JP2009034846A - Transfer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer film which can easily impart characteristics such as water-repellent and oil-repellent properties to an object to be transferred by a transfer method and is transferable also to an object having a fine complex shape. <P>SOLUTION: In the transfer film, a transfer layer comprising a resin composition containing fluorocyl sesquioxane (a) or a fluorocarbon polymer (b) having a constitutional unit derived from fluorocyl sesquioxane (a) is formed on the surface of a substrate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) or fluorosilsesquioxane (a) on the substrate surface, and, if necessary, a matrix resin (c) The present invention relates to a transfer film formed with a transfer layer containing a resin composition containing, a method for producing the transfer film, a laminate formed with a transfer layer on the transfer film, and uses of the laminate.

  Until now, various photosensitive resin compositions have been used as a material for a patterned film used for a liquid crystal display element, an EL display element or the like (for example, see Patent Document 1). The patterned film is formed by applying a photosensitive resin composition to a substrate, irradiating the coating film with light according to the pattern, and washing and removing the uncured film without being irradiated with light. Can do. As described above, many resist compositions for forming a patterned film have been proposed (see, for example, Patent Document 2).

  On the other hand, the resist composition may be used as a material for forming a permanent film such as a color filter partition wall, an ITO electrode partition wall of a liquid crystal display element, an organic EL display element partition wall, a circuit board partition wall, etc. Attention has been paid.

  For example, in the manufacture of color filters, a so-called ink jet method has been proposed that uses an ink jet recording method in which R (red), G (green), and B (blue) inks are spray-coated into minute pixels. Here, the pixel pattern is formed by photolithography using a resist composition, and a coating film of the resist composition is used as a partition between pixels. In the ink jet method, it is necessary to prevent the occurrence of ink color mixing between adjacent pixel regions and the phenomenon of ink sticking to portions other than a predetermined region. Therefore, the partition wall needs to have a property of repelling water or an organic solvent which is an inkjet coating liquid, so-called water and oil repellency.

  Disclosed is a negative resist containing a fluororesin having a perfluoroalkyl group, an alkali-soluble resin having a carboxyl group and a phenol hydroxyl group, and an acid crosslinking agent capable of crosslinking with the carboxyl group / phenol hydroxyl group as imparting water and oil repellency to the partition wall By applying, exposing, developing and baking this negative resist on the substrate, the fluororesin having a perfluoroalkyl group accumulates in the vicinity of the partition wall surface and exhibits water and oil repellency (for example, patents) Reference 3).

  However, since the partition formed by the negative resist exhibits a water / oil repellency function on the entire surface of the partition, the side of the partition also has a low surface tension, and when ink is injected by an ink jet method, The wettability is lowered and it becomes difficult to inject ink between the partition walls.

  In addition, as a method for imparting water and oil repellency to the surface of the partition wall, imparting characteristics to a transfer medium by a transfer method is used. For example, a layer made of a fluororesin such as polytetrafluoroethylene, polychlorotrifluoroethylene, or polyvinyl fluoride is formed on an easily peelable sheet, and the fluororesin layer is easily transferred to a transfer target by a transfer method. In addition, water and oil repellency can be imparted to the transfer target (see, for example, Patent Document 4).

However, for example, in the case of forming a fluororesin layer on the upper surface of the partition formed from the negative resist composition, the sheet on which the fluororesin layer is formed is transferred after being cut into the same shape as the partition, or Then, it is necessary to perform cutting after bonding the sheet on which the fluororesin layer is formed to the partition wall. As described above, when the fluororesin layer is transferred to a transfer target having a fine and complicated shape, the operation is very difficult.

  Also, in recent years, as a technology capable of dealing with environmental problems by eliminating the coating process that uses a large amount of solvent due to environmental problems, a coating material is applied to a resin molded product in a molding die when molding resin for synthetic resin parts. In-mold coating methods (hereinafter, in-mold molding) have been proposed (see, for example, Patent Document 5). However, it is not known to impart properties such as water and oil repellency to the surface of the resin molded body.

JP 2004-287232 A JP 2001-261761 A JP 2005-315984 A JP-A-5-213000 JP-A-8-332655

  An object of the present invention is to provide a transfer film that can easily impart properties such as water and oil repellency to a transferred object by a transfer method, and for a transferred object having a fine and complicated shape. Another object is to provide a transfer film that can be transferred.

The inventors of the present invention have made extensive studies to solve the above problems. As a result, fluorosilsesquioxane (a) or a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) on the substrate surface, and, if necessary, matrix resin (c) It has been found that the above-mentioned problems can be solved by forming a transfer film formed with a transfer layer containing a resin composition containing.
Further, the inventors of the present invention relate to a laminate in which a transfer layer comprising a curable resin composition and / or a thermoplastic resin composition is formed on the transfer film, and the use of the laminate. Fluorosilsesquioxane (a) or a fluorine-based unit having a structural unit derived from fluorosilsesquioxane (a) by, for example, peeling off a transfer film after forming or bonding a transfer layer on the transfer layer A resin composition containing the polymer (b) and, if necessary, the matrix resin (c) is transferred to the surface of the transferred layer, and the transferred layer has water / oil repellency, non-adhesive properties, releasability, and slipperiness. And the like.

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であり、Ａ¹は、水素、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、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、反応性官能基または重合性官能基である。
＜５＞
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であり、Ａ¹は、水素、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、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、シアノ、ヒドロキシル、アルコキシ、（メタ）アクリロイルオキシ、スチリル、（メタ）アクリル、イソシアナト、メルカプト、環状エーテルを含む一価の官能基、ハロゲン化アルキル、アミノおよびカルボキシルから選ばれることを特徴とする＜１＞〜＜４＞のいずれかに記載の転写フィルム。＜６＞
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であり、Ａ¹は、アクリロイルオキシ、メタクリロイルオキシ、スチリル、および（メタ）アクリルから選ばれることを特徴とする＜１＞〜＜５＞のいずれかに記載の転写フィルム。
＜７＞
フッ素系重合体（ｂ）が、付加重合性単量体（ｄ）に由来する構成単位をさらに有することを特徴とする＜１＞〜＜６＞のいずれかに記載の転写フィルム。
＜８＞
前記付加重合性単量体（ｄ）が、架橋性官能基を有する付加重合性単量体および架橋性官能基を有さない付加重合性単量体から選ばれる少なくとも１種の付加重合性単量体であることを特徴とする＜７＞に記載の転写フィルム。
＜９＞
前記架橋性官能基が、シアノ、ヒドロキシル、アルコキシ、アクリロイルオキシ、メタクリロイルオキシ、スチリル、イソシアナト、メルカプト、ビニルエーテル、環状エーテルを含む一価の官能基、ハロゲン化アルキル、アミノおよびカルボキシルから選ばれる架橋性官能基であることを特徴とする＜８＞に記載の転写フィルム。
＜１０＞
マトリックス樹脂（ｃ）が、硬化性樹脂および／または熱可塑性樹脂であることを特徴とする＜３＞〜＜９＞のいずれかに記載の転写フィルム。
＜１１＞
硬化性樹脂が、熱硬化性樹脂または光硬化性樹脂であることを特徴とする＜１０＞に記載の転写フィルム。
＜１２＞
粘着剤からなる粘着層を転写層と反対側の基材の面にさらに形成してなる、＜１＞〜＜１１＞のいずれか一項に記載の転写フィルム。
＜１３＞
基材表面に、フルオロシルセスキオキサン（ａ）またはフルオロシルセスキオキサン（ａ）に由来する構成単位を有するフッ素系重合体（ｂ）を含む樹脂組成物の層を形成する工程を含む転写フィルムの製造方法。
＜１４＞
＜１＞〜＜１１＞のいずれかに記載の転写フィルム上に硬化性樹脂組成物および／または熱可塑性樹脂組成物よりなる被転写層を形成してなる積層体。 That is, the present invention relates to a transfer film shown below, and a laminate obtained by forming a transfer layer comprising a thermoplastic resin composition and / or a curable resin composition on the transfer film. <1>
A transfer layer containing a fluorosilsesquioxane (a) or a resin composition containing a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) is formed on the substrate surface. Transfer film.
<2>
The transfer film according to <1>, wherein a transfer layer including a resin composition containing a fluorine-based polymer (b) having a structural unit derived from fluorosilsesquioxane (a) is formed on the surface of the substrate.
<3>
The transfer film according to <1> or <2>, wherein the resin composition further contains a matrix resin (c).
<4>
The transfer film according to any one of <1> to <3>, 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; at least one hydrogen is fluorine or trifluoro A fluoroaryl having 6 to 20 carbon atoms replaced by methyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and A ¹ is Hydrogen, alkyl having 1 to 20 carbon atoms, and arbitrary hydrogen may be replaced with fluorine, aryl having 6 to 20 carbon atoms, and arbitrary hydrogen being replaced with fluorine, carbon number 7 -20, arylalkyl, reactive functional group or polymerizable functional group where any hydrogen may be replaced by fluorine.
<5>
R _f ¹ ~R _f ⁷ in the formula (I) are each independently, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluoro-butyl, 3,3,4,4 , 5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro- 1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α , α-trifluoromethylphenyl, A ¹ is hydrogen, alkyl having 1 to 20 carbon atoms, alkyl in which arbitrary hydrogen may be replaced with fluorine, carbon atoms having 6 to 20 carbon atoms, and any hydrogen May be replaced by fluorine Reel, arylalkyl having 7 to 20 carbon atoms, and arbitrary hydrogen may be replaced by fluorine, cyano, hydroxyl, alkoxy, (meth) acryloyloxy, styryl, (meth) acryl, isocyanato, mercapto, cyclic ether The transfer film according to any one of <1> to <4>, wherein the transfer film is selected from a monovalent functional group containing, alkyl halide, amino and carboxyl. <6>
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. And A ¹ is selected from acryloyloxy, methacryloyloxy, styryl, and (meth) acrylic, The transfer film according to any one of <1> to <5>.
<7>
The transfer film according to any one of <1> to <6>, wherein the fluorine-based polymer (b) further has a structural unit derived from the addition polymerizable monomer (d).
<8>
The addition polymerizable monomer (d) is at least one addition polymerizable monomer selected from an addition polymerizable monomer having a crosslinkable functional group and an addition polymerizable monomer having no crosslinkable functional group. <7> The transfer film according to <7>, which is a polymer.
<9>
The crosslinkable functional group is selected from a monovalent functional group including cyano, hydroxyl, alkoxy, acryloyloxy, methacryloyloxy, styryl, isocyanato, mercapto, vinyl ether, cyclic ether, alkyl halide, amino and carboxyl. <8> The transfer film according to <8>, which is a base.
<10>
The transfer film according to any one of <3> to <9>, wherein the matrix resin (c) is a curable resin and / or a thermoplastic resin.
<11>
<10> The transfer film according to <10>, wherein the curable resin is a thermosetting resin or a photocurable resin.
<12>
The transfer film according to any one of <1> to <11>, wherein an adhesive layer made of an adhesive is further formed on the surface of the substrate opposite to the transfer layer.
<13>
Transfer including the step of forming a layer of a resin composition containing fluorosilsesquioxane (a) or a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) on the surface of the substrate A method for producing a film.
<14>
<1>-<11> The laminated body formed by forming the to-be-transferred layer which consists of a curable resin composition and / or a thermoplastic resin composition on the transfer film in any one of.

