JP2017052230A - Transfer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer film which can be wound in a roll shape without blocking.SOLUTION: There is provided a transfer film in which a hard coat layer and an adhesive layer are laminated in this order on a release film. The hard coat layer has a film thickness of 0.1 to 5 μm and the adhesive layer has a film thickness of 0.02 to 1 μm. The adhesive layer is formed by curing a resin composition for an adhesive layer which comprises (B) 5 to 25 pts.mass of a polyfunctional thiol compound and (C) 5 to 35 pts.mass of a polyfunctional ene compound based on (A) 100 pts.mass of a maleic anhydride-modified polyolefin resin. As the (A) component, a resin obtained by graft modification of a (co)polymer of an α-olefin having 2 to 4 carbon atoms with maleic anhydride or a resin obtained by graft modification of a copolymer of an α-olefin having 2 to 4 carbon atoms and maleic anhydride with maleic anhydride can be used.SELECTED DRAWING: None

Description

  The present invention relates to a transfer film that can be wound into a roll shape without blocking.

  Conventionally, as a method of forming a scratch-resistant protective layer (hard coat layer) on the surface of a resin molded product, an ultraviolet curable resin or a thermosetting resin is applied to the surface of the resin molded product by dipping or spraying, and then, The method of hardening according to the hardening method of resin was performed. However, this method has a problem that foreign matters are easily mixed during the coating process. Further, when the resin molded product is a polyvinyl chloride resin, chlorine gas is generated from the resin molded product when the ultraviolet curable resin is cured by ultraviolet rays on the resin molded product. As a result, there is also a problem that the hard coat layer made of the ultraviolet curable resin turns yellow.

  As a method for solving this problem, a transfer film in which a hard coat layer is laminated on a release film in advance is mounted on the inner surface of the mold, and a resin molded product is injection-molded. At the same time, the hard coat layer is transferred to the surface of the resin molded product. The method is known. For example, Patent Document 1 discloses a transfer in which a hard coat layer made of an active energy ray-curable resin composition and a primer layer made of an acrylic resin containing a quaternary ammonium salt structure are laminated in this order on a release film. A film is disclosed. This transfer film is bonded to the surface of the resin molded product via an adhesive layer, but it is disclosed that the adhesive layer may be laminated in advance on the primer layer of the transfer film. The adhesive layer is also made of an acrylic resin containing a quaternary ammonium salt structure. In order to transfer the hard coat layer onto the surface of the resin molded product using this transfer film, it is adhered to the resin molded product through the adhesive layer of the transfer film, and then the release film is peeled and removed, and then the hard coat layer is applied. It is cured by irradiation with active energy rays.

JP 2014-188749 A

  However, in Patent Document 1, the adhesive layer is made of an acrylic resin containing a quaternary ammonium salt. Therefore, when the transfer film provided with such an adhesive layer is wound up and stored in a roll shape, if the transfer film is exposed to high temperature and high humidity conditions, the adhesive layer is tacky and the surface becomes sticky. In this case, there arises a problem that the wound and laminated transfer films are blocked (joined), and the transfer film cannot be unwound from the roll.

  Therefore, the object of the present invention is that it can be wound into a roll shape without blocking, and is excellent in pencil hardness, scratch resistance, adhesion, solvent resistance, and moisture resistance when transferred to a resin molded product. It is to provide a transfer film.

（式中のａは２〜３の整数であり、ｂは０又は１であり、ｃは１〜２の整数であり、ａとｂとｃの和は４である。Ｒ^１は、メチレン基、エチレン基又はイソプロピレン基である。Ｒ^２は、下記（式２）又は（式３）で表される２価の官能基である。Ｒ^３は、メチル基又はエチル基である。Ｒ^４は、炭素数が１〜１２の炭化水素基である。）

（Ｒ^５は水素原子又はメチル基である。）

（Ｒ^５は水素原子又はメチル基である。）
（５）前記（Ｂ）成分が、下記（式４）で示される多官能チオール化合物である、（１）〜（３）のいずれかに記載の転写フィルム。

（式中のｄは２〜５の整数であり、ｅは０〜２の整数であり、ｆは１〜４の整数であり、ｄとｅとｆの和は６である。Ｒ^１は、メチレン基、エチレン基又はイソプロピレン基である。Ｒ^２は、下記（式２）又は（式３）で表される２価の官能基である。Ｒ^３は、メチル基又はエチル基である。Ｒ^４は、炭素数が１〜１２の炭化水素基である。Ｒ^６は下記（式５）で表される６価の官能基である。）

（Ｒ^５は水素原子又はメチル基である。）

（Ｒ^５は水素原子又はメチル基である。）

（６）前記（Ｂ）成分が、下記（式６）で示される多官能チオール化合物である、（１）〜（３）のいずれかに記載の転写フィルム。

（式中のｇは１であり、ｈは２である。Ｒ^７は下記（式７）で表される３価の基であり、Ｒ^８は下記（式２）又は下記（式３）で表される２価の基である。Ｒ^９は炭素数が１〜１２の炭化水素基である。）

（式中のＲ^１０は−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、又はＣＨ_２ＣＨ（ＣＨ_３）−である。）

（Ｒ^５は水素原子又はメチル基である。）

（Ｒ^５は水素原子又はメチル基である。）
（７）前記（Ａ）成分１００質量部に対し、さらに（Ｄ）光重合開始剤を０．０１〜１０質量部含有する、（１）〜（６）のいずれかに記載の転写フィルム。 For this purpose, the present invention adopts the following means.
(1) On the release film, a hard coat layer and an adhesive layer are laminated in this order from the release film side, and the film thickness of the hard coat layer is 0.1 to 5 μm. The film thickness is 0.02 to 1 μm, and the adhesive layer is (B) 5 to 25 parts by mass of (B) polyfunctional thiol compound and (C) polyfunctional with respect to 100 parts by mass of (A) maleic anhydride modified polyolefin resin. The transfer film which is a layer formed by hardening | curing the resin composition for contact bonding layers containing 5-35 mass parts of ene compounds.
(2) The (A) component is a (co) polymer of an α-olefin having 2 to 4 carbon atoms, a maleic anhydride graft-modified resin, that is, an (co) polymer of an α-olefin having 2 to 4 carbon atoms. The transfer film according to (1), which is a resin obtained by graft modification of maleic acid with maleic anhydride. In the present invention, “(co) polymer” means a polymer obtained by homopolymerizing only one type of monomer, or a copolymer obtained by copolymerizing a plurality of types of monomers.
(3) The component (A) is a maleic anhydride graft-modified resin of a copolymer of a C2-C4 α-olefin and maleic anhydride, that is, a C2-C4 α-olefin and maleic anhydride. The transfer film according to (1), which is a resin obtained by graft-modifying a copolymer with an acid with maleic anhydride.
(4) The transfer film according to any one of (1) to (3), wherein the component (B) is a polyfunctional thiol compound represented by the following (formula 1).

