JPWO2017213217A1 - Reactive polymer, photocurable resin composition and laminate - Google Patents

Abstract

The present invention relates to a reactive polymer, a photocurable resin composition containing the same, and a laminate having the cured film thereof. An object of the present invention is to improve the adhesion between a hard coat layer and a substrate and the light resistance of the hard coat layer. The reactive polymer of the present invention has an alkoxysilane group and a (meth) acrylate group in its side chain.

Description

This patent application claims priority to Japanese Patent Application No. 2016-116343 (filing date: June 10, 2016), which is incorporated herein by reference in its entirety. It shall be incorporated.
The present invention relates to a reactive polymer, a photocurable resin composition containing the same, and a laminate having a cured film thereof.

As a photocurable resin composition for forming a hard-coat layer on a transparent base film, the photocurable resin composition (patent document 1) which contains an ultraviolet absorber, urethane acrylate, and a photoinitiator, for example, There has been known a photocurable resin composition (Patent Document 2) containing a polyorganosiloxane, a bifunctional acrylate, a UV absorber and a photopolymerization initiator.
JP, 2009-6513, A (paragraph 0062) Patent No. 5576622

  When the hard coat layer is formed on the substrate from the photocurable resin composition described in Patent Documents 1 and 2, flexibility, hardness, adhesion between the hard coat layer and the substrate, hardness of the hard coat layer, etc. The light resistance was not all satisfied at the same time.

  Then, this invention aims at improving the adhesiveness of a hard-coat layer and a base material, and the light resistance of a hard-coat layer.

The present invention includes the inventions described in the following [1] to [15].
[1] A reactive polymer having an alkoxysilane group and a (meth) acrylate group in its side chain.
[2] A main chain comprising a (meth) acrylate polymer, and the (meth) acrylate group as the side chain is bonded to the end of the urethane polymer and / or urethane oligomer bonded to the main chain, [1 ] The reactive polymer as described in.
[3] The reactive polymer according to [1] or [2], wherein the weight average molecular weight Mw of the reactive polymer is 10000 to 250000.
[4] The reactive polymer according to any one of [1] to [3], wherein a double bond equivalent of the reactive polymer is 800 to 125000.
[5] The reactive polymer according to [2], wherein the glass transition point (Tg) of the (meth) acrylate polymer is 0 to 70 ° C.
[6] The reactive polymer according to any one of [1] to [5], wherein the alkoxysilane group is an ethoxysilane group.
[7] A photocurable resin composition comprising a polyfunctional (meth) acrylate monomer, the reactive polymer according to any one of [1] to [6], a photopolymerization initiator, and a UV absorber.
[8] The photocurable resin composition according to [7], wherein the content of the reactive polymer is 5 to 60 parts by mass with respect to a total of 100 parts by mass of the polyfunctional (meth) acrylate monomer and the reactive polymer object.
[9] The photocurable resin composition according to [7] or [8], wherein the content of the alkoxysilane group in the reactive polymer is more than 0% by mass and less than 40% by mass based on the reactive polymer object.
[10] The photocurable resin composition according to any one of [7] to [9], which further contains an inorganic compound.
[11] The photocurable resin composition according to [10], which contains at least one inorganic compound selected from the group consisting of columnar, plate-like and layered inorganic compounds.
[12] A base film, and a cured film which is a cured product of the photocurable resin composition according to any one of [7] to [11], laminated on at least one side of the base film. , Stacks.
[13] The laminate according to [12], wherein the substrate is a polyimide.
[14] A method for producing a laminate,
(1) A step of obtaining a composition layer by applying the photocurable resin composition according to any one of [7] to [11] onto a substrate, and (2) by exposing the composition layer Curing the composition layer.
[15] The method according to [14], wherein the substrate film is a substrate film made of polyimide.

  According to the reactive polymer according to one aspect of the present invention, when the cured film of the photocurable resin composition containing the reactive polymer is formed as a hard coat layer on a transparent base film, the hard coat is formed on the transparent base film It is possible to obtain a laminate (for example, a hard coat film) having excellent adhesion to the layer and good light resistance of the hard coat layer.

It is a typical sectional view showing one embodiment of a layered product.

10 substrate film 10a main surface 20 cured film 30 laminate

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments. First, the reactive polymer according to one aspect will be described.

[Reactive polymer]
The reactive polymer has alkoxysilane groups and (meth) acrylate groups in side chains. When the reactive polymer has an alkoxysilane group in the side chain, excellent adhesion can be obtained. In addition, when the reactive polymer has a (meth) acrylate group in its side chain, curing with ultraviolet light becomes possible. As used herein, “(meth) acrylate” is a generic term that includes both acrylate and methacrylate.

  As an alkoxysilane group, a methoxysilane group, an ethoxysilane group, a propoxysilane group, a butoxysilane group etc. are mentioned.

  The (meth) acrylate group may be an acrylate group or a methacrylate group.