  Fluoropolymer containing fluorosilsesquioxane (a) or fluorosilsesquioxane (a) by, for example, peeling off the transfer film after forming or bonding the transfer object on the transfer film of the present invention If necessary, the resin composition containing the matrix resin (c) can be transferred to the surface of the transferred material and impart properties such as water / oil repellency, non-adhesive properties, releasability, and slipperiness.

  Specifically, for example, a laminate obtained by applying a photosensitive resin composition (photosensitive layer) on a transfer film obtained by the present invention and bonding a protective film is first peeled off the protective film. Then, pressure bonding (lamination) is performed so as to directly touch a base material made of a metal plate or the like, while a patterned negative film is closely adhered to the transfer film. Subsequently, after irradiating and exposing to actinic rays such as ultraviolet rays, the transfer film is peeled off. By spraying the developer on this to remove unnecessary unexposed portions, water / oil repellency and the like can be imparted only to the upper surface of the fine partition formed by the negative resist.

  For example, in the transfer film of the present invention, a transfer film in which an adhesive layer is formed by applying an adhesive to the surface of the substrate opposite to the transfer layer is bonded to a mold part of an injection molding machine. The molded product released from the mold after injecting the thermosetting resin is imparted with characteristics such as water and oil repellency to the surface of the molded product due to the components transferred from the transfer film.

  The transfer film of the present invention can easily have properties such as water and oil repellency on the surface of the transferred body (layer) by pressure bonding with the transferred body (layer) and molding of the transferred body (layer) on the transfer film. And a transfer film that can be transferred to a transfer target (layer) having a fine and complicated shape.

The present invention provides a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) or fluorosilsesquioxane (a) on the substrate surface, and, if necessary, a matrix resin (c) The present invention relates to a transfer film formed by forming a transfer layer containing a resin composition containing, and a laminate obtained by forming a transfer layer comprising a curable resin composition and / or a thermoplastic resin composition on the transfer film.

<Fluorosilsesquioxane (a)>
Fluorosilsesquioxane (a) (hereinafter also referred to as “silsesquioxane (a)”) 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 this 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 has a cage structure of T ₈ type [(R—SiO _1.5 ) ₈ ].

When the above fluorosilsesquioxane (a) is used alone in the production of the transfer film of the present invention, it preferably has one non-crosslinkable functional group or one reactive functional group. That is, it is preferable that one of R in silsesquioxane [(R—SiO _1.5 ) ₈ ] has a non-crosslinkable functional group or one reactive functional group.

  Examples of the non-crosslinkable functional group are hydrogen, alkyl having 1 to 20 carbon atoms and arbitrary hydrogen may be replaced with fluorine, and having 6 to 20 carbon atoms and arbitrary hydrogen being replaced with fluorine. Or a group selected from arylalkyl which has 7 to 20 carbon atoms and in which any hydrogen may be replaced by fluorine.

  Examples of said reactive functional groups are selected from monovalent functional groups including cyano, hydroxyl, alkoxy, (meth) acryloyloxy, styryl, isocyanato, mercapto, cyclic ethers, alkyl halides, amino and carboxyl It is a group.

When the fluoropolymer (b) having a structural unit derived from the fluorosilsesquioxane (a) is used in producing the transfer film of the present invention, one polymerization is performed in the fluorosilsesquioxane (a). It preferably has a functional functional group. That is, it is preferable that one of R of silsesquioxane [(R—SiO _1.5 ) ₈ ] is a polymerizable functional group. The polymerizable functional group is more preferably a radical polymerizable functional group.

  The radical polymerizable functional group is not particularly limited as long as it is a radical polymerizable group. For example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N -Vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide 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 containing the (meth) acryl include a group represented by the following formula (I). In formula (I), Y ¹ is alkylene having 2 to 10 carbons, preferably alkylene having 2 to 6 carbons, more preferably alkylene (propylene) having 3 carbons. X is hydrogen or alkyl having 1 to 3 carbon atoms, preferably hydrogen or methyl.

Examples of the radical polymerizable functional group containing styryl include a group represented by the following formula (II). In formula (II), Y ² is 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, preferably bonded to carbon in the para position with respect to Y ² .

The fluorosilsesquioxane (a) is characterized by having at least one fluoroalkyl, fluoroarylalkyl, or fluoroaryl. That is, one or more of R of silsesquioxane (R—SiO _1.5 ) _n , preferably R other than non-crosslinkable functional group, reactive functional group or polymerizable functional group is all fluoroalkyl, fluoroarylalkyl and / or Or fluoroaryl.

The fluoroalkyl may be either linear or branched. This fluoroalkyl has 1 to 20 carbon atoms, preferably 3 to 14 carbon atoms. Furthermore, any methylene of the fluoroalkyl may be replaced with oxygen. Here, methylene includes —CH ₂ —, —CFH— or —CF ₂ —. That is, “any methylene may be replaced with oxygen” means that —CH ₂ —, —CFH—, or —CF ₂ — may be replaced with —O—. However, in fluoroalkyl, two oxygens are not bonded (—O—O—). That is, the fluoroalkyl may have an ether bond. Also, in the preferred fluoroalkyl, the methylene adjacent to Si is not replaced with oxygen, and the terminal opposite to Si is CF ₃ . Furthermore, it is preferable that —CF ₂ — be replaced with oxygen rather than —CH ₂ — or —CFH— to be replaced with oxygen. Preferred 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 aforementioned fluoroalkyl, fluoroarylalkyl, or fluoroaryl contained in fluorosilsesquioxane (a), a preferred group is fluoroalkyl,
Perfluoroalkylethyl is more preferable, and 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl is more preferable.

As described above, the fluorosilsesquioxane (a) preferably has a T ₈ type structure, has one non-crosslinkable functional group, a reactive functional group or a polymerizable functional group, and one or It has two or more fluoroalkyl, fluoroarylalkyl and / or fluoroaryl, and is represented by the following structural formula (I).

In the above formula (I), A ¹ is the above-mentioned non-crosslinkable functional group, reactive functional group or polymerizable functional group, and R _f ^{1 to} R _f ⁷ are each independently the above-described fluoroalkyl, fluoro Arylalkyl or fluoroaryl. R _f ^{1 to} R _f ⁷ may be different groups or all may be the same group.
R _f ^{1 to} R _f ⁷ in formula (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, α-trifluoromethylphenyl is preferred, and R _f ^{1 to} R _f ⁷ are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6. , 6-Nonafluorohexyl or trideca More preferably Ruoro 1,1,2,2-tetrahydrooctyl.

  When the fluorosilsesquioxane (a) is not used alone in the production of the transfer film of the present invention, a fluoropolymer (b) having a structural unit derived from the fluorosilsesquioxane (a) is used. Preferably, the fluoropolymer (b) may contain a structural unit derived from the addition polymerizable monomer (d) as necessary.

  When the fluoropolymer (b) contains a structural unit derived from the addition polymerizable monomer (d), the addition polymerizable monomer (d) is an addition having a crosslinkable functional group. It is preferably at least one addition polymerizable monomer selected from a polymerizable monomer and a monomer having no crosslinkable functional group.

<Addition polymerizable monomer (d)>
The addition polymerizable monomer (d) used in the present invention may have a crosslinkable functional group or may not have a crosslinkable functional group.

(Addition polymerizable monomer having a crosslinkable functional group (d))
Examples of the addition-polymerizable monomer (d) having a crosslinkable functional group include monovalent functional groups including cyclic ethers such as epoxy and oxetanyl such as glycidyl and epoxycyclohexyl, isocyanate, acid anhydride, carboxyl, and amine , Alkyl halide, thiol, siloxy, acryloyl, methacryloyl, hydroxyl and the like.

