents a trifluoromethylphenyl, surface protective film of claim 1, wherein. R _f ^{1 to} R _f ⁷ in the formula (I) are each independently 3,3,3-trifluoropropyl, or 3,3,4,4,5,5,6,6,6-nonafluoro. The surface protective film according to claim 2 , which shows hexyl. Surface protective film according to any one of claims 1 to 3, A ¹ in Formula (I) is characterized in that it presents a radically polymerizable functional group. Formula A ¹ is in (I), (meth) surface protective film according to any one of claims 1 to 4, characterized in that it comprises an acrylic or styryl. The surface protective film according to claim 5, wherein A ¹ in the formula (I) is represented by the following formula (II) or (III).

[In Formula (II), Y ¹ represents alkylene having 2 to 10 carbon atoms, X represents hydrogen or alkyl having 1 to 3 carbon atoms,
In the formula (III), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms. ] In the formula (II), Y ¹ represents alkylene having 2 to 6 carbon atoms, X represents hydrogen or alkyl having 1 to 3 carbon atoms, and in formula (III), Y ² represents a single bond or 1 to 1 carbon atoms. surface protective film according to claim 6, wherein indicating the 6 alkylene. The surface protective film according to claim 6, wherein in the formula (II), Y ¹ represents propylene, X represents hydrogen or methyl, and in the formula (III), Y ² represents a single bond or ethylene. The surface protective film according to any one of claims 1 to 8 , wherein the addition polymerizable monomer (b) is a (meth) acrylic acid compound or a styrene compound. The surface protective film according to any one of claims 1 to 9 , wherein at least a part of the addition polymerizable monomer (b) is an addition polymerizable monomer having a crosslinkable functional group. The surface protection film as described in any one of Claims 1-10 which contains an epoxy resin monomer in the mold release layer of the said surface protection film. A surface protective film having an adhesive layer, a base material layer, and a release layer, having an adhesive layer on one surface of the base material layer, and having a release layer on the opposite surface, The layer is a layer containing a thermoplastic resin, the adhesive layer is a layer containing an adhesive or a pressure-sensitive adhesive, and the release layer is
Addition copolymer of fluorosilsesquioxane (a) having one addition polymerizable functional group and organopolysiloxane (c) having addition polymerizable functional group, or having one addition polymerizable functional group A layer containing an addition copolymer of fluorosilsesquioxane (a), an organopolysiloxane (c) having an addition polymerizable functional group, and an addition polymerizable monomer (b) Surface protection film. The surface protective film according to claim 12 , wherein the fluorosilsesquioxane (a) is represented by the following formula (I).

[In Formula (I),
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;
C6-C20 fluoroaryl in which at least one hydrogen is replaced with fluorine or trifluoromethyl; or C7-C20 fluoro in which at least one hydrogen in aryl is replaced with fluorine or trifluoromethyl an aryl alkyl, a ¹ represents an addition polymerizable functional group. ] R _f ^{1 to} R _f ⁷ in formula (I) 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, The surface protective film according to claim 13, which represents α-trifluoromethylphenyl. R _f ^{1 to} R _f ⁷ in formula (I) are each independently 3,3,3-trifluoropropyl, or 3,3,4,4,5,5,6,6,6-nonafluorohexyl. The surface protective film according to claim 14, wherein The surface protective film according to any one of claims 12 to 15 , wherein the organopolysiloxane (c) is represented by the following formula (IV).