(In the formula, a is an integer of 2 to 3, b is 0 or 1, c is an integer of 1 to 2, and the sum of a, b and c is 4. R ¹ is a methylene group. R ² is a divalent functional group represented by the following (formula 2) or (formula 3), R ³ is a methyl group or an ethyl group, and R ⁴ is an ethylene group or an isopropylene group. Is a hydrocarbon group having 1 to 12 carbon atoms.)

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)
(5) The transfer film according to any one of (1) to (3), wherein the component (B) is a polyfunctional thiol compound represented by the following (formula 4).

(In the formula, d is an integer of 2 to 5, e is an integer of 0 to 2, f is an integer of 1 to 4, and the sum of d, e, and f is 6. R ¹ is methylene group, an ethylene group or an isopropylene group .R ² is .R ³ is a divalent functional group represented by the following (equation 2) or (formula 3) is a methyl group or an ethyl group. R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ is a hexavalent functional group represented by the following (formula 5).

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)

(6) The transfer film according to any one of (1) to (3), wherein the component (B) is a polyfunctional thiol compound represented by the following (formula 6).

(In the formula, g is 1 and h is 2. R ⁷ is a trivalent group represented by the following (Formula 7), and R ⁸ is the following (Formula 2) or the following (Formula 3). R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms.)

_(-CH 2 ^{R 10} in the formula _{-, - CH 2 CH 2 -} , or _CH 2 _{CH (CH 3)} - and is.)

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)
(7) The transfer film according to any one of (1) to (6), further containing 0.01 to 10 parts by mass of a photopolymerization initiator (D) with respect to 100 parts by mass of the component (A).

  In the transfer film of the present invention, the adhesive layer is formed of a resin composition that does not cause tackiness even when exposed to high-temperature and high-humidity conditions. Thereby, even if a transfer film is wound up and stored in a roll shape, blocking between adjacent transfer films via an adhesive layer can be prevented. In addition, by setting the film thickness of the hard coat layer and the adhesive layer within a predetermined range, excellent pencil hardness, scratch resistance, adhesion, solvent resistance, and moisture resistance after transfer to the resin molded product are achieved. It can be secured. Furthermore, in the present invention, the hard coat layer that has been cured in advance through the adhesive layer is transferred by heat during the molding of the resin molded product. Therefore, even if the resin molded product is made of polyvinyl chloride resin, the hard coat layer does not turn yellow after transfer.

  In the transfer film of this embodiment, a hard coat layer obtained by curing a resin composition for a hard coat layer is laminated on one side of a release film, and further, the resin composition for an adhesive layer is cured on the hard coat layer. The adhesive layer is laminated. Below, the component of this transfer film is demonstrated in order.

<Release film>
Although there is no restriction | limiting in particular as a constituent material of a release film, For example, a polypropylene resin, a polyethylene resin, a polyamide resin, a polyester resin, a polycarbonate resin, an acrylic resin, a polyvinyl chloride resin, a cellulose acetate resin A resin sheet such as a fluorine-based resin can be used.

  The thickness of the release film is preferably 20 to 200 μm. When the thickness of the release film is less than 20 μm, the strength of the release film is reduced, and the release film may be broken when the release film is peeled off after transfer. On the other hand, there is no technical problem even if the thickness of the release film is larger than 200 μm, but the cost is wasted.

  In addition, in order to improve the mold release property, a mold release material can also be apply | coated to a mold release surface (joint surface with a hard-coat layer). Examples of release materials include epoxy resin release agents, epoxy melamine resin release agents, melamine resin release agents, amino alkyd resin release agents, silicone resin release agents, and fluororesin release agents. 1 type (s) or 2 or more types, such as an agent, a cellulose derivative type release agent, a urea resin type release agent, a polyolefin resin type release agent, and a paraffin type release agent, can be used.

<Hard coat layer>
The hard coat layer is a layer for imparting a high-hardness film excellent in scratch resistance and the like to a resin molded product to be transferred. The material for the hard coat layer is not particularly limited as long as it is a known active energy ray-curable resin that has been conventionally used as a hard coat layer for resin molded products. For example, a hard coat layer resin composition obtained by mixing a reactive silicon compound such as tetraethoxysilane and an active energy ray-curable resin was cured with active energy rays such as ultraviolet rays (UV) or electron beams. A cured product is mentioned. Examples of the active energy ray-curable resin include monofunctional (meth) acrylate and polyfunctional (meth) acrylate. Among these, from the viewpoint of achieving both productivity and hardness, a cured product of a composition containing an active energy ray-curable resin having a pencil hardness (evaluation method: JIS-K5600-5-4) of HB or higher is preferable. . Examples of the composition containing such an active energy ray-curable resin include, for example, a mixture of two or more known active energy ray-curable resins, a commercially available ultraviolet curable hard coat material, or other than these In the range where the effects of the present invention are not impaired, those further added with other components can be used. In the present specification, “(meth) acrylate” refers to acrylate or methacrylate.

  The resin composition for a hard coat layer also contains a photopolymerization initiator. The photopolymerization initiator is used as a polymerization initiator when a hard coat layer resin composition is cured by an active energy ray such as ultraviolet (UV) to form a coating film. The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. Examples thereof include acetophenone polymerization initiators, benzoin polymerization initiators, benzophenone polymerization initiators, and thioxanthone polymerization initiators. Examples of the acetophenone polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2-methyl-1- [4- (methylthio) phenyl]. -2-morpholinopropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like. Examples of the benzoin-based polymerization initiator include benzoin and 2,2-dimethoxy 1,2-diphenylethane-1-one. Examples of the benzophenone polymerization initiator include benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ′, 4,4′-tetra (t- Butyl peroxycarbonyl) benzophenone. Examples of the thioxanthone polymerization initiator include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  The photopolymerization initiator is preferably contained in the hard coat layer in an amount of 0.1 to 10% by weight. When the content of the photopolymerization initiator is less than 0.1% by weight, the active energy ray curable resin is not sufficiently cured. On the other hand, when the content of the photopolymerization initiator exceeds 10% by weight, the photopolymerization initiator is unnecessarily increased, which is not preferable.