The reactive polymer has a main chain composed of a (meth) acrylate polymer, and a (meth) acrylate group as a side chain is reactive with the urethane oligomer bonded to the main chain and / or the terminal of the urethane polymer Polymers are preferred.
The (meth) acrylate polymer is a (meth) acrylic polymer having two or more hydroxyl groups in the molecule [hereinafter, also referred to as a hydroxyl group-containing (meth) acrylic polymer A].
The urethane oligomer is an acrylic urethane oligomer having one isocyanate group and one or more (meth) acrylate groups [hereinafter, also referred to as (meth) acrylic urethane oligomer B]. The urethane polymer is an acrylic urethane polymer having one isocyanate group and one or more (meth) acrylate groups [hereinafter, also referred to as (meth) acrylic urethane polymer C].
The reactive polymer may be a hydroxyl group-containing (meth) acrylic polymer A and a (meth) acrylic urethane oligomer B alone or a (meth) acrylic urethane polymer C alone or a (meth) acrylic urethane oligomer B and (meth) acrylic urethane polymer C The reactive polymer (hereinafter, also referred to as reactive polymer E) which is an addition reaction product of the addition reaction product with both and the isocyanate group-containing alkoxysilane D.

[Hydroxyl-containing (meth) acrylic polymer A]
The hydroxyl group-containing (meth) acrylic polymer A is a (meth) acrylic polymer containing two or more hydroxyl groups in the molecule. The weight average molecular weight Mw is not particularly limited, but is preferably 3,000 to 200,000, more preferably 10,000 to 160,000, and still more preferably 30,000 to 120,000. preferable. When the weight average molecular weight Mw is 3,000 or less, the hardness of the reactive polymer E may be high, and the flexibility may not be sufficiently expressed. Further, when the weight average molecular weight Mw is 200,000 or more, the reactivity of the reactive polymer E at the time of ultraviolet curing is significantly reduced, and as a result, the light resistance may be reduced. As used herein, “(meth) acrylate” is a generic term that includes both acrylate and methacrylate.

  The hydroxyl group-containing (meth) acrylic polymer A preferably has a glass transition temperature (Tg) of 0 to 70 ° C., more preferably 10 to 60 ° C., and still more preferably 20 to 50 ° C. When the glass transition point (Tg) of the hydroxyl group-containing (meth) acrylic polymer A is within the above range, sufficient hardness and flexibility can be obtained, but when the glass transition point (Tg) is 0 ° C. or less There may be a significant reduction in hardness. On the other hand, when the glass transition point (Tg) is 70 ° C. or higher, the hardness may be increased to decrease the flexibility. In the present invention, the glass transition point (Tg) is a value measured using a differential scanning calorimeter.

[(Meth) acrylic urethane oligomer B]
The (meth) acrylic urethane oligomer B is an acrylic urethane oligomer having one isocyanate group and one or more (meth) acrylate groups, and is a monofunctional (meth) acrylate or a polyfunctional (diisocyanate and one hydroxyl group) It is an acrylic urethane oligomer obtained by reacting meta) acrylate or these. There is no particular limitation on the composition. The molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the molecular weight is 3,000 or more, the ultraviolet curability of the reactive polymer E tends to decrease.

[(Meth) acrylic urethane polymer C]
The (meth) acrylic urethane polymer C is an acrylic urethane polymer having one isocyanate group and one or more (meth) acrylate groups, and one end of a prepolymer of both terminal isocyanate obtained by reacting an excess of diisocyanate and diol. Or a monofunctional (meth) acrylate or polyfunctional (meth) acrylate having one hydroxyl group, or an acrylic urethane polymer obtained by reacting these in combination. There is no particular limitation on the composition. 1,000-50,000 are preferable, as for a weight average molecular weight Mw, 3,000-20,000 are more preferable, and 5,000-10,000 are more preferable. When the weight average molecular weight Mw is 1,000 or less, the flexibility of the reactive polymer E may not be obtained at all or may not be sufficient. When the weight average molecular weight Mw is 50,000 or more, in order to obtain the reactive polymer E, the reaction rate at the time of addition reaction to the hydroxyl group-containing (meth) acrylic polymer A is significantly reduced, and the varnish is separated and clouded. Stability may be significantly reduced.

[Reactive polymer E]
The reactive polymer E is a hydroxyl group-containing (meth) acrylic polymer A, a (meth) acrylic urethane oligomer B alone or a (meth) acrylic urethane polymer C alone, or (meth) acrylic urethane oligomer B and (meth) acrylic urethane It is obtained by subjecting both of the polymers C to an addition reaction, and then subjecting the isocyanate group-containing alkoxysilane D to an addition reaction.

  The reactive polymer E has an alkoxysilane group and a (meth) acrylate group in its side chain. When the reactive polymer E has an alkoxysilane group in the side chain, excellent adhesion can be obtained. In addition, when the reactive polymer E has a (meth) acrylate group in its side chain, curing with ultraviolet light becomes possible.