  As the addition polymerizable monomer (d), a compound in which the crosslinkable functional group is introduced into the addition polymerizable monomer can be used. About the specific example of the said addition polymerizable monomer (d), the compound which comprises the part remove | excluding the said crosslinkable functional group from the said addition polymerizable monomer (d) (addition polymerizable monomer in this invention) Examples thereof include compounds having one or more addition-polymerizable double bonds, such as vinyl compounds, vinylidene compounds, and vinylene compounds, and more specifically, (meth) acrylic acid derivatives and styrene derivatives. Is mentioned.

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

  Specific examples of the addition polymerizable monomer (d) include the aforementioned derivatives having the aforementioned crosslinkable functional group. For example, the addition polymerizable monomer (d), which is a (meth) acrylic acid derivative having a monovalent functional group containing a cyclic ether as a crosslinkable functional group, contains an epoxy-containing (meth) such as glycidyl (meth) acrylate. Acrylate; alicyclic epoxy-containing (meth) acrylate such as 3,4-epoxycyclohexylmethyl (meth) acrylate; oxetanyl-containing (meth) acrylate such as 3-ethyl-3- (meth) acryloyloxymethyloxetane; 4- ( And dioxolane-containing (meth) acrylates such as (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane;

Specific examples of the addition polymerizable monomer (d) include an addition polymerizable monomer (d) which is a (meth) acrylic acid derivative containing active hydrogen in the molecule as a crosslinkable functional group. Active hydrogen is hydrogen bonded to an atom (for example, nitrogen, sulfur, oxygen) having an electronegativity value equal to or higher than carbon among hydrogen existing in the molecule of the organic compound. Examples of the group having active hydrogen include —OH, —SH, —COOH, —NH, —NH ₂ , —CONH ₂ , —NHCONH—, —NHCOO—, Na ⁺ [CH (COOC ₂ H ₅ )]. , —CH ₂ NO ₂ , —SiOH, —B (OH) ₂ , —PH _{3 and the} like, among which carboxyl, amino and hydroxyl are preferable.
The addition polymerizable monomer containing a group having active hydrogen may be any compound having a group having active hydrogen and an addition polymerizable double bond in the molecule, and a vinyl compound containing a group having active hydrogen. Any of vinylidene compounds and vinylene compounds may be used. An acrylic acid derivative or a styrene derivative containing a group having active hydrogen is preferable.
Examples of the addition polymerizable monomer containing such a group having active hydrogen include those described in JP-A-9-208681, JP-A-2002-348344, and JP-A-2006-158961. A monomer can be mentioned.
Specific examples include the following addition polymerizable monomers.
Carboxy group-containing vinyl monomers include (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol Examples include monoether, citraconic acid, monoalkyl ester of citraconic acid, hexadecane (meth) acrylate and cinnamic acid.
As the hydroxyl group-containing vinyl monomer, a hydroxyl group-containing monofunctional vinyl monomer, a hydroxyl group-containing polyfunctional vinyl monomer, or the like is used. As the hydroxyl group-containing monofunctional vinyl monomer, a vinyl monomer having one vinyl group is used. For example, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol , 2-hydroxyethylpropenyl ether (2-propenoxyethanol), 16-hydroxyhexadecane methacrylate and sucrose allyl ether. As the hydroxyl group-containing polyfunctional vinyl monomer, a vinyl monomer having a plurality of vinyl groups is used. For example, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, Diglycerin tri (meth) acrylate, sorbitan tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetraglycerin penta (meth) acrylate, glycerin di (meth) allyl ether, trimethylolpropane di (meth) allyl ether, Pentaerythritol tri (meth) allyl ether, diglycerin tri (meth) allyl ether, sorbitan tri (meth) allyl ether, dipentaerythritol penta (meth) allyl ether and Tetraglycerol penta (meth) allyl ether.
As amino group-containing vinyl monomers, aminoethyl (meth) acrylate, aminoisopropyl (meth) acrylate, aminobutyl (meth) acrylate, aminohexyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, crotylamine, amino Examples include styrene, methyl α-acetaminoacrylate, N-allylphenylenediamine, and 16-methacryloylhexadecanamine.

  A group having a polymerizable unsaturated bond can be introduced using a polymer containing a monomer which is a (meth) acrylic acid derivative containing active hydrogen in the molecule as the crosslinkable functional group. In this case, the crosslinkable functional group is preferably carboxyl, amino, or hydroxyl, and more preferably hydroxyl.

As described above, the group having a polymerizable unsaturated bond is a precursor of a polymer containing an addition polymerizable monomer (d) which is a (meth) acrylic acid derivative containing active hydrogen in the molecule as a crosslinkable functional group. By reacting a functional group capable of introducing a group having a polymerizable unsaturated bond (a group having active hydrogen) with a compound having a group having a polymerizable unsaturated bond in the same molecule as a body Can be introduced.
Examples of the compound having a functional group that reacts with a group having active hydrogen and a group having a polymerizable unsaturated bond in the same molecule include, for example, an isocyanate compound having a polymerizable unsaturated bond, and a polymerizable unsaturated bond. And acid halides having the following. Examples of the group having such a polymerizable unsaturated bond include (meth) acryl, allyl, styryl and the like.

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

In the formula, R ⁸ and R ⁹ are hydrogen or methyl, B is oxygen, alkylene having 1 to 3 carbons, or —OR ¹⁰ —; R ¹⁰ is alkylene having 2 to 12 carbons, 2 carbons It is -12 oxyalkylene or C6-C12 arylene.

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

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

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

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

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

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

As reaction temperature, it is 0-120 degreeC generally, Preferably it is 20-100 degreeC. If reaction temperature is 0-120 degreeC, reaction will advance and it may not cause superposition | polymerization.
The molar ratio during the reaction is isocyanato group: group having active hydrogen = 100: 1 to 0.01: 1, preferably 20: 1 to 0.1: 1.
In addition, a polymerization inhibitor may be present for the purpose of suppressing polymerization during the reaction between the isocyanato group and the group having active hydrogen. As polymerization inhibitors, p-benzoquinone, naphthoquinone, phenanthraquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p- Benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-diacyloxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,5-t-butylhydroquinone, mono-t-butylhydroquinone or 2,5 -Di-t-amylhydroquinone etc. can be mentioned, and the amount used is 10 to 10, with respect to the total amount of the polymer precursor used in the present invention and the isocyanate compound having a polymerizable unsaturated bond. 000 ppm, preferably 50 to 1,000 ppm.

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

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

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

(Addition polymerizable monomer having no crosslinkable functional group (d))
In the polymer used in the present invention, in order to control the compatibility with the resin, the leveling property, the content of the group having a crosslinkable functional group in the copolymer, etc., addition polymerization having no crosslinkable functional group is required. The monomer (d) can also be used in an arbitrary ratio.

  As the addition polymerizable monomer (d) having no crosslinkable functional group, for example, a (meth) acrylic acid compound having one addition polymerizable double bond and no group having active hydrogen, and Examples thereof include a styrene compound having one addition polymerizable double bond and no group having active hydrogen.

  Specific examples of such (meth) acrylic acid compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl Alkyl (meth) acrylates such as (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; phenyl (meth) acrylate, toluyl (meth) Aryl (meth) acrylates such as acrylate; Arylalkyl (meth) acrylates such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, etc. An alkoxyalkyl (meth) acrylate, an ethylene oxide adduct of (meth) acrylic acid, 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.

  Furthermore, as an optional addition polymerizable monomer (d), it has a main chain derived from styrene, (meth) acrylic acid ester, siloxane, alkylene oxide (for example, ethylene oxide, propylene oxide), etc. Also exemplified are macromonomers having one polymerizable double bond.

Examples of the addition polymerizable monomer (d) having no crosslinkability include compounds having two addition polymerizable double bonds.
Examples of compounds having two addition polymerizable double bonds include 1,3-butanediol = di (meth) acrylate, 1,4-butanediol = di (meth) acrylate, 1,6-hexanediol = di (Meth) acrylate, polyethylene glycol = di (meth) acrylate, diethylene glycol = di (meth) acrylate, neopentyl glycol = di (meth) acrylate, triethylene glycol = di (meth) acrylate, tripropylene glycol = di (meth) Acrylate, hydroxypivalate ester neopentyl glycol = di (meth) acrylate, trimethylolpropane = di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobisphenol A Bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol = di (meth) acrylate, hydroxypivalate ester neopentyl glycol compound Di (meth) acrylate and di (meth) acrylate monomers such as bis [(meth) acryloyloxypropyl] tetramethyldisiloxane, and divinylbenzene.
In addition, a macromonomer having a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide, propylene oxide, etc. and having two polymerizable double bonds is exemplified. .

Examples of the addition polymerizable monomer (d) having no crosslinkability 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. The

<Fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a)>
As described above, when the fluorosilsesquioxane (a) is not used alone in the production of the transfer film of the present invention, the fluoropolymer having a structural unit derived from the fluorosilsesquioxane (a). It is preferable to use (b), and the fluoropolymer (b) may contain a structural unit derived from the addition polymerizable monomer (d) as necessary.
The fluoropolymer (b) may be an ordered copolymer such as block copolymer or a random copolymer, but is preferably a random copolymer. In addition, the polymer used in the present invention may have a crosslinked structure or a graft copolymer.