  Moreover, the refractive index of the hard-coat layer after hardening should just be about 1.47-1.70. Further, the hard coat layer may contain a refractive index adjusting agent such as a metal oxide, if necessary, in order to adjust the refractive index. If the metal oxide used for refractive index adjustment is added to the resin composition for hard-coat layers in order to raise a refractive index, the kind in particular will not be restrict | limited. Examples of such metal oxides include zirconium oxide, zinc oxide, titanium oxide, cerium oxide, tin oxide, aluminum oxide, silane oxide, and indium tin oxide. Furthermore, the hard coat layer may be blended with acrylic, silicone, or fluorine additives for the purpose of imparting antifouling properties or surface smoothness, and for the purpose of imparting antistatic properties, an antistatic agent. May be blended.

  The film thickness of the hard coat layer after drying and curing is 0.1 to 5 μm. A film thickness of less than 0.1 μm is not preferable because scratch resistance is hardly exhibited. When the film thickness is thicker than 5 μm, the film becomes unnecessarily thick, which is not preferable because productivity and workability are lowered.

<Adhesive layer>
The adhesive layer is a layer for adhering the hard coat layer to the surface of the resin molded product, and is formed by drying and curing the resin composition for the adhesive layer. The adhesive layer resin composition comprises (A) a maleic anhydride-modified polyolefin resin, (B) a polyfunctional thiol compound, and (C) a polyfunctional ene compound as an essential component, and optionally further comprises (D) a photopolymerization initiator. It is a resin composition to contain.

<(A) Maleic anhydride modified polyolefin resin>
As the maleic anhydride-modified polyolefin resin, a maleic anhydride graft-modified resin of an α-olefin (co) polymer having 2 to 4 carbon atoms, that is, an (co) polymer of an α-olefin having 2 to 4 carbon atoms. Resin graft-modified with maleic anhydride can be used. Further, a maleic anhydride graft-modified resin of a copolymer of an α-olefin having 2 to 4 carbon atoms and maleic anhydride, that is, a copolymer of an α-olefin having 2 to 4 carbon atoms and maleic anhydride, Resins graft-modified with maleic anhydride can also be used.

  The graft weight of maleic anhydride in the maleic anhydride-modified polyolefin resin is preferably from 0.1 to 20% by weight, more preferably from 1.5 to 20% by weight. The content of maleic anhydride in the copolymer of α-olefin and maleic anhydride may be 0.1 to 50% by weight.

  The weight average molecular weight of the maleic anhydride-modified polyolefin resin is preferably 10,000 to 200,000. If the weight average molecular weight of the maleic anhydride-modified polyolefin resin is smaller than 10,000, tackiness during high-temperature storage tends to be easily developed. On the other hand, if the weight average molecular weight is larger than 200,000, the solubility in other components may be lowered.

<(B) Polyfunctional thiol compound>
The polyfunctional thiol compound has a thiol group at the terminal. Especially, the thioether containing (meth) acrylate derivative represented by the following (Formula 1), (Formula 4), or (Formula 6) is mentioned. The polyfunctional thiol compound can be used alone or in combination of two or more.

（式中のａは２〜３の整数であり、ｂは０又は１であり、ｃは１〜２の整数であり、ａとｂとｃの和は４である。Ｒ^１は、メチレン基、エチレン基又はイソプロピレン基である。Ｒ^２は、下記（式２）又は（式３）で表される２価の官能基である。Ｒ^３は、メチル基又はエチル基である。Ｒ^４は、炭素数が１〜１２の炭化水素基である。）

(In the formula, a is an integer of 2 to 3, b is 0 or 1, c is an integer of 1 to 2, and the sum of a, b and c is 4. R ¹ is a methylene group. R ² is a divalent functional group represented by the following (formula 2) or (formula 3), R ³ is a methyl group or an ethyl group, and R ⁴ is an ethylene group or an isopropylene group. Is a hydrocarbon group having 1 to 12 carbon atoms.)

（式中のｄは２〜５の整数であり、ｅは０〜２の整数であり、ｆは１〜４の整数であり、ｄとｅとｆの和は６である。Ｒ^１は、メチレン基、エチレン基又はイソプロピレン基である。Ｒ^２は、下記（式２）又は（式３）で表される２価の官能基である。Ｒ^３は、メチル基又はエチル基である。Ｒ^４は、炭素数が１〜１２の炭化水素基である。Ｒ^６は下記（式５）で表される６価の官能基である。）

(In the formula, d is an integer of 2 to 5, e is an integer of 0 to 2, f is an integer of 1 to 4, and the sum of d, e, and f is 6. R ¹ is methylene group, an ethylene group or an isopropylene group .R ² is .R ³ is a divalent functional group represented by the following (equation 2) or (formula 3) is a methyl group or an ethyl group. R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ is a hexavalent functional group represented by the following (formula 5).

（式中のｇは１であり、ｈは２である。Ｒ^７は下記（式７）で表される３価の基であり、Ｒ^８は下記（式２）又は下記（式３）で表される２価の基である。Ｒ^９は炭素数が１〜１２の炭化水素基である。）

(In the formula, g is 1 and h is 2. R ⁷ is a trivalent group represented by the following (Formula 7), and R ⁸ is the following (Formula 2) or the following (Formula 3). R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms.)

（Ｒ^５は水素原子又はメチル基である。）

（Ｒ^５は水素原子又はメチル基である。）

（式中のＲ^１０は−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、又はＣＨ_２ＣＨ（ＣＨ_３）−である。）

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)

_(-CH 2 ^{R 10} in the formula _{-, - CH 2 CH 2 -} , or _CH 2 _{CH (CH 3)} - and is.)

  The thioether-containing (meth) acrylate derivatives represented by (Formula 1), (Formula 4), and (Formula 6) are modified with a part of thiol group to reduce the polarity more than the thiol group, thereby providing a highly polar site. And a portion having a low polarity in a well-balanced manner, and (A) compatibility with the maleic anhydride-modified polyolefin resin is improved. Thereby, it is easy to form a crosslinked network in the whole resin composition for adhesive layers, and shows more favorable blocking resistance, solvent resistance, and wet heat resistance. Further, a thiol compound having a functionality of 5 or less is more preferable. In the case of a thiol compound having 6 or more functional groups, the adhesive strength may be reduced due to the high crosslinking density and the large shrinkage of curing.