〔式中、ｎ１及びｎ２はそれぞれ１〜１０の整数を表す。Ｒ_１、Ｒ_２、Ｒ_６及びＲ_７はそれぞれ独立に炭素原子数２〜６のアルキレン基を表す。Ｒ_３はポリウレタン鎖を表す。Ｒ_４、Ｒ_５及びＲ_１１はそれぞれ独立にメチル基または水素原子を表す。Ｒ_８及びＲ_９はそれぞれ独立にメチル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基を表す。Ｒ_１０はメトキシ基、エトキシ基、プロポキシ基、ブトキシ基を表す。
Ｒ_１、Ｒ_２、Ｒ_６及びＲ_７としての炭素原子数２〜６のアルキレン基としては、エチレン基、プロピレン基、ブチレン基、ペンタンジイル基、ヘキサンジイル基が挙げられる。〕
で示される構造単位を持つ。The reactive polymer has the formula (1):

[Wherein, n1 and n2 each represent an integer of 1 to 10]. R _1, represents an _R 2, _{R 6} and _{R 7} independently represents an alkylene group having 2 to 6 carbon atoms. R ₃ represents a polyurethane chain. R ₄ , R ₅ and R ₁₁ each independently represent a methyl group or a hydrogen atom. R ₈ and R ₉ each independently represent a methyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. R ₁₀ represents a methoxy group, an ethoxy group, a propoxy group or a butoxy group.
Examples of the alkylene group having 2 to 6 carbon atoms as R ₁ , R ₂ , R ₆ and R ₇ include ethylene group, propylene group, butylene group, pentanediyl group and hexanediyl group. ]
It has a structural unit indicated by.

The polyurethane chain as R ₃ may be a divalent group derived from a urethane polymer and / or a urethane oligomer. The divalent group derived from the urethane polymer and / or urethane oligomer is a group obtained by removing two hydrogen atoms from the (meth) acrylic urethane oligomer B and / or the (meth) acrylic urethane polymer C. The urethane polymer preferably has a weight average molecular weight Mw of 1,000 to 50,000. The urethane oligomer preferably has a weight average molecular weight Mw of 3,000 or less.

  The reactive polymer E can be produced by a conventionally known method. The reactive polymer E is a hydroxyl group-containing (meth) acrylic polymer A alone, (meth) acrylic urethane oligomer B alone, (meth) acrylic urethane polymer C alone, or (meth) acrylic urethane oligomer B ) After adding both of the acrylic urethane polymer C, it can be obtained by adding an isocyanate group-containing alkoxysilane D.

  The hydroxyl group-containing (meth) acrylic polymer A can be obtained by conventionally known methods such as solution polymerization, bulk polymerization and suspension polymerization. For example, in the case of solution polymerization, it can be obtained by dropping a (meth) acrylate monomer and a polymerization initiator into an organic solvent at a reaction temperature of 80 to 150 ° C. in a nitrogen stream to cause a polymerization reaction. The type of (meth) acrylate is not particularly limited, but at least one or more types due to addition reaction with (meth) acrylic urethane oligomer B, (meth) acrylic urethane polymer C and isocyanate-containing alkoxysilane D in the next step. It is necessary to include hydroxyl group-containing (meth) acrylates.

  The hydroxyl group-containing (meth) acrylic polymer A can be obtained, for example, by polymerizing a hydroxyl group-containing (meth) acrylate with an ester of alkyl (meth) acrylate or cycloalkyl and / or another vinyl monomer. .

  As a hydroxyl group containing (meth) acrylate monomer, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) And (iii) monofunctional (meth) acrylates such as acrylate and polypropylene glycol mono (meth) acrylate, and polyfunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of esters of alkyl (meth) acrylates or cycloalkyls and / or other vinyl-based monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, Isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylates, (meth) acrylic acid, butoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination. As used herein, “(meth) acrylic acid” is a generic term that includes both acrylic acid and methacrylic acid.

  Examples of the polymerization initiator include, but are not particularly limited to, azo polymerization initiators such as azobisisobutyronitrile, peroxide polymerization initiators such as benzoyl peroxide, and the like, which may be used alone or in combination. You may

  Examples of the organic solvent include aromatics such as toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate, n-butyl acetate and propyl acetate. These may be used alone or in combination. You may use it. Ketones are preferable from the viewpoint of good solubility of the hydroxyl group-containing (meth) acrylic polymer A.

  The (meth) acrylic urethane oligomer B is obtained by reacting the hydroxyl group of a hydroxyl group-containing (meth) acrylate monomer with one end of diisocyanate at a reaction temperature of 40 ° C. to 120 ° C. under a stream of mixed gas of nitrogen and oxygen . These may contain an organic solvent. As an organic solvent, the organic solvent described in the description regarding manufacture of the above-mentioned hydroxyl-containing (meth) acrylic polymer A can be used, and these may be used individually or in combination. Further, for example, a polymerization catalyst such as an organic tin compound such as dioctyltin, or a double bond reaction inhibitor during addition reaction such as methoquinone may be used.