When the fluoropolymer (b) used in the present invention contains a structural unit derived from the addition polymerizable monomer (d), the fluorosilsesquioxy in the fluoropolymer (b) is used. The molar fraction of the structural unit derived from sun (a) and the structural unit derived from any addition polymerizable monomer (d) is arbitrary, and (a) :( d) = 0.001: 99.999. ˜99.999: 0.001, and (a) :( d) = 1: 99 to 99: 1 is more preferable.
In addition, the presence of each structural unit and the molar fraction of each structural unit in the polymer of the present invention can be measured by ¹ H-NMR.

  The weight average molecular weight of the polymer used in the present invention varies depending on the molar fraction of the structural unit derived from the addition polymerizable monomer (d), but is 1,000 to 1,000,000 as a guide. 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.

  When a plurality of types of monomers are used as the addition polymerizable monomer (d), the ratio of each monomer may be appropriately determined according to the characteristics of the target polymer. 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 carried out using the compound described in 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 light. Compounds used as photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-mo Ruphorinophenyl) -butanone-ethyl 1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butyl) Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4' -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 '-Methoxystyryl) -4,6
-Bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) )]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl)- 5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonyl Bis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetraki (4-Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6- Trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-) 2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H- Pyrrol-1-yl) -phenyl) titanium, and the like. These compounds may be used alone or in combination of two or more. 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxy) Carbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone is preferred.
The amount of the polymerization initiator used in the above addition polymerization may be about 0.01 to 10 mol% with respect to the total number of moles of monomers.

In the addition polymerization, a chain transfer agent may be used. The molecular weight can be appropriately controlled by using the chain transfer agent. Examples of chain transfer agents include thio-β-naphthol, thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptopropionate), mercaptans such as pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate, diethyl disulfide; etc., as well as 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 shape A suspension polymerization method or a polymerization method using supercritical CO ₂ can be used.
In the case of the solution polymerization method, in a suitable solvent, dissolve fluorosilsesquioxane (a), optional addition polymerizable monomer (d), a polymerization initiator, a chain transfer agent, and the like. What is necessary is just to carry out addition polymerization reaction by heating or irradiating light.

Examples of the solvent used in the above polymerization reaction include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (salt chloride). Methylene, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, Propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethyl) Formamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbons Solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic Fluorine solvent (α, α, α-trifluorotoluene, hexafluorobenzene) and water are included. These may be used alone or in combination of two or more.
The amount of the solvent used 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 being lowered, and a polymer having an appropriately controlled molecular weight is obtained. Further, the polymerization reaction is preferably carried out in a polymerization system from which dissolved oxygen is removed under reduced pressure (after removing dissolved oxygen under reduced pressure, the polymerization reaction may be carried out under reduced pressure as it is).

The polymer obtained in the solution may be purified or isolated by a conventional method, and may be used for forming a coating film or the like in the solution.
When purifying the polymer used in the present invention, a purification method by reprecipitation operation is preferred. This purification method is performed as follows. First, in the polymerization reaction solution containing the polymer and the unreacted monomer, a solvent that does not dissolve the polymer but dissolves the unreacted monomer, a so-called precipitant is added to this solution to remove only the polymer. Precipitate. A preferred amount of the precipitating agent is 20 to 50 times based on the weight of the polymerization reaction solution.
A preferred precipitant is a solvent that is compatible with the solvent used in the polymerization, does not dissolve the polymer at all, dissolves only unreacted monomers, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitating agents are methanol, ethanol, 2-propanol, hexane or heptane. These may be used alone or in combination of two or more. Moreover, when mixing and using, you may purchase and use Solmix AP-1, A-11, etc. which are marketed as a denatured alcohol from Nippon Alcohol Sales Co., Ltd. And in order to raise the removal efficiency of an unreacted monomer further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, only the polymer can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

<Transfer film of the present invention>
In the present invention, fluorosilsesquioxane (a) or a resin composition containing a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) is a substrate such as a film substrate described later. It is used for the production of a transfer layer formed on the surface. In this case, the matrix resin (c) is combined with the resin composition as necessary, and dissolved or dispersed in various solvents, and used for the production of a transfer film. be able to. In the present application, the matrix resin (c) means not only a matrix resin but also a matrix resin monomer. With the use of transfer film production,
1) A transfer layer is formed by applying a solution or dispersion containing the polymer used alone in the present invention to the substrate of the transfer film,
2) A transfer layer made of a composite resin with a matrix resin (c) is prepared by applying a solution or dispersion containing the polymer used in the present invention and another matrix resin (c) to the substrate of the transfer film. And 3) applying a solution or dispersion containing the polymer used in the present invention and a matrix resin monomer capable of reacting with the polymer used in the present invention to the substrate of the transfer film. And forming a transfer layer made of a composite resin by curing the matrix resin monomer.
For example, fluorosilsesquioxane (a) or a resin composition containing a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) is applied to a transfer film substrate and dried. The transfer layer can be formed on the substrate by curing as necessary. The formed transfer layer imparts water / oil repellency, antifouling property, and the like to the surface of the transfer target by transfer.

  As described above, the polymer used in the present invention may be used alone for the production of a transfer film as in 1) above, but is used by mixing with other matrix resin (c) as in 2) above. Alternatively, it may be used by mixing with a matrix resin monomer (hereinafter also referred to as a reactive matrix resin monomer) capable of reacting with the polymer used in the present invention as in the above 3). In addition, when the polymer (b) and the matrix resin (c) or the matrix resin monomer are used in combination for the production of the transfer film as in the above 2) and 3), in the solution or dispersion containing these The weight ratio of the polymer (b) to the matrix resin (c) or the matrix resin monomer is preferably 0.1: 99.9 to 20:80.

The matrix resin (c) may be either a thermoplastic resin or a curable resin, and may be a plurality of types of resins.
Examples of the matrix resin (c) 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-methylpentene, syndiotactic polystyrene, polyamide (nylon 6: DuPont brand name, nylon 6,6: DuPont brand name, nylon 6,10: DuPont brand name, nylon 6, T: DuPont brand name, Nylon MXD6: DuPont brand name), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene oxide , Fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: Unitika Co., Ltd. trade name, Vectra: Polyplastics Co., Ltd.) Product name, etc.), polyimide (Kapton: Toray Co., Ltd. trade name, AURUM: Mitsui Chemicals Co., Ltd. trade name, etc.), polyetherimide, polyamideimide, phenol resin, alkyd resin, melamine resin, epoxy resin, urea Resins, bismaleimide resins, silicone resins and the like are included.
These resins may be used alone, or a plurality of resins may be used in combination.

The reactive matrix resin monomer may be either a thermosetting resin monomer or a photocurable resin monomer. Preferred examples include reactive matrix resin monomers that form epoxy resins. 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- -Hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4- Hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl-3,3 ′, 5,5′-tetramethylbiphenyl, bis (hydroxynaphthyl) methane, and 1,1′-binaphthol, 1,1′-bis ( Epoxy resins made from 3-t-butyl-6-methyl-4-hydroxyphenyl) butane and the like are included.

Furthermore, examples of the epoxy resin formed include phenol novolac epoxy resins that are glycidyl etherified products of reaction products with phenols such as phenol, o-cresol, catechol, and aldehydes such as formaldehyde; phenol, cresol, Polyglycidyl ether of trityl skeleton-containing polyphenols obtained by condensation of phenols such as methyl-t-butylphenol and aromatic aldehydes such as hydroxybenzaldehyde; reaction product of trityl skeleton-containing polyphenols and formaldehyde Polyglycidyl ethers of polyphenolic novolaks containing trityl skeleton; reaction of phenols such as phenol, o-cresol, catechol, etc. with xylylene dichloride, (hydroxymethyl) benzene, etc. Polyglycidyl ethers of polyaralkylphenol resins as components; phenols such as phenol, o-cresol and catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and unsaturated alicyclics such as dicyclopentadiene and limonene Alicyclic hydrocarbon-containing polyphenol resin-type epoxy resin or polynaphthol resin-type epoxy resin, which is a glycidyl ether of a reaction product with an aromatic hydrocarbon; alicyclic hydrocarbon-containing polyphenol resin or polynaphthol resin and formaldehyde Polyglycidyl ethers of cycloaliphatic hydrogen-containing polyphenol novolak resins or polynaphthol novolak resins that are reaction products of glycidyl of polyhydric phenols obtained by condensation reaction of phenols with aromatic carbonyl compounds Ether compounds; fluoroglycine, tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,3-bis [(4-hydroxyphenyl) methyl] benzene, 1 , 4-bis [(4-hydroxyphenyl) methyl] benzene and other trivalent or higher polyglycidyl ethers; glycidyl ether compounds derived from cyclic phenols such as calixarene; p-amino Phenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether 1,4-bis (4-aminopheno Ii) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4 -Aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis ( Methylamine), 1,3-cyclohexanebis (methylamine), amine-based epoxy resins derived from N, N-diglycidylaniline, etc .; p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid, etc. Glycidyl ester compounds derived from aromatic carboxylic acids of 5,5-dimethylhydantoin, etc. Hydantoin-based epoxy compounds derived from: 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexene dioxide, 3 Alicyclic epoxy resins such as 1,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; aliphatic epoxy resins obtained by oxidizing double bonds in unsaturated hydrocarbon compounds such as polybutadiene, etc. .