  The weight average molecular weight of the polyfunctional thiol compound is preferably 350 to 1,500. Even if the weight average molecular weight of the polyfunctional thiol compound is smaller than 350, there is no problem with respect to adhesiveness, but there is a tendency that the volatility becomes high and the odor becomes strong. On the other hand, if the weight average molecular weight is larger than 1,500, there is no problem with respect to adhesiveness, but the solubility in other components may be lowered.

<(C) Polyfunctional ene compound>
Examples of the polyfunctional ene compound include polyfunctional (meth) acrylate, polyfunctional allyl, and polyfunctional vinyl ether.

（式中のｉは２〜８の整数であり、Ｒ^１１は炭素数２〜２０の炭化水素基、炭素数２〜４０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基、又はイソシアヌレート環若しくはイソシアヌレート環と炭化水素基のみからなる基であり、Ｒ^１２は水素原子またはメチル基である。） The polyfunctional (meth) acrylate as the component (C) has a (meth) acryloxy group at the terminal, and a preferred example thereof includes a compound represented by the following (formula 8). In addition, the polyfunctional (meth) acrylate which is (C) component can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

(Wherein i is an integer of 2 to 8 and R ¹¹ is a hydrocarbon group having 2 to 20 carbon atoms, a group consisting of ether oxygen (—O—) having 2 to 40 carbon atoms and a hydrocarbon group, or (Isocyanurate ring or a group consisting of an isocyanurate ring and a hydrocarbon group alone, and R ¹² is a hydrogen atom or a methyl group.)

  The (meth) acrylate equivalent of the polyfunctional (meth) acrylate is preferably 80 to 400 g / mol. When the (meth) acrylate equivalent is less than 80 g / mol, the (meth) acryloxy group per unit volume becomes excessive, and a large amount of (B) polyfunctional thiol compound thiol group and unreacted (meth) acryloxy group remain. By doing, the toughness of the contact bonding layer which hardened | cured the resin composition falls, and there exists a possibility that adhesiveness may fall. On the other hand, when the (meth) acrylate equivalent is greater than 400 g / mol, the (meth) acryloxy group concentration is extremely low, and the reaction efficiency with the thiol group of the (B) polyfunctional thiol compound is reduced. May decrease and adhesiveness may decrease.

（式中のｊは２〜８の整数であり、Ｒ^１３は炭素数２〜２０の炭化水素基、炭素数２〜４０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基、またはイソシアヌレート環若しくはイソシアヌレート環と炭化水素基のみからなる基である。） The polyfunctional allyl which is the component (C) has an allyl group at the terminal, and a preferred example thereof is a compound represented by the following (formula 9). In addition, the polyfunctional allyl which is (C) component can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

(In the formula, j is an integer of 2 to 8, and R ¹³ is a hydrocarbon group having 2 to 20 carbon atoms, a group consisting only of C 2 to 40 ether oxygen (—O—) and a hydrocarbon group, or This is a group consisting of an isocyanurate ring or an isocyanurate ring and a hydrocarbon group only.)

  The allyl equivalent of the polyfunctional allyl is preferably 80 to 200 g / mol. When the allyl equivalent is less than 80 g / mol, the allyl group per unit volume becomes excessive and (B) the thiol group of the polyfunctional thiol compound and a large amount of unreacted allyl group remain, whereby the resin composition for the adhesive layer There is a possibility that the toughness of the adhesive layer obtained by curing the product is lowered and the adhesiveness is lowered. On the other hand, when the allyl equivalent is greater than 200 g / mol, the allyl group concentration is extremely low, so that the reaction efficiency with the thiol group of the (B) polyfunctional thiol compound decreases, and the toughness of the adhesive layer decreases, and the adhesiveness May decrease.

（式中のｋは２〜８の整数であり、Ｒ^１４は炭素数２〜２０の炭化水素基、炭素数２〜４０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基、またはイソシアヌレート環若しくはイソシアヌレート環と炭化水素基のみからなる基である。） The polyfunctional vinyl ether which is the component (C) has a vinyl ether group at the terminal, and preferred examples thereof include compounds represented by the following (formula 10). In addition, the polyfunctional vinyl ether which is (C) component can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

(In the formula, k is an integer of 2 to 8 and R ¹⁴ is a hydrocarbon group having 2 to 20 carbon atoms, a group consisting of ether oxygen (—O—) having 2 to 40 carbon atoms and a hydrocarbon group, or This is a group consisting of an isocyanurate ring or an isocyanurate ring and a hydrocarbon group only.)

  The vinyl ether equivalent of the polyfunctional vinyl ether is preferably 60 to 200 g / mol. When the vinyl ether equivalent is less than 60 g / mol, the vinyl ether group per unit volume becomes excessive, and (B) the thiol group of the polyfunctional thiol compound and a large amount of unreacted vinyl ether group remain, whereby the resin composition for the adhesive layer There is a possibility that the toughness of the adhesive layer obtained by curing the product is lowered and the adhesiveness is lowered. On the other hand, when the vinyl ether equivalent is larger than 200 g / mol, the vinyl ether group concentration is remarkably low, so that the reaction efficiency with the thiol group of the (B) polyfunctional thiol compound is lowered, so that the toughness of the adhesive layer is lowered, and the adhesiveness May decrease.

  The weight average molecular weight of the polyfunctional ene is preferably 100 to 1,000. Even if the weight average molecular weight of the polyfunctional ene is less than 100, there is no problem with respect to adhesiveness, but the volatility tends to increase and the odor tends to increase. On the other hand, when the weight average molecular weight is larger than 1,000, there is no problem with the adhesiveness, but the solubility in other components may be lowered.

<(D) Photopolymerization initiator>
The photopolymerization initiator is added to promote the reaction between the thiol group and the vinyl group, and can reduce the light irradiation necessary for curing the resin composition for the adhesive layer. Can be shortened. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator. The photoradical polymerization initiator is preferably used for shortening the reaction time, the photocationic polymerization initiator is preferably used for reducing curing shrinkage, and the photoanionic polymerization initiator is used in the field of electronic circuits and the like. It is preferable to use it when imparting adhesiveness. In addition, although it can accelerate | stimulate hardening of a resin composition by heating also in a thermal-polymerization initiator, since storage stability may fall, it is unpreferable.

  Examples of the radical photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. It is.

  Examples of the cationic photopolymerization initiator include bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylsulfonium tetrafluoroborate, and diphenyl. Iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, triphenylsulfonium tetrafluoroborate, Examples include triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, and the like.

