JPWO2020039857A1 - Dry film and decoration method - Google Patents

Abstract

An object of the present invention is to provide a dry film having less irritation and odor, excellent adhesion to an adherend, and not complicated operation at the time of decoration, and a decoration method using the dry film. The dry film of the present invention includes a support film and a resin composition layer, and the resin composition layer comprises a monomer unit represented by the following formula (1) and a monomer unit represented by the following formula (2). It contains a polymer containing at least one monomer unit selected from the group, and the weight average molecular weight of the polymer is 2000 or more and 2 million or less.

Description

The present invention relates to a dry film and a decoration method that exhibit excellent adhesion to an adherend.

Conventionally, colored paint is painted or printed on the surface of a molded product to give it a design, and hard coat paint is spray-painted or dipping-painted on the molded product to protect the surface. .. In recent years, there is a high demand for reducing the amount of VOC (volatile organic compound) used in such decoration applications, and a solvent-free method for decoration is desired. In particular, if the decorative material is a dry film, it should be finished by pasting a dry film of the same area on the required part without scattering like a spray or wasting it with a brush like painting. Becomes possible.

However, as a decorative dry film, a thermosetting composition obtained by adding an acid, a base, an active hydrogen-containing compound, an organic metal catalyst, or the like to a compound having an epoxy group, an isocyanato group, an alkoxysilane group, or the like was used. In this case, there is a limit in that the pot life is short, and in an active energy ray-curable composition in which a compound having an unsaturated bond in the molecule and a photopolymerization initiator are combined, it should be cured by irradiating an appropriate amount of light. However, if the color is dark, it blocks light and there is a limit in terms of colorability.

Further, Patent Document 1 discloses a decorative film composed of a laminate containing a hard coat layer and a base material layer, and an acrylic copolymer (A) in which the hard coat layer has a hydroxyl group and an isocyanate-based curing agent ( It is described as a cured product of a thermosetting coating material containing B), and as an isocyanate-based curing agent (B), an aromatic isocyanate having two or more isocyanato groups in one molecule, an aliphatic isocyanate, and an alicyclic. Group isocyanates are mentioned. However, since the isocyanate-based curing agent used here is a low molecular weight type, it is irritating and has an odor. Further, since the acrylic copolymer (A) having a hydroxyl group and the isocyanate-based curing agent (B) are reacted and used, it is complicated to package them separately and mix them immediately before use. be.

Patent Document 2 discloses a gas barrier film in which an anchor coat layer, an inorganic oxide layer, and an overcoat layer are laminated, and the anchor coat layer is made of a urethane resin in which an acrylic-styrene copolymer and an isocyanate compound are bonded. It is stated that it will be. The isocyanate compound is used to improve the interlayer adhesion with the inorganic oxide layer by utilizing the reactivity with the hydroxyl group contained in the acrylic-styrene copolymer. In this case as well, since low molecular weight types and their modified products are used as the isocyanate compounds, there is a concern about irritation.

Japanese Patent No. 6015877 Japanese Unexamined Patent Publication No. 2017-144603

The present invention provides a dry film having less irritation and odor, excellent transferability, excellent adhesion to an adherend, and not complicated operation at the time of decoration, and a decoration method using the dry film. Make it an issue.

The present inventor has made diligent studies to solve the above problems. As a result, by using a polymer containing a specific monomer unit containing an isocyanato group or a blocked isocyanato group and having a molecular weight of 2000 or more, the irritation and odor observed in the low molecular weight type isocyanate compound are reduced, and the transfer is performed. The present invention has been completed by finding that a dry film having excellent properties and adhesion to an adherend and which is not complicated to operate at the time of decoration can be obtained. That is, the present invention includes the following aspects.

[1] A dry film containing a support film and a resin composition layer.
The resin composition layer contains a polymer containing at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (1) and a monomer unit represented by the following formula (2).
A dry film having a weight average molecular weight of 2000 or more and 2 million or less.

式（１）および（２）中、Ｒ¹およびＲ⁴は炭素数１〜２６の２価の有機基を表し、Ｒ²およびＲ⁵は水素原子または炭素数１〜４のアルキル基を表し、Ｒ³は炭素数１〜１０の１価の有機残基または重亜硫酸塩残基を表し、＊は隣のモノマー単位との結合部を表す。

In formulas (1) and (2), R ¹ and R ⁴ represent divalent organic groups having 1 to 26 carbon atoms, and R ² and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. R ³ represents a monovalent organic residue or a bicarbonate residue having 1 to 10 carbon atoms, and * represents a bond with an adjacent monomer unit.

[2] The dry film according to Item [1], wherein the monomer unit represented by the formula (1) contains a monomer unit represented by the following formula (3).

式（３）中、Ｒ⁶は炭素数１〜２０の２価の有機基を表し、Ｒ²および＊は前記式（１）中のＲ²および＊と同義である。

In the formula (3), R ⁶ represents a divalent organic group having 1 to 20 carbon atoms, and R ² and * are synonymous with ^{R 2} and * in the formula (1).

[3] The dry film according to Item [1], wherein the monomer unit represented by the formula (1) contains a monomer unit represented by the following formula (7).

式（７）中、Ｒ⁸は炭素数１〜２０の２価の有機基を表し、Ｒ²および＊は前記式（１）中のＲ²および＊と同義である。

In the formula (7), R ⁸ represents a divalent organic group having 1 to 20 carbon atoms, and R ² and * are synonymous with ^{R 2} and * in the formula (1).

[4] The dry film according to item [3], ^{wherein R 8} is −CH ₂ − or −CH ₂ CH _{2 −.}
[5] The dry film according to any one of Items [1] to [4], ^{wherein R 2 is a hydrogen atom or a methyl group.}
[6] The dry film according to Item [1], wherein the monomer unit represented by the formula (2) contains a monomer unit represented by the following formula (4).

式（４）中、Ｒ⁷は炭素数１〜２０の２価の有機基を表し、Ｒ³、Ｒ⁵および＊は前記式（２）中のＲ³、Ｒ⁵および＊と同義である。

In formula (4), R ⁷ represents a divalent organic group having 1 to 20 carbon atoms, R ^3, R ⁵ and * are R ^3, R ⁵ and * synonymous in the formula (2).