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

  For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methyl Cyclohexyl carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydro Dioctyl phthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,2: 8,9 diepoxy limonene (trade name: CEL3000, Daicel Chemical Co., Ltd.), epoxidation -Cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (trade name: Epolide GT301, Daicel Chemical Industries), epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone (trade name: Epolide GT401, Daicel Chemical Co., Ltd.), 1,2-epoxy-4- (2-oxiranyl) cyclosoxane adduct of 2,2-bis (hydroxymethyl) -1-butanol (trade name) : EHPE3150, Daicel Chemical Co., Ltd.), 1,2-epoxy-4- (2-oxiranyl) cyclosexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and 3,4-epoxycyclohexenylmethyl- 3 ', 4'-epoxycyclohexenecarboxyl (Trade name: EHPE3150CE, Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400, Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (trade name) : Epoxy resin obtained from monomers such as Cyclomer M100, Daicel Chemical Co., Ltd.), and epoxidized polybutadiene (trade name: Epolide PB3600, Daicel Chemical Co., Ltd.), epoxidized thermoplastic elastomer (trade name: Epofriend, Daicel) Epoxy resin represented by Chemical Co., Ltd.).

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

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

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

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

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

  That is, the matrix resin monomer includes oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane and 3,3-dichloromethyloxetane; trioxane such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; 1,3-dioxolane Cyclic ether compounds such as 1,3,6-trioxacyclooctane; cyclic lactone compounds such as β-propiolactone, γ-butyrolactone, ε-caprolactone; thiirane compounds such as ethylene sulfide; trimethylene sulfide, 3,3 A thietane compound such as dimethylthietane; a cyclic thioether compound such as a tetrahydrothiophene derivative; a spiroorthoester compound obtained by reacting an epoxy compound with a lactone; a spiroorthocarbonate compound; a cyclic carbonate Products; vinyl ether compounds such as ethylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether; styrene, vinylcyclohexene, isobutylene , Ethylenically unsaturated compounds such as polybutadiene, amino group, hydroxyl, glycidyl, oxetanyl, polydimethylsiloxane having epoxy cyclohexyl, polyalkylene oxide (polyethylene oxide, polypropylene oxide, block copolymer comprising polyethylene oxide and polypropylene oxide, etc.) Fluorinated polyalkylene oxides (polyfluoroethylene oxide, polyfluoropropylene oxide, etc.) And the like in La.

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

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

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

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

α 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, for example, represented by the following general formula.
[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.

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

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

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

Among these onium salts, the curing reaction initiator in the present invention is more preferably an aromatic onium salt exemplified by the following (A) to (C). Among these, the 1 type can be used individually or in mixture of 2 or more types.
(I) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, and (b) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryl iodonium salts such as hexafluorophosphate and di (4-t-butylphenyl) iodonium hexafluorophosphate (c) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thio Phenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenyls Honium hexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4 , 4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis- Hexafluorophosphate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluoro Phenyl) sulfonium Kisa triarylsulfonium salts such as fluorophosphate

Further, the curing reaction initiator in the present invention may be a mixture of an iron arene complex or an aluminum complex and silanols such as triphenylsilanol. The iron arene complex includes (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron-hexa. Fluorophosphate and the like are included, 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 (c) is an epoxy resin, the content of the curing reaction initiator (preferably an acid generator) is 10 to 10 epoxy groups contained in the polymer and the epoxy resin monomer used in the present invention. It is preferable that it is 1 mol with respect to 500 mol.

Examples of preferable reactive matrix resin monomers in addition to the aforementioned epoxy resins include monomers that form urethane resins. A urethane resin is a compound having a urethane bond repeatedly in the composition, a polyisocyanate compound having two or more isocyanato groups (O═C═N—R—N═C═O), and two or more hydroxyl groups. Polyol compound (HO—R′—OH), polyamine (H ₂ N—R ″ —NH ₂ ), or compound having active hydrogen such as water (—NH ₂ , —NH, —CONH—, etc.) Accordingly, examples of the reactive matrix resin monomer include the following compounds having a plurality of isocyanato groups.

Examples of the compound having a plurality of isocyanato groups include low molecular weight polyisocyanates such as aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, prepolymers, isocyanurates, triions, And derivatives and modified products of these polyisocyanates.
Aliphatic polyisocyanates include diisocyanates (eg, trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene diisocyanate. , Pentamethylene diisocyanate, C _2-16 alkane diisocyanate such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate), polyisocyanate (for example, lysine) Ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloct Emissions, 1,3,6-tri-diisocyanatohexane, 2,5,7 C _6-20 alkane triisocyanate, etc.) such as trimethyl-1,8-diisocyanato-5-isocyanatomethyl octane.
Examples of the alicyclic polyisocyanate include diisocyanates (for example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ( Common names: isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) ) Cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, norbornane diisocyanate, etc.), polyisocyanate (for example, 1,3,5-triisocyanatocyclohex Sun, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanate Natopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2. 2.1) Heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) ) -2-Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3- Socyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) And triisocyanates such as heptane).
Examples of araliphatic polyisocyanates include diisocyanates (for example, 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4- Bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, polyisocyanate (for example, triisocyanate such as 1,3,5-triisocyanatomethylbenzene) Is mentioned.
Aromatic polyisocyanates include diisocyanates (eg, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate or Mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, etc.), polyisocyanates (for example, triphenylmethane-4,4 ′ , 4 ″ -triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene and the like, for example, 4,4′-diphenylmethane-2,2 ′, 5,5 ′ − Tiger tetra isocyanates of the isocyanate, and the like).
Examples of the polyisocyanate derivative include 2,4,6-, which can be obtained by reacting the polyisocyanate with a dimer, trimer (isocyanurate ring-containing polyisocyanate), biuret, allophanate, carbon dioxide and the above polyisocyanate monomer. Examples include polyisocyanate having an oxadiazine trione ring, carbodiimide, uretdione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI), and crude TDI.
Examples of the modified polyisocyanate include, for example, the above-mentioned polyisocyanate or a polyisocyanate derivative, and a low molecular weight polyol or a low molecular weight polyamine described later. Examples include polyol-modified products, polyamine-modified products, and the like obtained by reacting at an equivalent ratio in excess of amino groups.
The reactive matrix resin monomer used in the present invention also includes a urethane resin having an isocyanato group. Such urethane resins having an isocyanato group are commercially available as Coronate and Millionate manufactured by Nippon Polyurethane Industry Co., Ltd., Takenate of Mitsui Chemicals Polyurethane Co., Ltd., and MT olester. May be used.
These can be used alone or in combination of two or more.

Moreover, you may mix the compound which has several hydroxyl groups which can react with an isocyanato group as needed. Examples of such a compound having a hydroxyl group include polyhydric alcohols.
Examples of the polyhydric alcohols include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, and the like.
Specifically, examples of the polyether polyol include polyethylene glycol, polypropylene glycol, poly (ethylene / propylene) glycol, polytetramethylene ether glycol and the like.
Examples of the polyester polyol include a compound obtained by polycondensation of a low molecular weight diol and a dibasic acid, and a compound obtained by a ring opening reaction of a dibasic acid using a low molecular weight diol as an initiator. Examples of the low molecular weight diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and the like. . Examples of the dibasic acid used for the former polycondensation include adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid and the like. Examples of the dibasic acid used in the latter ring-opening reaction include polyε-caprolactone and polyβ-methyl-δ-valerolactone.
Examples of the polycarbonate polyol include 1,6-hexanediol polycarbonate polyol, 3-methyl-1,5-pentanediol polycarbonate polyol, and mixed diol polycarbonate polyol having 4 to 6 carbon atoms. Examples of the polybutadiene polyol include a polyol composed of 1,4-polybutadiene and 1,2-polybutadiene. Examples of the hydrogenated polybutadiene polyol include those having a paraffin skeleton obtained by hydrogenating polybutadiene polyol.
These can be used alone or in combination of two or more.
The blending ratio of the polymer used in the present invention and the compound having an isocyanato group may be arbitrary, but the OH group / NCO group equivalent is preferably 0.1 to 10.

  In addition to the aforementioned urethane resin, preferable examples of the reactive matrix resin monomer include a monomer that forms a curable resin capable of radical curing by ultraviolet irradiation and heat.

  As a resin that can be radically cured by ultraviolet irradiation, radical polymerization of unsaturated polyester resin, polyester (meth) acrylate resin, epoxy (meth) acrylate resin, urethane (meth) acrylate resin, (meth) acrylic resin, etc. is possible. A resin having an unsaturated bond can be exemplified.

As an unsaturated polyester resin that can be used in the present invention, a condensation product (unsaturated polyester) obtained by esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and a saturated polybasic acid if necessary) is polymerizable. The thing melt | dissolved in the monomer is mentioned.
The unsaturated polyester used as a raw material for the unsaturated polyester resin may be one produced by a known method. Specifically, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and other polybasic acids having no polymerizable unsaturated bond or anhydrides thereof and fumaric acid, maleic acid, itaconic acid A polymerizable unsaturated polybasic acid or an anhydride thereof such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A Polyhydric alcohol such as propylene oxide adduct of bisphenol A It reacted as Le component include those produced.
As unsaturated dicarboxylic acid used for terminal carboxyl polyester, dicarboxylic acid which does not have an active unsaturated group, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, etc. are mentioned. Examples of the unsaturated dicarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2 -Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. And monohydric alcohols.