  Examples of the photoanionic polymerization initiator include acetophenone o-benzoyloxime, nifedipine, 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4,4,0] deca- 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidinium 2- (3-benzoylphenyl) propionate, 1,2 -Dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate and the like.

<Composition ratio (blending balance) of resin composition for adhesive layer>
The resin composition for the adhesive layer is (A) 5 to 25 parts by mass of the polyfunctional thiol compound and (C) 5 to 35 parts by mass of the polyfunctional ene compound with respect to 100 parts by mass of the maleic anhydride-modified polyolefin resin. It mix | blends so that it may become. (B) When the compounding quantity of a polyfunctional thiol compound is less than 5 mass parts or exceeds 25 mass parts, it exists in the tendency for the heat resistance of the adhesive layer obtained, solvent resistance, and moisture resistance to be inferior. Moreover, when the compounding quantity of (C) polyfunctional ene compound is less than 5 mass parts or exceeds 35 mass parts, it exists in the tendency for heat resistance, solvent resistance, and moisture resistance to be inferior.

  (D) When mix | blending a photoinitiator as an arbitrary component, (D) A photoinitiator is 0.01-10 mass parts with respect to 100 mass parts of (A) maleic anhydride modified polyolefin resin, Preferably it is 0. It mix | blends so that it may become 1-5 mass parts. When the blending amount of the component (D) is less than 0.01 parts by mass with respect to 100 parts by mass of the component (A), a large amount of integrated light is required for the reaction between the thiol group and the vinyl group to proceed. On the other hand, when it exceeds 10 parts by mass, the crosslinking density is lowered, and the heat resistance and solvent resistance of the resulting adhesive layer may be lowered.

The resin composition for an adhesive layer can be cured by irradiating light. Examples of the light to be irradiated include active energy rays such as UV (ultraviolet rays) and EB (electron beams). Also, if the adhesive layer resin composition comprising the component (D), the amount of light irradiation to be usually 2,500 mJ / cm ² about required, it is possible to reduce to about 100 mJ / cm ^2.

  The resin composition for the adhesive layer may be used after diluting with an organic solvent in order to make the reaction system uniform and facilitate coating. Examples of such organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents, ether ester solvents, ketone solvents, and phosphate ester solvents. These organic solvents are preferably suppressed to a blending amount of less than 10,000 parts by weight with respect to 100 parts by weight of the resin composition, but basically the solvent is volatilized when it becomes a cured film. The physical properties of the resulting adhesive layer are not significantly affected.

  The thickness of the adhesive layer after drying and curing is 0.02 to 1 μm, and preferably 0.02 to 0.08 μm. A film thickness of less than 0.02 μm is not preferable because sufficient adhesive strength cannot be obtained. When the film thickness is thicker than 1 μm, the surface hardness such as scratch resistance becomes weak. If the film thickness is 0.08 μm or less, the surface hardness becomes higher.

<Formation of transfer film>
The hard coat layer is formed by applying a resin composition for a hard coat layer onto a release film and drying it as necessary, followed by curing by irradiation with active energy rays. A release agent may be applied on the release film as necessary. The adhesive layer is formed by applying the resin composition for the adhesive layer onto the hard coat layer, drying it as necessary, and then curing it by irradiation with active energy rays. The type of the active energy ray is not particularly limited, but it is preferable to use ultraviolet rays from the viewpoint of convenience and the like.

  The coating method of the hard coat layer resin composition, the adhesive layer resin composition, and the release agent applied as necessary is not particularly limited. For example, a roll coating method, a spin coating method, a dip coating method. Any known coating method such as spray coating method, bar coating method, knife coating method, die coating method, ink jet method, and gravure coating method can be employed.

  In addition, according to the application method, the hard coat resin composition and the adhesive layer resin composition are prepared using an appropriate organic solvent so that the viscosity becomes an appropriate viscosity. It is also possible. In this case, as a method for drying the solvent, hot air drying or far-infrared drying can be appropriately selected and used.

<Transfer method of transfer film>
Examples of the thermoplastic resin used for the resin molded product to be transferred from the transfer film include polyolefin resins such as polyethylene and polypropylene, polystyrene resins, polyvinyl chloride resins, poly (meth) acrylate resins, and acrylic resins. Any known thermoplastic resins such as polyacetal resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polycarbonate resins, polyphenylene sulfide resins and polyimide resins can be used. These resins can be used alone or in admixture of two or more.

  A method of transferring the adhesive layer and the hard coat layer from the transfer film onto the resin molded product is performed as follows. First, the transfer film is fed into the molding die so that the release film faces the die. After closing the molding die, molten resin for molding is injected and filled into the die from the gate, and then cooled and solidified to form a resin molded product. At this time, the adhesive layer adheres to the surface of the resin molded product by heat during injection molding. After the resin molded product is cooled, the molding die is opened and the resin molded product is taken out. Finally, when the release film is peeled off, the hard coat layer is transferred to the surface of the resin molded product, and the transfer process is completed. Thus, a resin molded product having a hard coat layer on the surface is formed.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples.

<Manufacture of resin composition for hard coat layer>
[Preparation of resin composition for hard coat layer (HC-1)]
96 parts by mass of dipentaerythritol hexaacrylate and 4 parts by mass of a photopolymerization initiator [trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.] were mixed to prepare a resin composition for hard coat layer (HC-1). did.

[Preparation of resin composition for hard coat layer (HC-2)]
96 parts by mass of dipentaerythritol hexaacrylate, photopolymerization initiator [trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.], 4 parts by mass, colloidal silica [trade name: MEK-ST, manufactured by Nissan Chemical Industries, Ltd. 50 parts by mass were mixed to prepare a resin composition for hard coat layer (HC-2).

[Preparation of resin composition for hard coat layer (HC-3)]
Dipentaerythritol hexaacrylate 46 parts by mass, hexafunctional urethane acrylate [trade name: UV-7600B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] 50 parts by mass, photopolymerization initiator [trade name: IRGACURE 184, Ciba Specialty Chemicals ( Ltd.] 4 parts by mass, colloidal silica [trade name: MEK-ST, manufactured by Nissan Chemical Industries, Ltd.] 50 parts by mass were mixed to prepare a resin composition for hard coat layer (HC-3).