[7] The dry film according to Item [1], wherein the monomer unit represented by the formula (2) contains a monomer unit represented by the following formula (8).

式（８）中、Ｒ⁹は炭素数１〜２０の２価の有機基を表し、Ｒ³、Ｒ⁵および＊は前記式（２）中のＲ³、Ｒ⁵および＊と同義である。

Wherein (8), R ⁹ represents a divalent organic group having 1 to 20 carbon atoms, R ^3, R ⁵ and * are R ^3, R ⁵ and * synonymous in the formula (2).

[8] The dry film according to item [7], ^{wherein R 9} is −CH ₂ − or −CH ₂ CH _{2 −.}
[9] The dry film according to any one of Items [1] and [6] to [8], ^{wherein R 5 is a hydrogen atom or a methyl group.}

[10] The R ³ is an alcohol compound, a phenol compound, an active methylene compound, a mercaptan compound, an acid amide compound, an acid imide compound, an imidazole compound, a urea compound, an oxime compound, or an amine compound. The dry item according to any one of Items [1] and [6] to [9], which is a residue excluding active hydrogen that reacts with an isocyanato group in an imine compound, a pyridine compound or a heavy sulfite. the film.

[11] The R ³ is the isocyanato group in ε-caprolactam, diethyl malonate, ethyl acetoacetate, acetoxime, methylethylketone oxime, phenol, cresol, imidazole, pyrazole, 3,5-dimethylpyrazole or 2-methylimidazole. Item 6. The dry film according to any one of Items [1] and [6] to [9], which is a residue excluding reactive hydrogen.

[12] Items [1] to [12], wherein the total of the number of monomer units represented by the formula (1) and the number of monomer units represented by the above (2) is 1% or more of the total number of monomer units. 11] The dry film according to any one of the items.

[13] The resin composition layer of the dry film according to any one of Items [1] to [12] is transferred to an adherend having a functional group in which active hydrogen is present on at least a part of the surface. A decoration method characterized by including a process.

[14] The decoration method according to Item [13], wherein the adherend is obtained by dry-treating at least a part of the surface thereof.
[15] The decoration method according to Item [14], wherein the dry treatment is at least one treatment selected from the group consisting of corona treatment, plasma treatment, frame treatment, itro treatment, ultraviolet irradiation treatment and excimer treatment. ..

According to the present invention, there is provided a dry film having less irritation and odor, excellent transferability, excellent adhesion to an adherend, and not complicated operation at the time of decoration, and a decoration method using the dry film. be able to.

Hereinafter, the present invention will be described in detail.
[Dry film]
The dry film of the present invention comprises a support film and a resin composition layer, the resin composition layer containing a polymer having an isocyanato group or a blocked isocyanato group.

<Support film>
The support film is not particularly limited, but for example, a polyester film (polyethylene terephthalate film), a polypropylene film, a polystyrene film, a vinylon film, or the like which has been subjected to an easy slip treatment is preferably used. The slippery treatment is performed by coating the surface of the film with a polyester resin, an acrylic resin, a urethane resin, a silicone resin, a fluorine resin, or the like.

The support film is preferably transparent. The thickness of the support film is preferably 300 μm or less, more preferably 10 to 200 μm. If the thickness of the support film is less than 10 μm, the film is too soft and inconvenient to handle, and if it exceeds 300 μm, it is too hard to follow the shape of the adherend.

<Resin composition layer>
Since the polymer contained in the resin composition layer has an isocyanato group or a blocked isocyanato group, thermosetting property can be exhibited. Hereinafter, the polymer is also referred to as "thermosetting polymer of the present invention" or simply "thermosetting polymer".

(Thermosetting polymer)
The thermosetting polymer of the present invention has a monomer unit represented by the following formula (1) (hereinafter, also referred to as “monomer unit (1)”) and a monomer unit represented by the following formula (2) (hereinafter, “monomer”). It contains at least one monomer unit selected from the group consisting of the unit (2).

式（１）および（２）中、Ｒ¹およびＲ⁴は炭素数１〜２６の２価の有機基を表し、Ｒ²およびＲ⁵は水素原子または炭素数１〜４のアルキル基を表し、Ｒ³は炭素数１〜１０の１価の有機残基または重亜硫酸塩残基を表し、＊は隣のモノマー単位との結合部を表す。

In formulas (1) and (2), R ¹ and R ⁴ represent divalent organic groups having 1 to 26 carbon atoms, and R ² and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. R ³ represents a monovalent organic residue or a bicarbonate residue having 1 to 10 carbon atoms, and * represents a bond with an adjacent monomer unit.

Examples of the divalent organic group in R ¹ and R ⁴ include a carbonyl group; a linear or branched alkylene group; a structure in which a linear or branched alkylene group and a divalent aromatic group are bonded. Group having; Examples thereof include a group having a structure in which a linear or branched alkylene group and an ester bond (-COO-) are bonded. As the alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group are preferable. Further, as the divalent aromatic group, a phenylene group is preferable.

The R ² and R ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
R ³ is a group derived from a blocking agent for protecting the isocyanato group, which will be described later, that is, a residue excluding active hydrogen that reacts with the isocyanato group in ^{the blocking agent (HR 3).}

In the thermosetting polymer, the total of the number of monomer units represented by the formula (1) and the number of monomer units represented by the above (2) is preferably 1% or more of the total number of monomer units, and more. It is preferably 2 to 70%, more preferably 4 to 50%.

From the viewpoint of imparting rigidity to the resin composition layer, the monomer unit (1) contains a monomer unit represented by the following formula (3) (hereinafter, also referred to as “monomer unit (3)”), or , The monomer unit (2) preferably includes a monomer unit represented by the following formula (4) (hereinafter, also referred to as “monomer unit (4)”).

式（３）および（４）中、Ｒ⁶およびＲ⁷は炭素数１〜２０の２価の有機基を表し、Ｒ²、Ｒ³、Ｒ⁵および＊は前記式（１）および（２）中のＲ²、Ｒ³、Ｒ⁵および＊と同義である。

In formulas (3) and (4), R ⁶ and R ⁷ represent divalent organic groups having 1 to 20 carbon atoms, and R ² , R ³ , R ⁵ and * represent the above formulas (1) and (2). Synonymous with R ² , R ³ , R ⁵ and * in.