The polyester (meth) acrylate resin that can be used in the present invention includes (1) a terminal carboxyl group polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol, and an α, β-unsaturated carboxylic acid. (Meth) acrylate obtained by reacting an epoxy compound containing an ester group, (2) a hydroxyl group-containing acrylate on a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol (Meth) acrylate obtained by reaction, (3) Saturated polybasic acid and / or obtained by reacting polyester of terminal hydroxyl group obtained from unsaturated polybasic acid and polyhydric alcohol with (meth) acrylic acid (meta ) Acrylates.
Examples of saturated polybasic acids used as raw materials for polyester (meth) acrylates include polyunsaturated unsaturated bonds such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples thereof include basic acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. Furthermore, as the polyhydric alcohol component, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2- Examples include methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, and the like. .
A typical example of the α, β-unsaturated carboxylic acid ester having an epoxy group used for the production of polyester (meth) acrylate is glycidyl methacrylate.

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

Examples of the urethane (meth) acrylate resin that can be used in the present invention include, after reacting a polyisocyanate and a polyhydroxy compound or a polyhydric alcohol, further a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl group. Examples include radical polymerizable unsaturated group-containing oligomers that can be obtained by reacting ether compounds.
Specific examples of the polyisocyanate used as a raw material for the urethane (meth) acrylate include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diene. Isocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Bannock D-750, Crisbon NK (trade name; manufactured by Dainippon Ink and Chemicals), Desmodur L (trade name; Sumitomo Bayer Urethane Co., Ltd.) Manufactured), Coronate L (trade name; manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), IONATE 143L ( Name; manufactured by Mitsubishi Chemical Co., Ltd.).
Examples of the polyhydroxy compound used as a raw material for the urethane (meth) acrylate include polyester polyol, polyether polyol, and the like. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct. Glycerin-ethylene oxide-propylene oxide adduct, trimethylol propane-ethylene oxide adduct, trimethylol propane-propylene oxide adduct, trimethylol propane-tetrahydrofuran adduct, trimethylol propane-ethylene oxide-propylene oxide adduct, dipentaethylene Tall-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofura Adduct, di pentaerythritol - ethylene oxide - propylene oxide adduct and the like.
Specific examples of the polyhydric alcohol used as a raw material for the urethane (meth) acrylate include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and 2-methyl-1. , 3-propanediol, 1,3-butanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4-diol, 2,6-decaling Call, 2,7-decalin glycol, and the like.
Although it does not specifically limit as a hydroxyl-containing (meth) acryl compound used as a raw material of the said urethane (meth) acrylate, A hydroxyl-containing (meth) acrylic acid ester is preferable, Specifically, for example, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanursannoji (meta ) Acrylate, pentaerythritol tri (meth) acrylate, and the like.
Specific examples of the hydroxyl group-containing allyl compound used as a raw material for the urethane (meth) acrylate include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol mono Allyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, Xylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glycol Syringe allyl ether, pentaerythritol triallyl ether.

  As the (meth) acrylic resin that can be used in the present invention, a methyl methacrylate (MMA) resin, a (meth) acrylic ester-based polymer, also called acrylic syrup, is dissolved in a (meth) acrylic ester monomer, Examples of the (meth) acrylate monomer include methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, Examples include (meth) acrylic acid esters such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.

<Curing method>
When the polymer used in the present invention is mixed with a monomer having an unsaturated bond as the reactive matrix resin monomer, a polymerization initiator can be used for the purpose of promoting curing. Such a polymerization initiator may be an initiator that generates radicals by heat or light. Examples of the thermal polymerization initiator used include 2,2′-azobisisobutyronitrile and 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-butyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (cyclohexane-1-carbohydrate Azo compounds such as nitrile); benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butylperoxyacetate , Peroxides such as t-butylperoxybenzoate, t-butylperoxyneodecanoate; and tetraethylthiuramdisulfi Etc. contains a radical polymerization initiator; dithiocarbamates etc. Specific examples of the photopolymerization initiator used is not particularly limited as long as it is a compound which generates a radical by irradiation of ultraviolet rays or visible light. Compounds used as photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-mo Ruphorinophenyl) -butanone-ethyl 1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butyl) Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4' -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 '-Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4 -[P-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s -Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4- Dichlorophenyl) -4,4 ', 5,5'-tetrafe 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 is preferably about 0.01 to 50% by weight, more preferably about 0.01 to about the total weight of the polymer used in the present invention and the reactive matrix resin containing the polymer. 30% by weight.

  As described above, the polymer used in the present invention can be dissolved or dispersed in a solvent and used for production of a transfer film. The concentration of the solid content (including the polymer and other resins used in the present invention) dissolved or dispersed in the solvent is not particularly limited, but is preferably 0.01 to 80% by weight, more preferably 0. 01 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 the solvent, and the solvent may be one kind or a combination of two or more kinds. Moreover, you may use the polymer and matrix resin monomer which are used for this invention, dissolving in a solvent. Examples of solvents used include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene). Etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, benzo Nitriles, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N , N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 or 6 carbon atoms), perfluorocarbon solvents (perfluorocarbons). Fluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroethers, fluoropolyethers, fluoroketones, fluoroalcohols), aromatic fluorine solvents ( α, α, α-trifluorotoluene, hexafluorobenzene) and water.

The substrate of the transfer film of the present invention is prepared by using the fluorosilsesquioxane (a) of the present invention or a resin composition solution containing a fluoropolymer (b) having a structural unit derived from the fluorosilsesquioxane (a). There are no particular restrictions on the method of forming the transfer layer by applying to the substrate, but spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating, rod coating, Examples include a bar coating method, a die coating method, a kiss coating method, a reverse kiss coating method, an air knife coating method, and a curtain coating method.
In the transfer film of the present invention, the thickness of the transfer layer is preferably 0.1 to 10 μm.
Examples of the substrate serving as a base material for the transfer film to be applied include polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, and other synthetic resin sheets and films; norbornene resin A transparent resin substrate used for optical applications such as cycloolefin resin, methacrylstyrene, polysulfone, alicyclic acrylic resin, polyarylate and the like is included.
These substrates may be pretreated. Examples of the pretreatment include chemical treatment with a silane coupling agent, sandblast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas phase. Reaction methods, vacuum deposition, etc. are included.
The applied solution can be dried in an environment of room temperature to 200 ° C.
When the transfer layer is formed by thermal drying, it can be performed in an environment of room temperature to about 200 ° C.
When the transfer layer is formed by irradiation with light or an electron beam, the active energy ray source is not particularly limited. However, depending on the properties of the photopolymerization initiator used, for example, a low pressure mercury lamp, a high pressure mercury lamp, or an ultrahigh pressure mercury lamp. , Metal halide lamp, carbon arc, xenon arc, gas laser, solid laser, electron beam irradiation device, and the like.

In the transfer film of the present invention, an adhesive layer made of an adhesive may be provided on the surface of the substrate opposite to the transfer layer.
Preferred examples of the pressure-sensitive adhesive include acrylic resin-based pressure-sensitive adhesives and silicone resin-based pressure-sensitive adhesives.
In addition, the adhesive layer has a pin coat method, a roll coat method, a slit coat method, a dipping method, a spray coat method, a gravure coat method, a reverse coat method, a rod coat method, a bar coat method, a die coat method, a kiss coat method, It can be provided by applying an adhesive by reverse kiss coating, air knife coating, curtain coating, or the like.
The thickness of the adhesive layer is preferably 0.1 to 10 μm.

As a specific use example of the transfer film of the present invention, for example, in the transfer film of the present invention, a transfer film in which an adhesive is applied to the opposite surface of the transfer layer as described above is formed. By adhering to a base material such as plastic, metal, or glass, water and oil repellency, antifouling property, slipperiness, and the like can be imparted to the surface of the base material. Specifically, the transfer film of the present invention can be used for dirt prevention applications such as prevention of fingerprint adhesion on display parts such as liquid crystal displays, plasma displays and touch panels, and waterproofing and dirt prevention applications such as glass windows and mirrors. it can.
In addition, when the transfer film of the present invention is attached to a mold part of an injection molding machine and a thermosetting resin is injected, the molded body made of the thermosetting resin is bonded to the surface, Easily peels off. The obtained molded product is provided with characteristics such as water and oil repellency on the surface.

<Laminated body of the present invention>
The laminate referred to in the present invention refers to a transfer object (hereinafter referred to as a transfer object) comprising a curable resin composition and / or a thermoplastic resin composition on the transfer layer surface or substrate surface of the transfer film obtained by the above-described method. It is obtained by molding a base material such as plastics, glasses, and metals as needed, and can be laminated to a transferred layer and further laminated.
Specific examples of substrates to be further bonded as necessary include transparent glass substrates such as white plate glass, blue plate glass, silica coated blue plate glass; polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, Sheets and films made of synthetic resin such as polyimide; transparent resin substrates used for optical applications such as cycloolefin resins including norbornene resins, methacrylstyrene, polysulfone, alicyclic acrylic resins, polyarylate; aluminum plates, copper plates, nickel plates And metal substrates such as stainless steel plates; other ceramic substrates and semiconductor substrates having photoelectric conversion elements. If necessary, these substrates may be pretreated. Examples of pretreatment include chemical treatment with a silane coupling agent, release treatment with a silicone compound, sandblast treatment, corona discharge treatment, Examples include ultraviolet treatment, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum deposition.

  The transferred body (transferred layer) is a molded body (layer) adjacent to the transfer layer of the transfer film or a molded body (layer) adjacent to the substrate surface of the transfer film, and the molded body is adjacent to the transfer layer. In this case, the transfer film is peeled to give the surface properties such as water and oil repellency, and when the molded body is adjacent to the substrate surface, the substrate surface opposite to the molded body The transfer layer imparts characteristics such as water and oil repellency to the surface. As described above, the transfer target (transfer target layer) is composed of the following curable resin composition and / or thermoplastic resin composition. As the resin composition used for the production of the transfer target (transfer target layer), any of the curable resin composition and the thermoplastic resin composition may be used alone, or a plurality of types may be used in combination. Also good.