[In the formula (IV), n is an integer of ^{1 to} 1,000; R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each hydrogen, 1 to 30 carbon atoms, 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 A group independently selected from arylalkyl composed of alkylene in which hydrogen may be replaced by fluorine or any —CH ₂ — may be replaced by —O— or cycloalkylene; A ² is an addition polymerizable functional group. ] R ¹ and R ² in formula (IV) are each independently hydrogen, phenyl or alkyl having 1 to 8 carbon atoms, and any hydrogen may be replaced by fluorine; R ³ and R ⁴ are independently Alkyl having 1 to 20 carbon atoms and optionally replacing hydrogen with fluorine, aryl having 6 to 20 carbon atoms and optionally replacing hydrogen with fluorine, or 7 to 7 carbon atoms 20 is an arylalkyl in which any hydrogen may be replaced with fluorine; R ⁵ is an alkyl having 1 to 20 carbon atoms and any hydrogen may be replaced with fluorine; 6 to 20 carbon atoms by and surface protection of any hydrogen according to claim 16, wherein aryl may be replaced by fluorine or carbon atoms, an aryl alkyl optionally replaced by arbitrary hydrogen fluorine is 7 to 20 Irumu. R ¹ and R ² in formula (IV) are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ³ and R ⁴ are each independently methyl or phenyl; R 18. The surface protective film according to claim 17 , wherein ⁵ is methyl, ethyl, propyl, butyl, isobutyl, or phenyl. The surface protective film according to claim 18 , wherein R ¹ , R ² , R ³ and R ⁴ are each simultaneously methyl. The surface protective film according to any one of claims 13 to 19 , wherein A ¹ in the formula (I) and A ² in the formula (IV) are addition polymerizable functional groups. The surface protective film according to claim 20, wherein A ¹ in the formula (I) and A ² in the formula (IV) are radically polymerizable functional groups. The surface protective film according to claim 21, wherein A ¹ in formula (I) and A ² in formula (IV) contain (meth) acryl or styryl. A ¹ in formula (I) is any of the following formulas (V) or (VII):
The surface protective film according to claim 22 , wherein A ² in the formula (IV) is any of the following formulas (V), (VI), or (VII).

[In the formula (V), Y ³ represents alkylene having 2 to 10 carbon atoms, R ⁶ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbon atoms; , 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, 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 (VII), Y ⁴ is a single bond or a carbon number of 1 to 10 Represents alkylene. ] In formula (V), Y ³ represents alkylene having 2 to 6 carbon atoms, R ⁶ represents hydrogen or alkyl having 1 to 3 carbon atoms, and in formula (VI), X ₁ represents —CH ₂ CH ₂ CH _2. - indicates, Y is -OCH ₂ CH ₂ - indicates, p is 0 or 1, R ⁷ represents alkyl of 1-3 carbon hydrogen or carbon, in formula (VII) Y ⁴ is a single bond or a carbon The surface protective film according to claim 23 , which represents an alkylene of formula 1 or 2. 25. The any one of claims 12 to 24 , wherein the addition polymerizable monomer (b) is at least one selected from an addition polymerizable monomer having a crosslinkable functional group and a monomer having no crosslinkable functional group. The surface protection film according to claim 1. The surface protective film according to any one of claims 12 to 24 , wherein the addition polymerizable monomer (b) is an addition polymerizable monomer having a crosslinkable functional group. The addition polymerizable monomer having a crosslinkable functional group has a radical polymerizable functional group, and one or more hydroxyl, glycidyl, oxetanyl, epoxycyclohexyl, alkyl halide, blocked isocyanate in the same molecule, 27. The surface protective film according to claim 26 , which is a compound having isocyanato, amino or carboxyl. The radical polymerizable functional group in the addition polymerizable monomer having a crosslinkable functional group is (meth)
The surface protective film according to claim 27, which is acrylic or styryl. The surface protection film according to any one of claims 12 to 28 , wherein the release layer contains a thermoplastic resin and / or a thermosetting resin. The surface protection film according to any one of claims 12 to 28 , wherein the release layer contains a thermosetting resin. The surface protection film according to claim 30 , wherein the thermosetting resin is a compound having hydroxyl, glycidyl, oxetanyl, epoxycyclohexyl, alkyl halide, blocked isocyanato, isocyanato, amino or carboxyl. 32. The surface protective film according to claim 31 , wherein the thermosetting resin is a compound having glycidyl, oxetanyl, or epoxycyclohexyl.

Images