The R ⁶ and R ⁷ are preferably divalent hydrocarbon groups having 1 to 10 carbon atoms, and more preferably alkylene groups having 1 to 6 carbon atoms.
Examples of the monomer giving the structure of the monomer unit (3) or (4) include 4-isopropenyl-α, α-dimethylbenzylisocyanate and a block thereof.

Further, the monomer unit (1) includes a monomer unit represented by the following formula (5) (hereinafter, also referred to as “monomer unit (5)”), or the monomer unit (2) is represented by the following formula (2). By including the monomer unit represented by 6) (hereinafter, also referred to as "monomer unit (6)"), the concentration of the -NCO group or -NC (= O)-structure of the eutectic can be increased.

式（５）および（６）中、Ｒ²、Ｒ³、Ｒ⁵および＊は前記式（１）および（２）中のＲ²、Ｒ³、Ｒ⁵および＊と同義である。

In the formula (5) and (6), R ^2, R ^3, R ⁵ and * are the formula (1) and (2) R ² in, R ^3, R ⁵ and * as synonymous.

Examples of the monomer giving the structure of the monomer unit (5) or (6) include (meth) acryloyl isocyanate and its block body. In the present specification, (meth) acryloyl means methacrylic or acryloyl, (meth) acrylic means methacrylic or acrylic, and (meth) acrylate means methacrylate or acrylate.

From the viewpoint of availability, the monomer unit (1) includes a monomer unit represented by the following formula (7) (hereinafter, also referred to as “monomer unit (7)”), or the monomer unit (2). ) Contains a monomer unit represented by the following formula (8) (hereinafter, also referred to as “monomer unit (8)”).

式（７）および（８）中、Ｒ⁸およびＲ⁹は炭素数１〜２０の２価の有機基を表し、Ｒ²、Ｒ³、Ｒ⁵および＊は前記式（１）および（２）中のＲ²、Ｒ³、Ｒ⁵および＊と同義である。

In formulas (7) and (8), R ⁸ and R ⁹ represent divalent organic groups having 1 to 20 carbon atoms, and R ² , R ³ , R ⁵ and * represent the above formulas (1) and (2). Synonymous with R ² , R ³ , R ⁵ and * in.

The R ⁸ and R ⁹ are preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent alkylene group having 1 to 5 carbon atoms, and particularly preferably -CH _2- or -CH ₂ CH. ₂ −.

Examples of the monomer giving the structure of the monomer unit (7) or (8) include 2- (meth) acryloyloxyethyl isocyanate and a block thereof. Further, a compound having an ethylenic double bond and an isocyanato group and a compound obtained by reacting an asymmetric diisocyanate compound such as isophorone diisocyanate or tolylene diisocyanate with a compound having both a hydroxyl group and an ethylenic double bond. The block body can also be mentioned.

Examples of the compound having both a hydroxyl group and an ethylenic double bond include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and the above. Caprolactone or alkylene oxide adduct of each (meth) acrylate, allyl alcohol, allyl oxyethanol and the like can be mentioned.

(Blocking agent; HR ³ )
The blocking agent for protecting the isocyanato group, which is used to obtain the block and is ^{represented by HR 3} , is a compound having only one active hydrogen in one molecule capable of reacting with the isocyanato group. It is preferable that the compound dissociates at a temperature of 170 ° C. or lower even after reacting with the isocyanato group.

Examples of such blocking agents include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, imidazole compounds, urea compounds, oxime compounds, amine compounds, and imide compounds. Examples thereof include compounds and pyridine compounds. These may be used alone or in combination of two or more. Specific examples of these blocking agents are shown below.

The alcohol-based compound is a compound having a hydroxyl group (excluding phenolic hydroxyl group), and is, for example, methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclo. Hexanol and the like can be mentioned.

Examples of the phenolic compound include compounds having a phenolic hydroxyl group, such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid ester.

The active methylene compound is a compound having a methylene group (−CH ₂ −) sandwiched between two electron-withdrawing groups, and is, for example, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. And so on.

Examples of the mercaptan-based compound include compounds having a mercapto group, such as butyl mercaptan and dodecyl mercaptan.
Examples of the acid amide compound include acetanilide, acetic acid amide, ε-caprolactam, γ-butyrolactam and the like, which are compounds having a structure in which ammonia or a primary or secondary amine and an oxo acid are dehydrated and condensed.

Examples of the acidimide-based compound are compounds in which two acyl groups are bonded to an imino group, and examples thereof include succinimide and maleateimide.
Examples of the imidazole-based compound include compounds having an imidazole ring, such as imidazole and 2-methylimidazole.

The urea-based compound is a compound having a structure represented by-(NH) -C (= X)-(NH)-(where X is an oxygen atom or a sulfur atom), and is, for example, urea or thiourea. , Ethylene urea and the like.

Examples of the oxime-based compound include compounds having a structure represented by −C (= N—OH) −, such as formaldehyde, acetoaldoxime, acetooxime, methylethylketone oxime, and cyclohexanone oxime.

The amine compound is a compound having an amine structure, for example, diphenylamine, aniline, carbazole, unsubstituted pyrazole, 3,5-dimethylpyrazole, 3-acetylaminopyrazole, pyrazole-3,5-dicarboxylic acid diethyl ester. And so on.

Examples of the imine-based compound include compounds having an imine structure, such as ethyleneimine and polyethyleneimine.
Examples of the pyridine-based compound include compounds having a pyridine structure, such as 2-hydroxypyridine and 2-hydroxyquinoline.

Examples of the heavy sulfite salt include sodium sulfite and the like.
Of these, ε-caprolactam, diethyl malonate, ethyl acetoacetate, acetoxime, methylethylketone oxime, phenol, cresol, imidazole, pyrazole, 3,5-dimethylpyrazole and 2-methylimidazole are preferred.

(Other copolymerizable monomers)
The thermosetting polymer of the present invention may contain a monomer unit other than the monomer unit represented by the above formula (1) or the formula (2). The other monomer unit is preferably 30 to 98%, more preferably 50 to 96% of all the monomer units. Other copolymerizable monomers giving other monomeric units include, for example, (meth) acrylic acid esters and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, (meth) acrylonitrile and derivatives thereof, and organic carboxylic acids. Vinyl esters and derivatives thereof, allyl esters of organic carboxylic acids and derivatives thereof, dialkyl esters of fumaric acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, N-vinylamide derivatives of organic carboxylic acids, maleimides and derivatives thereof, terminal non-terminal Examples thereof include saturated hydrocarbons and derivatives thereof. Specific examples of these are shown below.