As diisocyanates used for the production of (meth) acrylic urethane oligomer B, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), methylenebisphenyl diisocyanate (MDI), xylene diisocyanate (XDI), dicyclohexylmethane And diisocyanates (HMDI) and the like, which may be used alone or in combination.
As a hydroxyl-containing (meth) acrylate monomer, 2-hydroxyethyl acrylate etc. are mentioned, for example.
As (meth) acrylic urethane oligomer B, for example, 2-hydroxyethyl acrylate adduct of isophorone diisocyanate, 2-hydroxyethyl acrylate adduct of hexamethylene diisocyanate, 2-hydroxyethyl acrylate adduct of toluene diisocyanate, methylene bisphenyl diisocyanate Examples thereof include 2-hydroxyethyl acrylate adduct, 2-hydroxyethyl acrylate adduct of xylene diisocyanate, 2-hydroxyethyl acrylate adduct of dicyclohexylmethane diisocyanate and the like, and these may be used alone or in combination. The weight-average molecular weight Mw of the acrylic urethane oligomer is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

  The (meth) acrylic urethane polymer C is obtained by reacting an excess of diisocyanate and diol in the range of 40 ° C. to 120 ° C. in a stream of a mixed gas of nitrogen and oxygen to obtain a urethane polymer of both terminal isocyanate groups. Then, it is obtained by reacting the hydroxyl group of the hydroxyl group-containing (meth) acrylate monomer with the isocyanate at one end of the urethane polymer. They may also contain organic solvents. As an organic solvent, the organic solvent described in the description regarding manufacture of the above-mentioned hydroxyl-containing (meth) acrylic polymer A can be used. Further, for example, a polymerization catalyst such as an organic tin compound such as dioctyltin, or a double bond reaction inhibitor during addition reaction such as methoquinone may be used.

  Examples of diisocyanates of (meth) acrylic urethane polymer C include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), methylenebisphenyl diisocyanate (MDI), xylene diisocyanate (XDI), dicyclohexylmethane diisocyanate ( HMDI) etc. are mentioned. These may be used alone or in combination.

  Examples of the diol of the (meth) acrylic urethane polymer C include polyether diol, polycarbonate diol, polyester diol, 1,6-hexanediol, 1,5-pentanediol, 1,12-dodecanediol and the like. These may be used alone or in combination.

  As the hydroxyl group-containing (meth) acrylate monomer, one similar to (meth) acrylic urethane oligomer B, for example, 2-hydroxyethyl acrylate can be used.

  1,000-50,000 are preferable, as for the weight average molecular weight Mw of the (meth) acryl urethane polymer C, 3,000-20,000 are more preferable, and 5,000-10,000 are more preferable.

  The reactive polymer E is a monomer of (meth) acrylic urethane oligomer B alone at the hydroxyl group of the hydroxyl group-containing (meth) acrylic polymer A at a reaction temperature in the range of 50 ° C. to 120 ° C. under a stream of mixed gas of nitrogen and oxygen Alternatively, after reacting the single terminal isocyanate group of (meth) acrylic urethane polymer C or both (meth) acrylic urethane oligomer B and (meth) acrylic urethane oligomer polymer, the isocyanate group of isocyanate-containing alkoxysilane D is hydroxylated It can be obtained by reacting with the hydroxyl group remaining in the contained (meth) acrylic polymer A. In the above reaction, a double bond inhibitor during addition reaction such as methoquinone may be used

  As an alkoxysilane group of isocyanate group containing alkoxysilane D, a methoxysilane group, an ethoxysilane group, a propoxysilane group, butoxysilane group etc. are mentioned. Among these, an ethoxysilane group is preferable because the photocurable resin composition is excellent in adhesion and storage stability, and appropriate reactivity is obtained. Examples of the isocyanate group-containing alkoxysilane D include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldiethoxysilane and the like. The compounds can be used alone or in combination.

  The content of the alkoxysilane group in the reactive polymer E is preferably more than 0% by mass and less than 40% by mass, more preferably 1% by mass to 35% by mass, still more preferably 5% by mass based on the reactive polymer It contains 30% by mass. When the content of the alkoxysilane group in the reactive polymer is in the above range, the photocurable composition containing the reactive polymer has sufficient adhesion.

  The double bond equivalent of the reactive polymer E is not particularly limited, but is preferably 800 to 125,000, more preferably 1,000 to 100,000, and still more preferably 1,500 to 70,000. When the double bond equivalent of the reactive polymer is within the above range, the flexibility and the light resistance will be sufficient. When the double bond equivalent is 800 or less, the hardness of the cured coating is too high, sufficient flexibility can not be obtained, and when the double bond equivalent is 125,000 or more, the ultraviolet curability decreases, and as a result, light resistance There is a concern that

  The weight average molecular weight Mw of the reactive polymer E is not particularly limited, but is preferably 10,000 to 250,000, more preferably 15,000 to 200,000, and 20,000 to 150,000. It is further preferred that When the weight average molecular weight of the reactive polymer is within the above range, sufficient ultraviolet curability, flexibility, and adhesiveness can be obtained. When the weight average molecular weight is 10,000 or less, the flexibility is reduced, and when it is 250,000 or more, the ultraviolet curability and storage stability are reduced.