  Examples of the curable resin composition include a photosensitive resin composition containing at least a compound having an ethylenically unsaturated end group and a photopolymerization initiator; a monovalent containing at least an epoxy such as glycidyl and epoxycyclohexyl and a cyclic ether such as oxetanyl. An epoxy resin composition comprising a compound having a functional group and a curing agent selected from a thermal latent cationic curing agent, a photocationic curing agent, an acid anhydride, or an amine compound; a compound having at least one hydroxyl group or carboxyl group And a urethane resin composition containing a compound having at least one isocyanato group, and any components can be mixed and dissolved as necessary, and the concentration of nonvolatile components in the resin composition is not limited.

  Examples of thermoplastic resin compositions 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-methylpentene, syndiotactic polystyrene, polyamide (nylon 6: DuPont brand name, nylon 6,6: DuPont brand name, nylon 6,10: DuPont brand name, nylon 6, T: DuPont brand name, Nylon MXD6: DuPont brand name, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene oxide Fluorine resin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: Unitika Co., Ltd. trade name, Vectra: Polyplastics Co., Ltd.) Name, etc.), 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 , Resin compositions containing bismaleimide resin and silicone resin, and the like. These resins may be used singly or in combination, and if necessary, arbitrary components can be mixed and dissolved. The concentration of the non-volatile component of the product is not limited.

<Manufacturing method of laminate>
The laminate of the present invention is formed by laminating the transfer layer comprising the curable resin composition and / or the thermoplastic resin composition on the surface of the transfer layer or the substrate surface of the transfer film of the present invention. The method of laminating on the transfer film is not particularly limited, but spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating, rod coating, bar coating, and die coating. Method, kiss coat method, reverse kiss coat method, air knife coat method, curtain coat method and the like. In the laminate of the present invention, the thickness of the layer to be laminated is preferably 0.1 to 10 μm.

<Use of the laminate of the present invention>
The laminate of the present invention described above is obtained by pressing the transfer target (transfer target layer) or forming the transfer target (transfer target layer) on the transfer film. In addition, it is possible to impart water and oil repellency and the like, and transfer is possible even to a transfer target having a fine and complicated shape, and water and oil repellency can be imparted.
As a specific aspect of the laminate of the present invention, for example, a transfer layer made of a photosensitive resin composition is provided on the transfer layer of the transfer film of the present invention, and a substrate that serves as a protective film on the transfer layer And dry film resists.
In addition, specific examples of use of the laminate of the present invention are described in the following examples, and examples thereof include the following.
A layer made of a photosensitive resin composition of a laminate obtained by applying the photosensitive resin composition on the transfer film of the present invention is laminated on a copper layer, exposed, and then peeled off by peeling off the transfer film. Water / oil repellency and the like can be imparted to the surface of the layer made of the conductive resin composition.

<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. In addition, the data of the weight average molecular weight in a present Example were calculated | required by GPC (gel permeation chromatography method) by using poly (methyl methacrylate) as a standard substance. All ¹ H-NMR measurements were performed in deuterated chloroform (400 MHz).

[Production Example 1]
Synthesis of γ-methacryloxypropylhepta (trifluoropropyl) -T ₈ -silsesquioxane (A) Into a 4-liter flask with an internal volume of 1 L equipped with a reflux condenser, thermometer and dropping funnel, trifluoropropyltri Methoxysilane (100 g), THF (500 mL), deionized water (10.5 g) and sodium hydroxide (7.9 g) were charged, and the mixture was stirred with a magnetic stirrer from room temperature to the temperature at which THF was refluxed. Heated. Stirring was continued for 5 hours from the start of reflux to complete the reaction. Thereafter, the four-necked flask was lifted from the oil bath and allowed to stand at room temperature overnight, then set again in the oil bath and concentrated by heating under constant pressure until a solid precipitated.
The precipitated product was collected by filtration with a pressure filter equipped with a membrane filter having a pore size of 0.5 μm. Subsequently, 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 allowed to stand at room temperature overnight. After washing with deionized water three times, the dichloromethane layer was dehydrated with anhydrous magnesium sulfate, and magnesium sulfate was removed by filtration. The mixture was concentrated with a rotary evaporator until a viscous solid was precipitated, and 260 g of methanol was added and stirred until powdery. The powder was filtered using a pressure filter equipped with 5 μm filter paper, and dried in a vacuum dryer at 65 ° C. for 3 hours to obtain 41.5 g of a colorless powdery solid. GPC and ¹ H-NMR of the obtained solid were measured and found to be a compound (a-1) having a structure represented by the following formula.

[Production Example 2] Synthesis of polymer (B) 2- (perfluorobutyl) was added to a four-necked flask with an internal volume of 50 ml equipped with a reflux condenser, a thermometer, a dropping funnel and a septum cap with a syringe for argon bubbling. ) 4.53 g of ethyl methacrylate (M-1420), 1.33 g of glycidyl methacrylate (GMA, hereinafter simply referred to as GMA), oxetane methacrylate (trade name: OXE-30, hereinafter also simply referred to as OXE-30) 1.21 g, 0.54 g of 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M100, hereinafter, also simply referred to as M100), single-end methacryloxy-modified polydimethylsiloxane (trade name: Silaplane FM0721, hereinafter, 4.27g, simply referred to as FM0721) Methacrylate (MMA, hereinafter, simply referred to as MMA) and 0.10 g, methyl ethyl ketone (MEK) was introduced 17.93G, with argon sealed. It was set in an oil bath maintained at 95 ° C. and refluxed, and deoxygenated for 10 minutes. Next, a solution of 0.0441 g of 2,2′-azobis-isobutyronitrile (AIBN) and 0.0247 g of mercaptoacetic acid (AcSH) dissolved in 0.6195 g of MEK was introduced and kept at the reflux temperature. Polymerization was started. After polymerization for 3 hours, a solution in which 0.0441 g of AIBN was dissolved in 0.3968 g of MEK was introduced, and the polymerization was further continued for 2 hours. After completion of the polymerization, 15 mL of denatured alcohol (Solmix AP-1, manufactured by Nippon Alcohol Sales Co., Ltd.) was added to the polymerization solution, and then poured into 300 mL of Solmix AP-1 to precipitate a polymer. The supernatant was removed and dried under reduced pressure (80 ° C., 3 hours) to obtain 6.8 g of polymer (B). The weight average molecular weight determined by GPC analysis of the obtained polymer was 53,500, and the molecular weight distribution (Mw / Mn) was 1.70. Moreover, the composition molar fraction of the monomer component calculated | required from the < ¹ > H-NMR measurement of the polymer (B) is M-1420: GMA: OXE-30: M100: FM0721: MMA = 42.5: 27.0: 18. 5: 7.8: 2.2: 2.0. Furthermore, the fluorine concentration determined from ¹ H-NMR measurement of the polymer (B) was 19.67% by weight.

[Production Example 3] Preparation of transfer film (C) 0.24 g of the obtained polymer (B), and 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate (celloxide 2021, epoxy equivalent: 3.76 g of 131 g / mol, manufactured by Daicel Chemical Industries, Ltd.) to 36.0 g of a mixed solvent (methyl 2-butanone / cyclohexanone / 2-propanol / 3-methoxypropionate = weight ratio 50/20/15/15) Dissolved. Furthermore, 0.065 g of a cationic polymerization initiator (epoxy group / cationic polymerization initiator = 228/1 (molar ratio), epoxy amount: 28.7 mmol) was added as a curing agent to obtain a coating liquid.
The obtained coating liquid was applied onto a polyethylene terephthalate film (thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.) using a coating rod (# 4, manufactured by RD Specialties). did. The obtained coating film was cured and dried in a high temperature chamber at 150 ° C. for 30 seconds, and a transfer film comprising a transfer layer (C-1) having a film thickness of about 0.9 μm and a polyethylene terephthalate substrate layer (C-2). (C) was obtained.

[Production Example 4] Preparation of Transfer Film (D) 15.0 g of ethyl acetate was added to 5.0 g of the above fluorosilsesquioxane (a-1) to obtain a coating solution. The obtained coating liquid was applied onto a polyethylene terephthalate film (thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.) using a coating rod (# 4, manufactured by RD Specialties). did. The obtained coating film was cured and dried for 60 seconds in a high temperature chamber at 80 ° C. to obtain a transfer layer (D-1) having a film thickness of about 2.3 μm. By applying an adhesive to the surface of the polyethylene terephthalate substrate layer (D-2) opposite to the surface on which the transfer layer is formed, the transfer layer (D-1), the substrate layer (D-2) and A transfer film comprising the adhesive layer (D-3) can be obtained.

[Production Example 5] Preparation of transfer film (E) 0.24 g of the obtained polymer (B), and 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate (celloxide 2021, epoxy equivalent: 3.76 g of 131 g / mol, manufactured by Daicel Chemical Industries, Ltd.) to 36.0 g of a mixed solvent (methyl 2-butanone / cyclohexanone / 2-propanol / 3-methoxypropionate = weight ratio 50/20/15/15) Dissolved. Furthermore, 0.065 g of a cationic polymerization initiator (epoxy group / cationic polymerization initiator = 228/1 (molar ratio), epoxy amount: 28.7 mmol) was added as a curing agent to obtain a coating liquid.
The obtained coating solution was applied onto a polyethylene sheet having a thickness of 100 μm using a coating rod (# 4, manufactured by RD Specialties). The obtained coating film is cured and dried in a high temperature chamber at 100 ° C. for 60 seconds, whereby a transfer film (E-1) having a film thickness of about 0.9 μm and a transfer film (E-2) composed of a polyethylene layer (E-2). ) Can be obtained.