Examples of (meth) acrylic acid esters and derivatives thereof include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, -n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth) acrylic. Acid-n-butyl, isobutyl (meth) acrylate, -sec-butyl (meth) acrylate, hexyl (meth) acrylate, -2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (meth) Isobornyl acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate, (meth) -3-Hydroxypropyl acrylate, -2-hydroxybutyl (meth) acrylate, -2-hydroxyphenylethyl (meth) acrylate, -4-hydroxybutyl (meth) acrylate, N, N-dimethyl (meth) In addition to monofunctional (meth) acrylates such as acrylamide, N, N-diethyl (meth) acrylamide and N-acryloylmorpholin, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylpropandi (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol Examples thereof include polyfunctional (meth) acrylates such as hexa (meth) acrylates.

Examples of styrene and its derivatives include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,4,6- Examples thereof include trimethylstyrene, o-chlorostyrene, 2-vinylbiphenyl, 1-vinylanthracene, p-isopropenyltoluene, divinylbenzene and divinylbiphenyl.

Examples of vinyl esters of organic carboxylic acids and their derivatives include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl adipic acid and the like.
Examples of the allyl ester of an organic carboxylic acid and its derivative include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate and the like.

Examples of the dialkyl ester of fumaric acid and its derivative include dimethyl fumarate, diethyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

Examples of the dialkyl ester of maleic acid and its derivative include dimethyl maleate, diethyl maleate, di2-ethylhexyl maleate, and dibenzyl maleate.

Examples of the dialkyl ester of itaconic acid and its derivative include dimethyl itaconic acid, diethyl itaconic acid, -2-ethylhexyl itaconic acid, and dibenzyl itaconic acid.

Examples of the N-vinylamide derivative of the organic carboxylic acid include N-methyl-N-vinylacetamide and the like.
Examples of maleimide and its derivatives include N-phenylmaleimide and N-cyclohexylmaleimide.

Examples of the terminal unsaturated hydrocarbon and its derivative include 1-butene, 1-pentene, 1-hexene, vinylcyclohexane, vinyl chloride, allyl alcohol and the like.
Of these, the polyfunctional monomer needs to be used within a range that does not gel.

(Manufacture of thermosetting polymer)
The thermosetting polymer of the present invention can be produced, for example, by radical polymerization or radical copolymerization of a specific compound having an ethylenic double bond and an isocyanato group and, if necessary, another copolymerizable monomer. .. In addition, the isocyanato group of this polymer is protected by a blocking agent, or a specific compound having an ethylenic double bond with the isocyanato group previously protected by the blocking agent and, if necessary, another copolymerizable monomer are radically polymerized. Alternatively, radical copolymerization may be performed. When protecting the isocyanato group after copolymerization, it is preferable to select a radically polymerizable monomer that does not have a group that reacts with the isocyanato group as the other copolymerizable monomer.

The thermosetting polymer of the present invention can be produced in the absence of a solvent or in the presence of a solvent. Examples of the organic solvent that can be used include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, and diethylene glycol. Ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethyl ethoxypropionate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, Examples thereof include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylsulfoxide, chloroform, methylene chloride and the like.

The concentration of the reaction solution is preferably adjusted so that the resin concentration is 10 to 100% by mass, more preferably 40 to 80% by mass.
The polymerization initiator that can be used in the production of the thermosetting polymer may be any that serves as an initiator for radical polymerization, and examples thereof include an azo-based or organic peroxide-based initiator. Specifically, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, and 2,2'-azobis (2,4-dimethylvaleronitrile); methyl ethyl ketone. Ketone peroxides such as peroxide, methylisobutylketone peroxide, cyclohexanone peroxide, acetylacetone peroxide; isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide , P-chlorobenzoyl peroxide and other diallyl peroxides; 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-butyl peroxide and other hydroperoxides Dialkyl peroxides such as dicumylperoxide, t-butylcumylperoxide, di-t-butylperoxide, tris (t-butylperoxy) triazine; 1,1-di-t-butylperoxycyclohexane, Peroxyketals such as 2,2-di (t-butylperoxy) butane; t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, Di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyacetate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate , Alkyl peroxides such as di-t-butylperoxytrimethyl adipate; peroxycarbonates such as diisopropylperoxycarbonate, disec-butylperoxydicarbonate, t-butylperoxyisopropylcarbonate and the like.

Examples of the radical polymerization initiator that can be used for polymerization with ultraviolet rays include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and 4,4-bis (diethylamino). ) Benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, benzoin, benzoin ethyl ether, benzyl dimethyl ketal, methyl anthraquinone, carbonyl such as chlorothioxanthone Examples include compounds, anthraquinone or thioxanthone derivatives and sulfur compounds.

It is desirable that the reaction for producing the thermosetting polymer of the present invention be carried out by dehydration and nitrogen gas atmosphere. The reaction temperature is preferably set to an optimum temperature according to the polymerization initiator used, and the polymerization in a situation where the isocyanato group is not blocked is preferably 120 ° C. or lower. In the polymerization in a situation where the isocyanato group is blocked, the blocking agent dissociates when the temperature is too high, so a temperature at which the blocking agent does not dissociate is preferable.

The weight average molecular weight of the thermosetting polymer of the present invention thus obtained is 2000 or more and 2 million or less, preferably 2000 or more and 1 million or less, and more preferably 2200 or more and 100,000 or less. In the present invention, the weight average molecular weight is measured by a gel permeation chromatograph (gel permeation chromatograph: GPC) using a standard polystyrene calibration curve. "HLC-8320GPC" (manufactured by Tosoh Corporation) is used as the GPC device, and one "Shodex GPC KF-801" (manufactured by Showa Denko) and three "Shodex GPC LF-804" (manufactured by Showa Denko) are used as columns. It is used, and a differential refractometer is used as a detector, and measurement is performed under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., and flow velocity: 1 mL / min.