  The reactive polymer according to one embodiment can be suitably used for a photocurable resin composition because it has an alkoxysilane group and an ultraviolet curable (meth) acrylate group in a side chain.

[Photo-curable resin composition]
The photocurable resin composition contains a bifunctional or higher polyfunctional (meth) acrylate monomer, a reactive polymer, a photopolymerization initiator, and a UV absorber.

  The polyfunctional (meth) acrylate monomer is a compound having two or more (meth) acrylate groups. As a polyfunctional (meth) acrylate monomer, bifunctional (meth) acrylate having two (meth) acrylate groups, trifunctional (meth) acrylate having three (meth) acrylate groups, four (meth) acrylate groups And tetrafunctional (meth) acrylates and mixtures of two or more of these, such as mixtures of trifunctional (meth) acrylates and tetrafunctional (meth) acrylates. For example, the content of the polyfunctional (meth) acrylate monomer or the mixture thereof in the photocurable resin composition is 40 to 95 parts by mass with respect to 100 parts by mass in total of the polyfunctional (meth) acrylate monomer and the reactive polymer And 50 to 90 parts by mass.

  As a polyfunctional (meth) acrylate monomer having two or more functions, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) Acryloyloxypropionate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, tri (2-hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1,2-Butadiene di (meth) acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nona ethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate 3,8-bis (meth) acryloyloxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) Propane, 1,4- Bis ((meth) acryloyloxymethyl) cyclohexane, hydroxypivalate neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and epoxy-modified bisphenol A di (meth) acrylate. These can be used singly or in combination of two or more.

  As the reactive polymer, the above-mentioned reactive polymer of the present invention is used. For example, the content of the reactive polymer in the photocurable resin composition is 5 to 60 parts by mass, or 10 to 50 parts by mass with respect to 100 parts by mass in total of the polyfunctional (meth) acrylate monomer and the reactive polymer It may be. When the content of the reactive polymer is in the above range, the hardness and adhesion of the surface of the laminate tend to be sufficient. The content of alkoxysilane groups in the reactive polymer may be similar to the content of alkoxysilane groups in the reactive polymer of the present invention described above.

  The total content of the polyfunctional (meth) acrylate monomer and the reactive polymer is preferably 4.5% by mass or more, more preferably 9% by mass or more, further preferably, based on the total mass of the photocurable resin composition. Is preferably 18% by mass or more, particularly preferably 36% by mass or more, preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less.

  The photopolymerization initiator may be a photopolymerization initiator capable of exhibiting a photopolymerization initiation ability by light irradiation in the presence of an ultraviolet absorber. As such a photopolymerization initiator, for example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl-2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6-trimethyl benzoyl diphenyl Phosphine oxide, bis ( , 4,6-trimethylbenzoyl) phenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoisopropyl ether, Benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra-tert-butylperoxycarbonylbenzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl]- 2- (phenylmethyl) -1-butanone, 4-benzoyl-4'-methyl diphenyl sulfide, and benzyl.

  The photopolymerization initiator can be used alone or in combination of two or more. For example, in the case of forming a thick cured film having a thickness of 10 μm or more, the use of two or more photopolymerization initiators tends to improve the curability. When the curability is improved, the photocurable resin composition can be cured more easily and sufficiently.

  The content of the photopolymerization initiator may be, for example, 1 to 15 parts by mass, or 3 to 10 parts by mass with respect to a total of 100 parts by mass of the polyfunctional (meth) acrylate monomer and the reactive polymer. When the content of the photopolymerization initiator is large, the photopolymerization initiator which has not been used for initiating the photopolymerization may remain, which may cause an adverse effect such as a decrease in the visible light transmittance of the cured film. On the other hand, when the content of the photopolymerization initiator is small, the photopolymerization initiation ability is not sufficiently expressed, and it tends to be difficult to obtain sufficient curing of the ultraviolet curable resin.

  As the UV absorber, known ones may be used, and in order to obtain UV absorbing ability (UV blocking ability) to be used in an electronic image display device, which has high UV absorbing ability, benzotriazole-based or hydroxyphenyltriazine-based UV-based UV absorbing agent. An absorbent may be used. In order to widen the absorption width of ultraviolet light, two or more types of ultraviolet light absorbers having different maximum absorption wavelengths may be used in combination.

  As a benzotriazole-based ultraviolet absorber, 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl ] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyhexyl) phenyl]- 2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl -3 '-(Methacryloyloxyethyl) phenyl] -2H-ben Triazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5 -Methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxy) Ethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, 2- (2-hydroxy) -5-tert-Butylphenyl) -2H-benzotriazole, benzene Lopanoic acid 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-, C7-9 branched linear alkyl ester, 2- (2H-benzotriazole) 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4 -(1,1,3,3- tetramethyl butyl) phenol etc. are mentioned.