[Example 1] Preparation of Laminate 1 Photocurable resin composition (NK Hard B100, manufactured by Shin-Nakamura Chemical Co., Ltd.) was transferred using a coating rod (# 4, manufactured by RD Specialties). It apply | coated on the transfer layer (C-1) of a film. The obtained coating film was dried in a high temperature chamber at 70 ° C. for 60 seconds to obtain a coating film having a thickness of about 7 μm. A polyethylene terephthalate film (thickness: 100 μm, brand name: Lumirror 100-U34, manufactured by Toray Industries, Inc.) is bonded onto the obtained coating film and pressure-bonded with a rubber roller, and then a conveyor-type UV irradiation device (ECS-301G1). The laminate 1 was obtained by curing at an illuminance of 110 kW / cm ² and an exposure amount of 500 mJ / cm ² . The transfer film (C) was peeled off, and the contact angle of the surface (layer to be transferred) of the photocurable resin composition that was in contact with the transfer layer (C-1) of the transfer film was measured. Measured contact angle using distilled water (for measuring nitrogen and phosphorus, manufactured by Kanto Chemical Co., Inc.) and methylene iodide (99%, manufactured by Aldrich) as probe liquid, and surface free according to Kaelble-Uy theory The energy was calculated.

[Comparative Example 1] Preparation of Laminate 2 A photocurable resin composition (NK Hard B100, manufactured by Shin-Nakamura Chemical Co., Ltd.) was coated with polyethylene using a coating rod (# 4, manufactured by RD Specialties). It was applied on a terephthalate film (thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.). The obtained coating film was dried in a high temperature chamber at 70 ° C. for 60 seconds to obtain a coating film having a thickness of about 7 μm. A polyethylene terephthalate film (thickness: 100 μm, brand name: Lumirror 100-U34, manufactured by Toray Industries, Inc.) is bonded onto the obtained coating film and pressure-bonded with a rubber roller, and then a conveyor-type UV irradiation device (ECS-301G1). The laminate 2 was obtained by curing at an illuminance of 110 kW / cm ² and an exposure amount of 500 mJ / cm ² . A polyethylene terephthalate film (thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.) is peeled off, and a layer made of a photocurable resin composition in contact with the polyethylene terephthalate film (thickness: 75 μm) (transferred) The contact angle of the layer) surface was measured. The contact angle measurement and surface free energy calculation were performed in the same manner as in Example 1.

  Table 1 shows the results of “Example 1” and “Comparative Example 1”.

[Example 2]
1A to 1B show an in-mold process using an injection molding machine. As shown in FIG. 1A, the mold 1 is composed of a movable upper mold 1a and a fixed lower mold 1b, and the upper mold 1a is clamped to the lower mold 1b. A cavity 2 having a required product shape is formed between the lower mold 1b and the lower mold 1b. In addition, a resin supply port 3b connected to the resin supply path 3 is provided at substantially the center of the cavity inner surface 2b of the lower mold 1b, and the molten thermoplastic resin 4 passes through the resin supply path 3 from the injection machine (not shown). It is configured to be injected into the tee.
At the time of injection molding, first, as shown in FIG. 1 (b), the adhesive layer surface (D-3) of the transfer film (D) produced in Production Example 4 is bonded to the cavity 2a of the upper mold 1a, and the mold is molded. The upper mold 1a and the lower mold 1b are brought into contact with each other and closed, and the mold 1 is clamped by a mold clamping device (not shown) so as to resist the injection pressure during injection filling. As shown in FIG. 1C, molten thermoplastic resin 4 is injected and filled into the cavity 2 of the mold 1 through the resin supply port 3b of the supply path 3 from an unillustrated injection machine. When the cavity 2 is filled with resin, the resin supply path 3 is blocked by an appropriate blocking means to complete the injection filling process.
While the mold 1 is clamped, the upper mold 1 a and the lower mold 1 b are cooled to a predetermined temperature, and the molded product 5 of the thermoplastic resin 4 is peeled from the mold 1. A transfer film is adhered to the surface of the molded product 5, and the molded product 5 having water and oil repellency and the like on the surface can be obtained.

[Example 3]
2A to 2D show an in-mold process using an injection molding machine. As shown in FIG. 2, the mold 1 includes a movable upper mold 1a and a fixed lower mold 1b. The upper mold 1a and the lower mold are clamped by clamping the upper mold 1a to the lower mold 1b. A cavity 2 having a required product shape is formed between 1b and 1b. In addition, a resin supply port 3b connected to the resin supply path 3 is provided at substantially the center of the cavity inner surface 2b of the lower mold 1b, and the molten thermoplastic resin 4 passes through the resin supply path 3 from the injection machine (not shown). It is configured to be injected into the tee.
At the time of injection molding, first, as shown in FIG. 2 (b), the base material layer surface (E-2) of the transfer film (E) produced in Production Example 5 faces the cavity 2a side of the upper mold 1a. Then, the upper mold 1a and the lower mold 1b of the mold 1 are brought into contact with each other and closed, and the mold 1 is clamped by a mold clamping device (not shown) so as to resist the injection pressure at the time of injection filling. Next, as shown in FIG. 2C, molten thermoplastic resin 4 is injected and filled into the cavity 2 of the mold 1 through the resin supply port 3b of the supply path 3 from an unillustrated injection machine. When the cavity 2 is filled with resin, the resin supply path 3 is blocked by an appropriate blocking means to complete the injection filling process.
While the mold 1 is clamped, the upper mold 1 a and the lower mold 1 b are cooled to a predetermined temperature, and the molded product 5 of the thermoplastic resin 4 is peeled from the mold 1. The transfer surface 5a of the molded product 5 shown in FIG. 2 (d) can be obtained a molded product 5 in which the transfer component is transferred from the transfer layer (E-1) and the surface is given water and oil repellency. .

The figure which shows an example of the in-mold process using an injection molding machine The figure which shows an example of the in-mold process using an injection molding machine

Claims (14)

  A transfer layer containing a fluorosilsesquioxane (a) or a resin composition containing a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) is formed on the substrate surface. Transfer film.   The transfer film according to claim 1, wherein a transfer layer comprising a resin composition containing a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) is formed on the surface of the substrate.   The transfer film according to claim 1, wherein the resin composition further contains a matrix resin (c). The transfer film according to claim 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 a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoro A fluoroaryl having 6 to 20 carbon atoms replaced by methyl; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and A ¹ is Hydrogen, alkyl having 1 to 20 carbon atoms, and arbitrary hydrogen may be replaced with fluorine, aryl having 6 to 20 carbon atoms, and arbitrary hydrogen being replaced with fluorine, carbon number 7 -20, arylalkyl, reactive functional group or polymerizable functional group where any hydrogen may be replaced by fluorine. R _f ¹ ~R _f ⁷ in the formula (I) are each independently, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluoro-butyl, 3,3,4,4 , 5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro- 1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, or α, α , α-trifluoromethylphenyl, A ¹ is hydrogen, alkyl having 1 to 20 carbon atoms, alkyl in which arbitrary hydrogen may be replaced with fluorine, carbon atoms having 6 to 20 carbon atoms, and any hydrogen May be replaced by fluorine Reel, arylalkyl having 7 to 20 carbon atoms, in which arbitrary hydrogen may be replaced by fluorine, cyano, hydroxyl, alkoxy, (meth) acryloyloxy, styryl, (meth) acryl, isocyanato, mercapto, cyclic ether The transfer film according to claim 1, wherein the transfer film is selected from a monovalent functional group containing, alkyl halide, amino, and carboxyl. 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 transfer film according to claim 1, wherein A ¹ is selected from acryloyloxy, methacryloyloxy, styryl, and (meth) acryl.   The transfer film according to any one of claims 1 to 6, wherein the fluorine-based polymer (b) further has a structural unit derived from the addition polymerizable monomer (d).   The addition polymerizable monomer (d) is at least one addition polymerizable monomer selected from an addition polymerizable monomer having a crosslinkable functional group and an addition polymerizable monomer having no crosslinkable functional group. The transfer film according to claim 7, wherein the transfer film is a polymer.   The crosslinkable functional group is selected from a monovalent functional group including cyano, hydroxyl, alkoxy, acryloyloxy, methacryloyloxy, styryl, isocyanato, mercapto, vinyl ether, cyclic ether, alkyl halide, amino and carboxyl. The transfer film according to claim 8, wherein the transfer film is a base.   The transfer film according to any one of claims 3 to 9, wherein the matrix resin (c) is a curable resin and / or a thermoplastic resin.   The transfer film according to claim 10, wherein the curable resin is a thermosetting resin or a photocurable resin.   The transfer film according to any one of claims 1 to 11, wherein an adhesive layer made of an adhesive is further formed on the surface of the substrate opposite to the transfer layer.   Transfer including the step of forming a layer of a resin composition containing fluorosilsesquioxane (a) or a fluoropolymer (b) having a structural unit derived from fluorosilsesquioxane (a) on the surface of the substrate A method for producing a film.   The laminated body formed by forming the to-be-transferred layer which consists of a curable resin composition and / or a thermoplastic resin composition on the transfer film as described in any one of Claims 1-11.

Images