(Other ingredients)
The resin composition for forming the resin composition layer (hereinafter, also referred to as “composition of the present invention”) is other than the thermosetting polymer of the present invention as long as the object of the present invention is not impaired. May contain the components of. For example, the solvent and the polymerization initiator from the production of the thermosetting polymer may remain.

Examples of other components preferably contained include carbon materials, pigments, dyes, coloring materials such as pearl photovolatile materials, and inorganic fillers.
Examples of the carbon material include carbon black, acetylene black, lamp black, and graphite.

Examples of the pigment include black pigments such as iron black, aniline black, cyanine black, and titanium black. Further, the composition of the present invention may contain organic pigments such as red, green and blue, and for example, commercially available pigments for gel nails and UV crafts may be used. Examples of such pigments include Pikaace coloring pigments (701, 731, 741, 755, 762) and transparent pigments (900, 901, 910, 920, 921, 922, 924, 930, 932, 941, 942, 945). , 947, 950, 955, 957, 960, 963, 968, 970, 980, 981, 982, 985) and the like.

Examples of the dye include direct dyes, acidic dyes, basic dyes, medium dyes, acidic medium dyes, construction dyes, disperse dyes, reactive dyes, fluorescent whitening dyes, and plastic dyes. The dye means a substance that has solubility in a solvent or compatibility with a resin and has a property of coloring a dissolved or compatible substance.

Examples of the pearl photovolatile material include aluminum flakes, vapor-deposited aluminum flakes, metal oxide-coated aluminum, colored aluminum flakes, and flaky mica coated with a metal oxide such as titanium oxide and iron oxide.

The coloring material can be used alone or in combination of two or more.
The inorganic filler is not particularly limited as long as it is dispersed in the thermosetting polymer of the present invention to form a paste. Examples of such an inorganic filler include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), titanium oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si). ₃ N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum dilconate titanate (PLZT) , gallium oxide (Ga ₂ O _3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite _{(2MgO · 2Al 2 O 3 /} 5SiO 2), talc (3MgO · 4SiO ₂ · H ₂ O), aluminum titanate (TiO ₂ -Al _2O3), yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate ( CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO / TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C), glass powder, synthetic mica, boron nitride Fiber reinforcing materials such as fibers, inorganic supports mixed with silicone oil and powdered, silicone resin or silicone rubber powdered can be used, and one or more of these can be used. You can also do it.

Among the inorganic fillers exemplified above, fine particle silica is preferable from the viewpoint of adjusting the viscosity of the composition of the present invention and the sheet moldability of the cured product formed from the composition of the present invention. Fine particle silica is available from Nippon Aerosil Co., Ltd. under the trade name Aerosil (trademark). As fine particle silica under the trade name of Aerosil (trademark), Aerosil (trademark) OX50, RX50, RY50, 50, NAX50, NY50, NA50H, NA50Y, 90G, NX90G, 130, R972, RY200S, 150, R202, 200, R974 , R9200, RX200, R8200, RY200, R104, RA200H, RA200HS, NA200Y, R805, R711, R7200, 300, R976, R976S, RX300, R812, R812S, RY300, R106, 380, P25, T805, P90, NKT90, Aluc , AluC805 and the like, of which RX200 is more preferable from the viewpoint of dispersibility.

The content of the inorganic filler is not particularly limited, but is preferably less than 10 parts by mass with respect to 100 parts by mass of the thermosetting polymer of the present invention from the viewpoint of moldability of the cured product formed from the composition of the present invention. , 2 to 6 parts by mass is more preferable.

In addition to the coloring material and the inorganic filler, the composition of the present invention contains (a) a thermoplastic resin; (b) a deodorant; (c) a silane coupling agent and a titanium coupling agent as other components. Adhesion improvers such as; (d) Antioxidants such as hindered amines, hydroquinones, hindered phenols; (e) Ultraviolet absorbers such as benzophenones, benzotriazoles, salicylates, metal complex salts; f) Stabilizers for metal soaps, inorganic and organic salts of heavy metals (eg zinc, tin, lead, cadmium, etc.), organic tin compounds, etc .; (g) acetic acid, acrylic acid, palmitic acid, oleic acid, mercaptocarboxylic acid, etc. PH adjusters such as aromatic organic acids such as aliphatic carboxylic acids, phenols, naphthols, benzoic acids and salicylic acids; (h) phthalic acid esters, phosphate esters, fatty acid esters, epoxidized soybean oils, castor oil, liquid paraffin alkyl polycycles. Plastics such as aromatic hydrocarbons; (i) Waxes such as paraffin wax, microcrystalinwanks, polymerized wax, dense wax, whale wax low molecular weight polyolefin; (j) Non-reactive such as benzyl alcohol, tar, pitumen, etc. Diluting agent; (k) filler such as acrylic resin powder, phenol resin powder; (l) solvent such as ethyl acetate, toluene, alcohols, ethers, ketones; (m) foaming agent; (n) silane coupling Dehydrating agents such as agents, monoisocyanate compounds, carbodiimide compounds; (o) antistatic agents; (p) antibacterial agents; (q) antifungal agents; (r) viscosity modifiers; (s) fragrances; (t) flame retardants It can contain (u) leveling agent; (v) sensitizer; and (w) dispersant and the like. These other components may be used alone or in combination of two or more at any ratio.

(Method of forming the resin composition layer)
The resin composition layer is laminated on the support film. As a laminating method, for example, the composition of the present invention was applied onto a support film with a film thickness of 10 to 500 μm by a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, or the like. After that, a method of drying at 60 to 110 ° C. can be mentioned.

<Protective film>
When the dry film of the present invention is used in the form of a roll, the resin composition layer is transferred to the support film, dust or the like adheres to the resin composition layer, and the influence of moisture (water) during storage. The protective film may be laminated on the resin composition layer in the order of the support film / resin composition layer / protective film for the purpose of preventing the above.

Examples of the protective film include polyester film, polyethylene film, polypropylene film, polyvinyl alcohol film, Teflon film and the like. The thickness of the protective film is not particularly limited, but is preferably 10 to 50 μm in consideration of cost.

<Design layer>
For the purpose of improving the design of the dry film of the present invention, a color layer exhibiting a paint color or a metallic color, a wood grain, a geometric pattern, a pattern layer giving a leather pattern or a pattern, and a relief for providing an uneven shape on the surface. The layers and the like and combinations thereof may be laminated as the design layer in the order of, for example, the support film / resin composition layer / design layer / protective film.