  As a hydroxyphenyl triazine type ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] 4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- [4- (2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 dimethylphenyl) -1,3,6 5-triazine, 2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine, 2- (2- (2-hydroxy) Hydroki -4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 ,, 2'-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2'-dihydroxy-4, 4'-Dimethoxy-5,5'-disulfobenzophenone Disodium salt.

  The content of the ultraviolet light absorber can be appropriately adjusted according to the desired ultraviolet light transmittance and the absorbance of the ultraviolet light absorber, but for example, it is 1 per 100 parts by weight in total of the polyfunctional (meth) acrylate monomer and the reactive polymer. It may be 10 parts by mass, or 3 to 8 parts by mass. When the content of the ultraviolet light absorber is large, the curability of the photocurable resin composition by ultraviolet light tends to decrease, and the visible light transmittance of the obtained cured film may decrease. On the other hand, when the content of the ultraviolet absorber is small, there is a possibility that the cured film can not exhibit sufficient ultraviolet absorptivity.

  The photocurable resin composition can further contain an inorganic compound. As the inorganic compound, inorganic particles and those known as columnar, plate-like and layered inorganic compounds can be used, but those which have been subjected to an organic treatment so as to be able to be dispersed in a solvent are preferable.

  As the inorganic compound, at least one selected from the group consisting of glass frit, silica particles, alumina particles, aluminum hydroxide particles, magnesium hydroxide particles, tin oxide particles, and clay minerals can be used.

The clay mineral may be an inorganic compound in which ultra-thin unit crystal layers overlap to form one layered particle. In particular, clay compounds having a water-swelling property can be preferably used. More specifically, it is a clay compound having the property of coordinating water between very thin unit crystal layers, and absorbing and swelling, and generally, a tetrahedral structure in which Si ⁴⁺ coordinates to O ^2- And the layer which composes the octahedral structure by coordinating to O ^{2 −} and OH ⁻ such as Al ³⁺ , Mg ²⁺ , Fe ²⁺ , Fe ^3+, etc. 1 is a compound that combines and stacks to form a layered structure. This clay compound may be natural or synthetic.

  Representative compounds of clay minerals include hydrous silicates such as phyllosilicate minerals such as kaolinite clay minerals such as halloysite, kaolinite, enderite, dickite and nacrite, antigorite and chrysotile, etc. Antigolite clay minerals, montmorillonite, beidellite, nontronite, saponite, hectorite, hectorite, soconite, and smectite clay minerals such as stevensite, vermiculite clay minerals such as vermiculite clay, mica such as muscovite and phlogopite, margarite And mica clays, such as teniolite, etc. These clay minerals may be used alone or in combination of two or more. Among these clay minerals, smectite clay minerals such as montmorillonite are particularly preferable.

  Examples of alumina particles include gibbsite, bayerite, boehmite, pseudoboehmite, diaspore, aluminum hydroxide such as amorphous (alumina hydrate), and alumina of γ, 、, 、, 、, 、, 、, χ, χ, α form. A crystal etc. are mentioned. The metal aluminum or hydrolyzable aluminum compound is hydrolyzed with a specified amount of water in an organic solvent to form an alumina slurry, which is subsequently peptized in the presence of a specified amount of organic sulfonic acid to reach a predetermined alumina concentration It may be concentrated to These alumina particles can be used alone or in combination of two or more.

  The inorganic compound can be used preferably in an amount of 5 to 50 parts by mass with respect to 100 parts by mass in total of the polyfunctional (meth) acrylate monomer having two or more functions and the reactive polymer. If the content of the inorganic compound is within the above range, the ultraviolet curability of the curable composition is good, and the reduction of the visible light transmittance of the resulting cured film tends to be difficult to occur.

  The particle diameter of the inorganic compound is preferably 0.001 to 0.1 μm, and more preferably 0.005 to 0.05 μm. When the particle diameter is in the above range, industrial production is easy, and the transparency of the resulting cured film tends to be less likely to decrease. The particle diameter of the inorganic compound was measured by a dynamic light scattering method according to JIS 8828.

  The photocurable resin composition may further contain an antistatic agent. Such antistatic agents may be metal oxides and / or metal salts. Examples of metal oxides include ITO (indium-tin complex oxide), ATO (antimony-tin complex oxide), tin oxide, antimony pentoxide, zinc oxide, zirconium oxide, titanium oxide, and aluminum oxide. . Examples of the metal salt include zinc antimonate and the like.

  The content of the antistatic agent can be appropriately adjusted in accordance with the desired antistatic performance, but is, for example, 1 to 100 parts by mass with respect to a total of 100 parts by mass of the polyfunctional (meth) acrylate monomer and the reactive polymer. . When the content of the antistatic agent is in the above range, the ultraviolet curability of the photocurable resin composition is sufficiently obtained, and it tends to be difficult to reduce the visible light transmittance of the obtained cured film. In addition, when the content of the antistatic agent is large, the abrasion resistance of the resulting cured film tends to decrease, or the film forming property tends to decrease. When the content of the antistatic agent is small, it tends to be difficult to obtain a sufficient antistatic effect.