<Manufacture of component A>
(Production of A-1)
Mixing 100 parts by weight of polypropylene (weight average molecular weight 10,000), 3 parts by weight of maleic anhydride, and 5 parts by weight of di-t-butyl peroxide in a four-necked flask made of slenless equipped with a stirrer with an internal volume of 10 liters The mixture was kneaded at 230 ° C. for 3 minutes using a twin-screw kneading extruder. The polymer taken out was cooled to form pellets, and then dissolved in an equal weight of xylene until the solid matter could not be visually confirmed while heating to 140 ° C. The pellet solution after dissolution by heating was cooled to room temperature, and twice the weight of acetone was added to xylene as a solvent to obtain a suspension in which maleic anhydride-modified polyolefin resin was precipitated. This suspension was filtered, and the reprecipitated maleic anhydride-modified polyolefin resin was dried under reduced pressure until there was no change in weight to obtain 101.7 parts by mass of maleic anhydride-modified polyolefin resin (A-1). It was. The maleic anhydride-modified polyolefin resin (A-1) had a weight average molecular weight of 10,000 and a maleic anhydride graft weight of 1.7% by weight.

(Production of A-2)
In a four-necked flask made of slenless equipped with a stirrer with an internal volume of 10 liters, 100 parts by mass of propylene-ethylene copolymer (propylene / ethylene = 92/8 mol%, weight average molecular weight 55,000), maleic anhydride 20 Part by mass and 5 parts by mass of di-t-butyl peroxide were mixed and kneaded at 230 ° C. for 3 minutes using a twin-screw kneading extruder. The polymer taken out was cooled to form pellets, and then dissolved in an equal weight of xylene until the solid matter could not be visually confirmed while heating to 140 ° C. The pellet solution after dissolution by heating was cooled to room temperature, and twice the weight of acetone was added to xylene as a solvent to obtain a suspension in which maleic anhydride-modified polyolefin resin was precipitated. This suspension was filtered, and the reprecipitated maleic anhydride-modified polyolefin resin was dried under reduced pressure until there was no change in weight to obtain 116.1 parts by mass of maleic anhydride-modified polyolefin resin (A-2). It was. The maleic anhydride-modified polyolefin resin (A-2) had a weight average molecular weight of 55,000 and a maleic anhydride graft weight of 13.9% by weight.

(Production of A-3)
100 mass of propylene-butene-ethylene copolymer (propylene / butene / ethylene = 68/20/12 mol%, weight average molecular weight 200,000) in a four-necked flask made of slenless equipped with a stirrer with an internal volume of 10 liters Parts, 30 parts by weight of maleic anhydride, and 5 parts by weight of di-t-butyl peroxide were mixed and kneaded at 230 ° C. for 3 minutes using a twin-screw kneading extruder. The polymer taken out was cooled to form pellets, and then dissolved in an equal weight of xylene until the solid matter could not be visually confirmed while heating to 140 ° C. The pellet solution after dissolution by heating was cooled to room temperature, and twice the weight of acetone was added to xylene as a solvent to obtain a suspension in which maleic anhydride-modified polyolefin resin was precipitated. This suspension was filtered, and the reprecipitated maleic anhydride-modified polyolefin resin was dried under reduced pressure until there was no change in weight to obtain 125.0 parts by mass of maleic anhydride-modified polyolefin resin (A-3). It was. The maleic anhydride-modified polyolefin resin (A-3) had a weight average molecular weight of 200,000 and a maleic anhydride graft weight of 20% by weight.

(Production of A-4)
In a four-necked flask made of slenless equipped with a stirrer with an internal volume of 10 liters, 100 parts by mass of an ethylene-maleic anhydride copolymer (ethylene / maleic anhydride = 87/13 mol%, weight average molecular weight 30,000), 20 parts by mass of maleic anhydride and 5 parts by mass of di-t-butyl peroxide were mixed and kneaded at 230 ° C. for 3 minutes using a twin-screw kneading extruder. The polymer taken out was cooled to form pellets, and then dissolved in an equal weight of xylene until the solid matter could not be visually confirmed while heating to 140 ° C. The pellet solution after dissolution by heating was cooled to room temperature, and twice the weight of acetone was added to xylene as a solvent to obtain a suspension in which maleic anhydride-modified polyolefin resin was precipitated. This suspension was filtered, and the reprecipitated maleic anhydride-modified polyolefin resin was dried under reduced pressure until there was no change in weight to obtain 114.4 parts by mass of maleic anhydride-modified polyolefin resin (A-4). It was. The maleic anhydride-modified polyolefin resin (A-4) had a weight average molecular weight of 30,000 and a maleic anhydride graft weight of 12.6% by weight.

In addition, the graft weight of maleic anhydride of A-1 to A-3 was calculated by the following formula.

On the other hand, the graft weight of maleic anhydride of A-4 was calculated by the following formula.

  The weight of maleic anhydride in the maleic anhydride-modified polyolefin resin and the weight of maleic anhydride in the olefin-maleic anhydride copolymer were calculated by an alkali dropping method using a potassium hydroxide-ethanol solution. Further, the weight average molecular weight of the maleic anhydride-modified polyolefin resin was measured by gel permeation chromatography using tetrahydrofuran as a solvent. Conversion to the weight average molecular weight was calculated based on a polystyrene calibration curve.

The compositions of A-1 to A-4 are summarized in Table 1.

[Preparation of resin composition for adhesive layer]
Use the raw materials described in Tables 2 to 5 as the resin composition for the adhesive layer, blend the raw materials in the blending ratios shown in Tables 2, 3, 4, and 5, and melt and knead them with a pressure kneader. Adhesive layer resin compositions AD1-1 to AD1-23, AD2-1 to AD2-23, AD'1-1 to AD'1-18, and AD'2-1 to AD'2-18 were prepared.