As the color layer, the above-mentioned pigments, dyes and pearl photovolatile materials dispersed in acrylic resin, polyurethane resin and the like can be used.
As the pattern layer, gravure direct printing, gravure offset printing, inkjet printing, laser printing, screen printing and other printing, gravure coating, roll coating, die coating and other coatings, films with patterns and logos, sheets, metal foil, etc. are used. can do.

As the relief layer, a thermoplastic resin film having a concavo-convex shape on the surface can be used by a conventionally known method such as embossing, scratching, or heat pressing. A relief layer can also be formed by applying a curable acrylic resin on a release film having an uneven shape on the surface and curing the release film with heat or light to remove the release film. The thermoplastic resin and curable resin used for the relief layer are not particularly limited, but are fluororesin, polyester resin, acrylic resin, polyethylene, polypropylene, thermoplastic elastomer, polycarbonate, polyamide, ABS resin, acrylonitrile / styrene resin, and porstyrene. , Vinyl chloride, polyurethane and the like can be used.
The thickness of the design layer may vary and is generally less than 0.2 mm.

[Decoration method]
The decoration method of the present invention is characterized by including a step of transferring the resin composition layer of the dry film of the present invention described above to an adherend having a functional group in which active hydrogen is present on at least a part of the surface. And.

<Subject>
Conventionally, when the adherend is decorated with a dry film, the primer composition is applied to the adhesive surface, and then the adhesive is applied and bonded. On the other hand, in the case of the present invention, since a sensitive reaction between the isocyanato group and the active hydrogen can be utilized, if the adherend has a functional group in which the active hydrogen such as a hydroxyl group, a carboxyl group, an amino group or a mercapto group is present, chemistry Can be firmly adhered. Even in the case of a blocked isocyanato group, by heating to a temperature at which the blocked portion dissociates, the functional group in the adherend and the dissociated isocyanato group can be reacted and chemically strongly adhered. can.

Examples of the material of the adherend having a functional group in which active hydrogen such as a hydroxyl group is present include an epoxy resin. Further, even in the case of a thermoplastic resin, an adherend having a functional group in which active hydrogen is present can be obtained by dry-treating at least a part of the surface thereof.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene and polybutylene, methacrylic resins such as polymethylmethacrylate, polystyrene resins such as polystyrene, ABS and AS, polyethylene terephthalate (PET) and polyvetylene terephthalate (PBT). Polyester resins such as polytrimethylene terephthalate, polyethylene naphthalate, (PEN), poly 1,4-cyclohexyldimethylene terephthalate (PCT), polycaproamide (nylon 6), polyhexamethylene sebacamide (nylon 610), Polyhexamethylene dodecamide (nylon 612) polydodecaneamide (nylon 6T), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66) Polyene resin selected from nylon resin such as / 6T) and nylon copolymer resin, polyvinyl chloride resin, polyoxymethylene (POM), polycarbonate resin (PC), polyphenylene sulfide resin (PPS), modified polyphenylene ether resin (PPE) , Polyetherimide resin (PEI), Polysulfone resin (PSF) Polyethersulfone resin (PES), Polyketone resin, Polyethernitrile resin (PEN) Polyetherketone resin (PEK), Polygonide resin (PI), Polyamideimide resin ( PAI), fluororesin and the like can be mentioned.

The dry treatment preferably irradiates a high-energy gas in a plasma state. The dry treatment may be applied to the entire surface of the member or a part of the surface of the member.
The type of dry treatment for irradiating a high-energy gas in a plasma state is not particularly limited, but at least one selected from the group consisting of corona treatment, plasma treatment, frame treatment, itro treatment, ultraviolet irradiation treatment, and excimer treatment. It is preferable, and frame treatment, plasma treatment, and corona treatment are more preferable. The dry treatment may consist of one dry treatment (one pass or one sweep) or a plurality of unit dry treatments (multiple passes or multiple sweeps). When the dry treatment is a plurality of unit dry treatments, the next unit dry treatment may be performed without intervals, or the members may be allowed to cool after the unit treatment and then the next dry treatment may be performed.

When the dry treatment comprises a plurality of unit dry treatments, the surface free energy of the member surface increases with each unit dry treatment, so that the adhesion between the dry film and the adherend can be further improved.

Plasma treatment is a method of surface treatment by plasma discharge, and examples thereof include atmospheric pressure plasma treatment and vacuum plasma treatment. The plasma gas (process gas) used for plasma treatment is not particularly limited, and examples thereof include nitrogen gas, helium gas, argon gas, and gas obtained by mixing oxygen gas, carbon dioxide gas, or hydrogen gas with these gases. Be done. The conditions for plasma treatment are generally a speed of 10 to 1500 mm / sec and a distance of 1 to 100 mm between the plasma discharge nozzle and the surface of the member.

Corona treatment is a method of surface treatment by corona discharge. The conditions for corona treatment are generally a speed of 10 to 1000 mm / sec and a distance of 5 to 100 mm between the corona discharge nozzle and the surface of the member.

Frame treatment is a method of surface treatment with a frame (flame). For the frame processing, a conventionally known method such as a method using a burner can be used. Generally, the conditions for frame processing are a gas pressure of 0.005 to 10 MPa, a frame processing speed of 100 to 2000 mm / sec, and a distance of 10 to 600 mm between the frame and the surface of the member.

The itro treatment is a treatment in which a silane compound or the like is introduced into a fuel gas to form a frame (flame), and the surface is treated with the flame to form a nano-level silicon oxide film on the surface. The conditions for the itro treatment are generally a gas pressure of 0.005 to 10 MPa, a speed of 100 to 2000 mm / sec, and a distance of 10 to 600 mm between the burner and the surface of the member.

The ultraviolet irradiation treatment is a method of surface treatment using a high-pressure mercury lamp, a metal halide lamp, a microwave-type electrodeless lamp, a low-pressure mercury lamp, a xenon lamp, or the like as a light source, and a hydroxy group is newly generated and amplified. The light source is preferably a xenon lamp containing a component having a wavelength of 200 nm or less, and the integrated exposure amount is generally ^{2 J / cm 2.} Also. The oxygen concentration during the treatment is preferably 1% or less, more preferably 0.5% or less, although it may be under atmospheric pressure or reduced pressure. As a method of adjusting the oxygen concentration, there is a method of lowering the oxygen concentration by using nitrogen gas.