  The particle size of the antistatic agent may be 0.001 to 0.1 μm. Antistatic agents with extremely small particle sizes are difficult to industrially produce. An antistatic agent having an excessively large particle size tends to reduce the transparency of the resulting cured film. The particle size of the antistatic agent was measured by the dynamic light scattering method according to JIS 8828.

  The photocurable resin composition may contain, if necessary, additives such as a stabilizer, an antioxidant, a colorant, and a leveling agent. When a leveling agent is included, the smoothness and scratch resistance of the cured film can be enhanced.

  The photocurable resin composition may further contain a solvent in order to apply to a base film as described later. As such solvent, for example, methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol, 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol), 2 Alcohol solvents such as -methyl-2-propanol (tert-butyl alcohol); 2-ethoxyethanol, 2-butoxyethanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol Alkoxy alcohol solvents such as ketol solvents such as diacetone alcohol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate And the like.

  The content of the solvent is, for example, 20 to 10000 parts by mass with respect to 100 parts by mass in total of the polyfunctional (meth) acrylate monomer and the reactive polymer.

  The photocurable resin composition contains a polyfunctional (meth) acrylate monomer, a reactive polymer, a photopolymerization initiator, an ultraviolet light absorber, and, if necessary, a solvent, an inorganic compound, an antistatic agent, and other additives. It is obtained by mixing with an agent. There is no particular limitation on the order of mixing, etc.

[Laminate]
FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminate. A laminate 30 shown in FIG. 1 has a base film 10 and a cured film 20 laminated on one main surface 10 a of the base film 10. The cured film 20 is formed from the photocurable resin composition which concerns on the above-mentioned embodiment. That is, the cured film is a cured product of the photocurable resin composition. The laminate according to one embodiment is excellent in adhesion.

  The laminate according to one embodiment may have a substrate film and a cured film which is a cured product of the above-described photocurable resin composition of the present invention on at least one surface of the substrate film.

The substrate film may have transparency. The base film may be, for example, a film made of polyester such as polyethylene terephthalate (PET), polycarbonate (PC), polyarylate (PAR), polyether sulfone (PES), or polyimide (PI). The base film may be a film made of polyimide (PI) in that the effect on the cured film can be particularly remarkably exhibited. The base film may also contain an inorganic material. When the substrate film contains an inorganic material, the content thereof is in the range of more than 0% by weight and 60% by weight or less based on the weight of the substrate film, for example, in the range of 5 to 55% by weight, 10 to 50% by weight It may be in the range of
As an inorganic material, what was illustrated about the inorganic compound which may be contained in the above-mentioned photocurable composition can be used.

  The adhesion of the laminate can be measured in accordance with JIS K 5600-5-6. For example, the surface of the hard coat of the laminate is scratched in a grid of 10 squares × 10 squares at 2 mm intervals, and an adhesive tape (manufactured by Nichiban) is attached and peeled off in the direction of about 60 ° to the surface. Count the number of grids remaining.

  Moreover, the light resistance of a laminated body can be evaluated by performing the above-mentioned adhesion test after a QUV test. The QUV test uses UVCON (lamp: UVB 313 nm) manufactured by Atlas, is set so that the coated surface is irradiated with light, and is subjected to a 24 hr irradiation test. Thereafter, as described above, the adhesion is evaluated.

  The laminate according to one embodiment preferably has a number of squares remaining after peeling in the adhesion evaluation test of 90 or more, more preferably 95 or more, and still more preferably 100.

  In the adhesion evaluation test after the QUV test, the laminate according to one embodiment preferably has a number of grids remaining after peeling of 90 or more, more preferably 95 or more, and still more preferably 100.

  The flexibility of the laminate can be judged based on the amount of cracking in the laminate fragments in a flexing test in accordance with JIS K 5600-5-1: 1999. For example, the following bending test may be performed. First, the laminate is cut into a size of 1 cm long × 8 cm wide to prepare strip-like pieces of the laminate (hereinafter referred to as measurement samples). Next, a roll having a desired diameter is placed at the center of the measurement sample, and the measurement sample is bent about 10 times along the roll. Then, the presence or absence of the crack which arose in the cured film of the measurement sample is confirmed.

  In the above-mentioned bending test, when the measurement sample is wound on a roll with the cured film of the measurement sample inside, compressive stress acts on the cured film constituting the laminate and tensile stress acts on the base film. On the other hand, when the measurement film is wound around a roll with the cured film on the outside, compressive stress acts on the base film constituting the laminate and tensile stress acts on the cured film. The flexibility of the laminate can be evaluated by conducting a bending test in each of the two methods and confirming a crack in the cured film.

  As the diameter of the roll used for measurement is reduced, ie the winding diameter is reduced, more stress is exerted on the measurement sample in the test. Therefore, when the diameter of the roll is small, if the occurrence of cracking in the measurement sample is suppressed, it can be said that the measurement sample is excellent in flexibility.