Ｂ−５：チオエーテル含有アクリレート誘導体；下記（式１２）

Ｂ−６：チオエーテル含有アクリレート誘導体；下記（式１３）

Ｃ−１：ジメチロール-トリシクロデカンジアクリレート
Ｃ−２：ジペンタエリスリトールヘキサアクリレート
Ｃ−３：エトキシ化イソシアヌル酸トリアクリレート
Ｃ−４：ビスフェノールＡのＥＯ付加物ジメタクリレート
Ｃ−５：トリメチロールプロパントリメタクリレート
Ｃ−６：１，６−ヘキサンジオールジメタクリレート
Ｃ−７：１，３−ジアリル−５−メチル−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン
Ｃ−８：トリアリルイソシアヌレート
Ｃ−９：ペンタエリスリトールトリアリルエーテル
Ｃ−１０：１，４−ブタンジオールジビニルエーテル
Ｃ−１１：シクロヘキサンジメタノールジビニルエーテル
Ｄ−１：２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン
Ａ’−１：フェノキシ樹脂（ユニオンカーバイト社製、「ＰＫＨＣ」、平均分子量４５,０００）
Ａ’−２：ポリウレタン樹脂（東ソー株式会社製「エラクトランＥ３９０ＰＮＡＴ」）
Ｂ’−１：１−オクタンチオール
Ｃ’−１：イソボルニルアクリレート
Ｃ’−２：２−エチルヘキシルメタクリレート
Ｃ’−３：アリルエチルエーテル
Ｃ’−４：シクロヘキシルビニルエーテル In addition, each raw material described in Tables 2-5 is as follows.
B-1: Trimethylolpropane tris (3-mercaptopropionate); TMMP
B-2: Dipentaerythritol hexakis (3-mercaptopropionate); DPMP
B-3: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate; TEMPIC
B-4: Thioether-containing acrylate derivative;

B-5: Thioether-containing acrylate derivative;

B-6: Thioether-containing acrylate derivative;

C-1: Dimethylol-tricyclodecane diacrylate C-2: Dipentaerythritol hexaacrylate C-3: Ethoxylated isocyanuric acid triacrylate C-4: EO adduct dimethacrylate of bisphenol A C-5: Trimethylolpropane tri Methacrylate C-6: 1,6-hexanediol dimethacrylate C-7: 1,3-diallyl-5-methyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione C -8: triallyl isocyanurate C-9: pentaerythritol triallyl ether C-10: 1,4-butanediol divinyl ether C-11: cyclohexanedimethanol divinyl ether D-1: 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one A′-1: Fe Carboxymethyl resin (Union Carbide Corporation, "PKHC", average molecular weight 45,000)
A′-2: Polyurethane resin (“Elactolan E390PNAT” manufactured by Tosoh Corporation)
B'-1: 1-octanethiol C'-1: isobornyl acrylate C'-2: 2-ethylhexyl methacrylate C'-3: allyl ethyl ether C'-4: cyclohexyl vinyl ether

[Evaluation of storage stability]
About each obtained resin composition for contact bonding layers, the storage stability was evaluated as follows. A 20% solution was prepared by dissolving in methylcyclohexane, and the initial viscosity was measured. Separately, the adhesive layer resin composition was allowed to stand at 50 ° C. for 60 days in a sealed container, and after 60 days, it was dissolved in methylcyclohexane to prepare a 20% solution, and the viscosity was measured. The value of viscosity / initial viscosity after 60 days was calculated and evaluated. This evaluation result is also shown in Tables 2-5.
A: (viscosity after 60 days / initial viscosity) less than 1.02 ○: (viscosity after 60 days / initial viscosity) of 1.02 or more and less than 1.50 x: (after 60 days) (Viscosity / initial viscosity) value of 1.50 or more

<Manufacture of transfer film>
(Example 1-1)
Resin composition for hard coat (HC1-1) and solvent (release name: E7002, film thickness: 50 μm, width: 140 mm, length: 1000 m, manufactured by Toyobo Co., Ltd.) A coating solution for hard coat layer in which methylethylketone) is mixed at a ratio of 1: 1 is applied with a roll-to-roll gravure coater so that the film thickness after curing is 1 μm, and irradiated with 400 mJ ultraviolet rays with a 120 W high-pressure mercury lamp. Then, 900 m of a hard coat film was produced. Subsequently, an adhesive layer coating solution prepared by mixing the adhesive layer resin composition (AD-1) and the solvent (methylcyclohexane) in a ratio of 1: 4 on the hard coat layer is obtained using a roll-to-roll gravure coater. The transfer film of Example 1-1 was produced in an amount of 800 m by coating the film so that the film thickness after curing was 0.05 μm and irradiating it with ultraviolet light of 400 mJ with a 120 W high-pressure mercury lamp.

(Examples 1-2 to 1-31, 2-1 to 2-31, Comparative Examples 1-1 to 1-21, 2-1 to 2-21)
Except for the release film, the resin composition for hard coat, and the resin composition for adhesive layer, and the thickness and thickness of each layer described in Tables 6 to 9, the same manner as in Example 1-1, A transfer film was prepared. About the obtained transfer film, winding property was evaluated by the following method. The results are also shown in Tables 6-9.

[Evaluation of winding property]
The designated length was unwound from the produced transfer film 800 m, and the presence or absence of blocking between the films was evaluated. In order to serve the purpose of the present application, an evaluation of ◯ or higher is required.
A: Blocking is not observed when unrolled 800 m. O: Blocking is observed after unwinding 700 m. X: Blocking is observed after unwinding 100 m.

<Manufacture of transfer molded products>
(Example 3-1)
In the state which match | combined the adhesive layer surface of the transfer film of Example 1-1 with the thermoplastic resin (polyvinyl chloride sheet | seat, film thickness: 100 micrometers) used for the resin molded product for forming a transfer molded product, SUS board Transfer with 19kgf / cm ² , 90 ° C, 180 seconds heat-pressed with a heating press machine, after cooling, release the release film, and transfer the hard coat layer onto the surface of the polyvinyl chloride sheet A molded product was produced.

(Examples 3-2 to 3-31, 4-1 to 4-31, Comparative Examples 3-1 to 3-21, 4-1 to 4-21)
A transfer molded product was produced in the same manner as in Example 3-1, except that the transfer film was made of the material described in Tables 10-13. About the obtained transfer molded article, pencil hardness, scratch resistance, adhesiveness (adhesive strength), solvent resistance, and moisture resistance were evaluated by the following methods. The results are also shown in Tables 10-13.

[Evaluation of pencil hardness]
The pencil hardness of the low friction film was evaluated in accordance with JIS K5600-1999 5.4. In order to serve the purpose of the present application, the evaluation requires H or higher.