The excimer treatment is a method of activating oxygen in the air with vacuum ultraviolet rays having a wavelength of 180 nm or less in which Xe is enclosed to generate ozone and oxygen radicals for surface treatment. The oxygen concentration is preferably in the range of 300 ppm to 5%, and the oxygen concentration can be adjusted by introducing an inert gas such as nitrogen gas into the irradiation chamber and adjusting the flow rate thereof.

The adherend used in the present invention may be a composite member containing an inorganic substance. Examples of inorganic substances include silica, titanium oxide, magnesium oxide, antimony oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, mica, glass fiber, carbon black, graphite, and carbon fiber. Can be mentioned.

The method for transferring the resin composition layer of the dry film of the present invention to the adherend is not particularly limited, and a known method can be adopted. That is, when transferring the resin composition layer of the dry film of the present invention to an adherend, the support film is peeled off to expose the resin composition layer, and then the exposed surface is brought into contact with the adherend to transfer. do it.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
<Synthesis Examples A to D>
In a 500 mL four-necked separable flask equipped with an induction stirrer, a thermometer, and a cooling tube, the monomer was dissolved in a solvent at the blending ratio shown in Table 1, and then a polymerization initiator was added at 25 ° C. to 70 ° C. The temperature was raised and the reaction (copolymerization) was carried out to obtain a mixture containing a copolymer.

After completion of synthesis, measurement of polystyrene-equivalent weight average molecular weight (Mw) by GPC and measurement of solid content by heating residue of the sample (1 g of sample was removed of volatile matter in an atmosphere of 50 ° C. for 3 hours, and the initial stage was The mass of the remaining portion with respect to the mass was calculated). In addition, the functional group equivalent was calculated for the obtained copolymer. The functional group equivalent is the molecular weight per isocyanato group or block type isocyanato group, and is represented by the following formula.
Functional group equivalent (g / mol) = solid content (g) / number of moles of monomer having isocyanato group or block type isocyanato group (mol)

The meanings of the abbreviations of the compounds in Table 1 are as follows.
* 1 PGM-Ac: Propylene glycol monomethyl ether acetate * 2 AOI-VM (trademark, manufactured by Showa Denko KK): 2-acryloyloxyethyl isocyanate (molecular weight 141)
* 3 AOI-BP (trademark, manufactured by Showa Denko KK): 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate (containing isocyanato group protected by a blocking agent; molecular weight 237)
* 4 MMA: Methyl methacrylate (molecular weight 100)
* 5 BMA: Butyl methacrylate (molecular weight 142)
* 6 V-601 (Product name, manufactured by Wako Pure Chemical Industries, Ltd.): Dimethyl 2,2'-azobis (2-methylpropionate)

<Subject>
As the adherend, a polypropylene film subjected to corona treatment under the following conditions (thickness 60 μm, hereinafter also referred to as “PP film (corona treatment)”), and a polypropylene film not subjected to the corona treatment (thickness 60 μm, hereinafter “corona treatment”). "PP film (untreated)") and the following epoxy substrate were prepared.
(Corona processing conditions)
Corona discharge surface treatment device CTW-0212 (manufactured by Wedge Co., Ltd.)
50 W / min / m ² (radiation width 0.3 m, speed 2 m / min, output 30 W)
(Epoxy substrate)
An epoxy compounding solution containing the following components (1) to (3) is applied onto a glass fiber-impregnated epoxy substrate having a thickness of 1.5 mm so as to have a film thickness of 0.3 mm, and cured by heating at 130 ° C. for 1 hour. bottom.
(1) jER828 (manufactured by Mitsubishi Chemical, bisphenol A type epoxy resin) 61 parts by mass (2) PEMP (manufactured by SC Organic Chemistry Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate)) 39 parts by mass (3) 2 , 4,6-Tris (dimethylaminomethyl) phenol 1 part by mass

<Peel test base material>
As a base material for the peel test, a polypropylene film (thickness 60 μm) subjected to the above-mentioned corona treatment was prepared.

[Examples 1 to 3 and Comparative Examples 1 to 2]
In Examples 1 to 3, dry films were prepared using the mixtures obtained in Synthesis Examples A to C as resin compositions containing a copolymer having an isocyanato group or a blocked isocyanate group.

In Comparative Example 1, as a resin composition containing a compound having an isocyanato group but not a polymer or a copolymer, the solid content of the mixture containing the copolymer obtained in Synthesis Example D was 100 parts by mass with respect to 100 parts by mass. A composition obtained by mixing 30 parts by mass of "Duranate (trademark) TLA-100" manufactured by Asahi Kasei Co., Ltd. (a nurate compound of 1,6-hexamethylene diisocyanate, a molecular weight of 860, hereinafter abbreviated as "TLA-100"). A dry film was made using the material.

In Comparative Example 2, as a resin composition containing a compound having a block isocyanate group but not a polymer or a copolymer, 100 parts by mass (solid content) of the mixture containing the copolymer obtained in Synthesis Example D was added. , Asahi Kasei Co., Ltd. "Duranate (trademark) SBB-70P (pyrazole type)" (Pyrazol derivative blocked isocyanate of 1,6-hexamethylene diisocyanate, molecular weight 1740, hereinafter may be abbreviated as "SBB-70P") A dry film was prepared using a composition in which 30 parts by mass was mixed.
The dry film was prepared and evaluated as follows.

<Making a dry film>
Each of the above compositions is applied to a PET separator "HY-S10" (manufactured by Higashiyama Film Co., Ltd., film thickness 50 μm) as a support film with a bar coater No. 32, dried at 130 ° C. for 2 minutes to form a film thickness. A dry film having a coating film (resin composition layer) of 30 μm was obtained, and the tactile sensation, transferability and peel strength were evaluated by the following methods. The results are shown in Table 2.

(Tactile)
The coating film on the obtained dry film was touched. The evaluation criteria are as follows.
A: No stickiness (no tack).
B: I feel sticky, but the coating film does not transfer to my fingers.
C: The coating film is almost liquid and peels off from the PET separator when rubbed with a finger.

(Transcribability)
The coating film surface of the obtained dry film is placed toward the adherend, and the coating film is applied to the adherend under the following conditions using an ACF crimping device (heat crimping controller PHC-500, manufactured by Seiwa Seisakusho Co., Ltd.). Transferred.
Indenter area: 2 mm x 50 mm
Pressure: 100N
Indenter temperature: 110 ° C
Pressing time: 40 seconds The evaluation criteria are as follows.
A: Completely transcribed.
B: A coating film remained on the support in part.
C: No transcription was done.

(Peel strength)
Instead of the support film, each of the above-mentioned compositions was applied to the above-mentioned peel test base material with a bar coater No. 32, dried at 130 ° C. for 2 minutes, and a coating film (resin composition layer) having a film thickness of 30 μm. The coating film surface having the above was placed toward the adherend and attached under the same conditions using an ACF crimping device as described above, and the peeling strength (peel strength) of the crimped portion (2 mm × 50 mm) was measured. As a measuring method, a tensile tester (Shimadzu small desktop tester EZTest series TRAPEZIUM2, manufactured by Shimadzu Corporation) is used, one of which fixes the adherend and the other of which is a dry film for peel strength test (base material for peel test / resin composition). The laminate of the material layer) was fixed, and the interface between the adherend and the cured surface of the resin composition layer was peeled off at a speed of 50 mm / min for measurement.

(Odor)
The presence or absence of odor of the obtained dry film (layered body of support film / resin composition layer) was evaluated by a sensory test.

In Table 2, the resins A to D mean the copolymers obtained in Synthesis Examples A to D, respectively.
The dry film (Examples 1 to 3) prepared by using a copolymer having an isocyanato group or a block type isocyanato group is not sticky and is coated on an epoxy substrate or a corona-treated polypropylene film (resin composition layer). Was able to be transferred. On the other hand, in the dry film (Comparative Examples 1 and 2) prepared by using a compound having an isocyanato group or a block type isocyanato group but not a copolymer, the dry film was sticky and the transfer was incomplete.

When the untreated polypropylene film having active hydrogen and no functional group was an adherend, it was not transferred in any of Examples 1 to 3 and Comparative Examples 1 and 2.
The peel strength was highest in Example 2 having a high concentration of isocyanato groups in the resin, but Example 1 having a low concentration of isocyanato groups and Example 3 having a block-type isocyanato group also showed adhesion. Numerical values were obtained. On the other hand, Comparative Examples 1 and 2 using a compound having an isocyanato group or a block-type isocyanato group but not a copolymer were peeled off during attachment to a jig for performing a peel test, and the measurement itself. I couldn't.

Claims (15)

A dry film containing a support film and a resin composition layer.
The resin composition layer contains a polymer containing at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (1) and a monomer unit represented by the following formula (2).
A dry film having a weight average molecular weight of 2000 or more and 2 million or less.

[In formulas (1) and (2), R ¹ and R ⁴ represent divalent organic groups having 1 to 26 carbon atoms, and R ² and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. , R ³ represents a monovalent organic residue or a bicarbonate residue having 1 to 10 carbon atoms, and * represents a bond with an adjacent monomer unit. ] The dry film according to claim 1, wherein the monomer unit represented by the formula (1) contains a monomer unit represented by the following formula (3).

[In the formula (3), R ⁶ represents a divalent organic group having 1 to 20 carbon atoms, and R ² and * are synonymous with ^{R 2} and * in the formula (1). ] The dry film according to claim 1, wherein the monomer unit represented by the formula (1) contains a monomer unit represented by the following formula (7).

[In the formula (7), R ⁸ represents a divalent organic group having 1 to 20 carbon atoms, and R ² and * are synonymous with ^{R 2} and * in the formula (1). ] The dry film according to claim 3, wherein R ⁸ is −CH ₂ − or −CH ₂ CH _{2 −.} The dry film according to any one of claims 1 to 4, wherein R ^{2 is a hydrogen atom or a methyl group.} The dry film according to claim 1, wherein the monomer unit represented by the formula (2) contains a monomer unit represented by the following formula (4).

[In formula (4), R ⁷ represents a divalent organic group having 1 to 20 carbon atoms, R ^3, R ⁵ and * has the same meaning as R ^3, R ⁵ and * in the formula (2) .. ] The dry film according to claim 1, wherein the monomer unit represented by the formula (2) contains a monomer unit represented by the following formula (8).

[In the formula (8), R ⁹ represents a divalent organic group having 1 to 20 carbon atoms, and R ³ , R ⁵ and * are synonymous with ^{R 3} , R ⁵ and * in the formula (2). .. ] The dry film according to claim 7, wherein R ⁹ is −CH ₂ − or −CH ₂ CH _{2 −.} The dry film according to any one of claims 1 and 6 to 8, wherein R ^{5 is a hydrogen atom or a methyl group.} R ³ is an alcohol compound, a phenol compound, an active methylene compound, a mercaptan compound, an acid amide compound, an acid imide compound, an imidazole compound, a urea compound, an oxime compound, an amine compound, and an imine compound. The dry film according to any one of claims 1 and 6 to 9, which is a residue of a compound, a pyridine compound or a heavy sulfite, excluding active hydrogen that reacts with an isocyanato group. The ^{activity of R 3 in} reacting with an isocyanato group in ε-caprolactam, diethyl malonate, ethyl acetoacetate, acetoxime, methylethylketone oxime, phenol, cresol, imidazole, pyrazole, 3,5-dimethylpyrazole or 2-methylimidazole. The dry film according to any one of claims 1 and 6 to 9, which is a residue excluding hydrogen. Any one of claims 1 to 11, wherein the total of the number of monomer units represented by the formula (1) and the number of monomer units represented by the above (2) is 1% or more of the total number of monomer units. The dry film described in the section. It is characterized by including a step of transferring the resin composition layer of the dry film according to any one of claims 1 to 12 to an adherend having a functional group in which active hydrogen is present on at least a part of the surface. How to decorate. The decoration method according to claim 13, wherein at least a part of the surface of the adherend is dry-treated. The decoration method according to claim 14, wherein the dry treatment is at least one treatment selected from the group consisting of corona treatment, plasma treatment, frame treatment, itro treatment, ultraviolet irradiation treatment, and excimer treatment.