[Evaluation of scratch resistance]
The surface of the hard-coating layer surface of the transfer molded product was subjected to a load of 500 gf on # 0000 steel wool and rubbed 10 times at a stroke width of 25 mm and a speed of 30 mm / sec. It was evaluated with. In order to serve the purpose of the present application, an evaluation of ◯ or higher is required.
* Steel wool was gathered to about 10 mmφ, cut so that the surface was uniform, and rubbed and averaged.
◎: No scratch ○: 1 to 10 scratches ×: 11 or more scratches

[Evaluation of adhesion]
JIS K 5600-5-6: 1999 “Paint General Test Method-Part 5: Mechanical Properties of Coating Film—Section 6: Adhesion (Crosscut Method)” on the Hard Coat Layer Surface of Transfer Molded Products The adhesion was evaluated in accordance with the standards. To serve the purpose of the present application, the evaluation requires 100/100.
A: 100/100
○: 100/100, but lacked edge x: less than 100/100

[Evaluation of solvent resistance]
The transfer molded article was immersed in the following solvent for 30 minutes. Then, after taking out the sample and drying it, it conforms to JISK 5600-5-6: 1999 “Paint General Test Method-Part 5: Mechanical Properties of Coating Film—Section 6: Adhesion (Crosscut Method)” Evaluation of adhesiveness and appearance after taking out were observed. The solvent resistance was evaluated with toluene, xylene, tetrachloroethylene, gasoline, acetone, isopropyl alcohol, and hexane.
◎: All of the above solvents showed the same adhesion as before immersion ○: All of the above solvents showed the same adhesion as before immersion, but immediately after removing the sample from the solvent with some of the solvents , Whitening confirmed Δ: Some of the above-mentioned solvents whose adhesiveness was lower than before immersion x: Some of the above-mentioned solvents were peeled off during immersion

[Evaluation of wet adhesion resistance]
The transfer molded product was allowed to stand in a constant temperature and humidity chamber at 85 ° C. and 85% for 200 hours. Thereafter, the moisture adhesion resistance was evaluated in accordance with JISK 5600-5-6: 1999 “General test method for coating materials—Part 5: Mechanical properties of coating film—Section 6: Adhesion (cross-cut method)”. . In order to serve the purpose of the present application, the evaluation needs to be ○.
A: 100/100
○: 100/100, but lacked edge Δ: less than 100/100 90/100 or more x: less than 90/100

<Consideration of results>
From the results of Tables 6 and 7, Examples 1-1 to 1-6, 1-24, 1-25, 1-31, 2-1 to 2-6, 2-24, 2-25, 2- The transfer film No. 31 could be wound into a roll shape without blocking. Furthermore, the transfer films of Examples 1-7 to 1-23, 1-26 to 1-30, 2-7 to 2-23, and 2-26 to 2-30 are more preferable than those in the resin composition for adhesive layers. By using the preferred component (B), it was possible to wind up into a roll shape without blocking.

  On the other hand, from the results of Tables 8 and 9, Comparative Example 1-1 to Comparative Example 1-14, Comparative Example 1-16 to Comparative Example 1-18, Comparative Example 2-1 to Comparative Example 2-14, and Comparative Example 2- Since the resin composition for adhesion layers was outside the range prescribed | regulated by this invention in 16- Comparative Examples 2-18, when it rolled up in roll shape, it resulted in blocking.

  From the results of Table 10 and Table 11, Examples 3-1 to 3 are transfer molded products prepared using the transfer films prepared in Examples 1-1 to 1-31 and 2-1 to 2-31. -31, Example 4-1 to Example 4-31 resulted in excellent pencil hardness, surface hardness indicated by scratch resistance, and excellent adhesion, solvent resistance, and moisture resistance adhesion.

On the other hand, from the results of Tables 12 and 13, Comparative Example 3-1 to Comparative Example 3-18 and Comparative Example 4-1 to Comparative Example 4-18 are not compositions defined by the resin composition for adhesive layers according to the present invention. Therefore, any of adhesiveness, solvent resistance, and moisture resistance was inferior. In Comparative Examples 3-19 and 4-19, since the film thickness of the hard coat layer of the transfer film was outside the range defined in the present invention, the pencil hardness and scratch resistance were inferior and the surface hardness was weak. . In Comparative Examples 3-20 and 4-20, the film thickness of the adhesive layer was thinner than the range defined in the present invention, and thus the adhesiveness was inferior. Since Comparative Example 3-21 and 4-21 were thicker than the range prescribed | regulated by this invention in the adhesive layer film thickness, it resulted in inferior surface hardness.

Claims (7)

A hard coat layer and an adhesive layer are laminated in this order on the release film.
The hard coat layer has a thickness of 0.1 to 5 μm,
The thickness of the adhesive layer is 0.02-1 μm,
The adhesive layer is
(A) For 100 parts by mass of maleic anhydride-modified polyolefin resin,
(B) 5 to 25 parts by mass of a polyfunctional thiol compound,
(C) 5 to 35 parts by mass of a polyfunctional ene compound,
The transfer film which is a layer formed by hardening | curing the resin composition for adhesive layers to contain.   The transfer film according to claim 1, wherein the component (A) is a maleic anhydride graft-modified resin of an (co) polymer of an α-olefin having 2 to 4 carbon atoms.   The transfer film according to claim 1, wherein the component (A) is a maleic anhydride graft-modified resin of a copolymer of an α-olefin having 2 to 4 carbon atoms and maleic anhydride. The transfer film according to any one of claims 1 to 3, wherein the component (B) is a polyfunctional thiol compound represented by the following (formula 1).

(In the formula, a is an integer of 2 to 3, b is 0 or 1, c is an integer of 1 to 2, and the sum of a, b and c is 4. R ¹ is a methylene group. R ² is a divalent functional group represented by the following (formula 2) or (formula 3), R ³ is a methyl group or an ethyl group, and R ⁴ is an ethylene group or an isopropylene group. Is a hydrocarbon group having 1 to 12 carbon atoms.)

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.) The transfer film according to any one of claims 1 to 3, wherein the component (B) is a polyfunctional thiol compound represented by the following (formula 4).

(In the formula, d is an integer of 2 to 5, e is an integer of 0 to 2, f is an integer of 1 to 4, and the sum of d, e, and f is 6. R ¹ is methylene group, an ethylene group or an isopropylene group .R ² is .R ³ is a divalent functional group represented by the following (equation 2) or (formula 3) is a methyl group or an ethyl group. R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ is a hexavalent functional group represented by the following (formula 5).

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)

The transfer film according to any one of claims 1 to 3, wherein the component (B) is a polyfunctional thiol compound represented by the following (formula 6).

(In the formula, g is 1 and h is 2. R ⁷ is a trivalent group represented by the following (Formula 7), and R ⁸ is the following (Formula 2) or the following (Formula 3). R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms.)

_(-CH 2 ^{R 10} in the formula _{-, - CH 2 CH 2 -} , or _CH 2 _{CH (CH 3)} - and is.)

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.) The transfer film according to any one of claims 1 to 6, further comprising 0.01 to 10 parts by mass of a photopolymerization initiator (D) with respect to 100 parts by mass of the component (A).