  The laminate according to one embodiment is a case where the cured film is wound inside a roll having a diameter of 6 mm (winding diameter: 3 mm) in a bending test in accordance with JIS K 5600-5-1: 1999, Even when wound on the outside, cracking tends not to occur easily. As described above, in the laminate in which the occurrence of the cracking is suppressed, the cured film can absorb the stress, so the flexibility is excellent.

  The laminate according to one embodiment is a case where the cured film is wound inside a roll (winding diameter: 1 mm) with a diameter of 2 mm in a bending test according to JIS K 5600-5-1: 1999, Even when wound on the outside, cracking tends not to occur easily. The laminate according to one embodiment exhibits excellent flexibility because the cured film can absorb stress even when the winding diameter is smaller and a larger stress acts on the measurement sample. it can.

  The laminate according to one embodiment has a pencil hardness of 2H or more, or 3H or more according to JIS K 5600-5-4: 1999, measured with a load of 1 kg. You may When the pencil hardness is 2H or more, the laminate tends to exhibit sufficient hardness as a hard coat film. The pencil hardness measured by the above method is the pencil hardness of the laminate. When another layer is provided on the cured film, the pencil hardness of the laminate including the other layer is obtained.

  The laminate according to one embodiment may be such that no cracks occur in the cured film and the pencil hardness of the cured film is 2H or more in the bending test of the laminate using the above-described roll having a diameter of 6 mm. The laminate according to another embodiment may be such that no cracks occur in the cured film and the pencil hardness of the cured film is 3H or more in the bending test of the laminate using the above-mentioned roll having a diameter of 6 mm .

A laminate having a cured film formed from the photocurable resin composition according to one embodiment exhibits light resistance because discoloration (yellowing) of the substrate film due to light is suppressed. The light resistance can be judged by the amount of change (ΔYI) of the YI value of the laminate before and after light irradiation. The smaller the value of ΔYI, the better the light resistance of the laminate. Here, the YI value is calculated by tristimulus values X, Y and Z calculated by the calculation method defined in JIS Z 8701: 1982 and the following equation.
YI = 100 (1.28X-1.06Z) / Y

  The YI value can be measured using a commercially available spectrophotometer, for example, a product "U-4100" manufactured by Hitachi, Ltd., or the like.

  For example, when the base film is a resin film containing no ultraviolet light absorber or a resin film having photosensitivity, the light resistance of the laminate may be significantly improved.

  The cured film which comprises a laminated body is formed in the at least single side | surface side of a base film. The thickness of the cured film may be, for example, 3 μm or more and 20 μm or less. The thickness of the cured film may be 5 μm or more and 10 μm or less. When the thickness of the cured film is in the above range, the laminate including the base film and the cured film tends to be particularly excellent in flexibility, hardness, and light resistance. If the cured film is too thick, the pencil hardness is improved, but in the bending test, when the cured film is wound outward, cracking tends to occur easily.

  Since the layered product concerning one embodiment is excellent in flexibility and hardness, it can constitute a display with a polarizing plate etc. as a hard court film, for example. The laminate may have other layers in addition to the base film and the cured film. For example, another functional layer may be provided on the cured film of the laminate. The functional layer includes a hard coat layer and a surface treatment layer such as an antireflective layer or an antiglare layer. The functional layer may be laminated to the laminate via an adhesive or an adhesive. As the adhesive and the pressure-sensitive adhesive, known ones may be appropriately selected.

  Since the layered product concerning one embodiment is excellent in flexibility and hardness, while providing sufficient functional layer, while showing sufficient flexibility, it can have high hardness.

  The cured film which comprises a laminated body is formed in the at least single side | surface side of a base film. The thickness of the cured film may be, for example, 3 μm or more and 20 μm or less. The thickness of the cured film may be 5 μm or more and 10 μm or less. When the thickness of the cured film is in the above range, the laminate including the base film and the cured film tends to be particularly excellent in adhesion, flexibility, hardness, and light resistance. If the cured film is too thick, the pencil hardness is improved, but in the bending test, when the cured film is wound outward, cracking tends to occur easily.

  Since the layered product concerning one embodiment is excellent in adhesiveness, it can constitute a display with a polarizing plate etc., for example as a hard court film. The laminate may have other layers in addition to the base film and the cured film. For example, another functional layer may be provided on the cured film of the laminate. The functional layer includes a top hard coat layer and a surface treatment layer such as an antireflective layer or an antiglare layer. The functional layer may be laminated to the laminate via an adhesive or an adhesive. As the adhesive and the pressure-sensitive adhesive, known ones may be appropriately selected.

  The laminate according to one embodiment can have sufficient adhesion to the additional functional layer.

[Method of manufacturing laminate]
Next, the method to manufacture the laminated body which has a cured film formed from the photocurable resin composition of one Embodiment is demonstrated.

The method for producing a laminate having a cured film includes, for example, the following steps (1) and (2).
(1) A step of obtaining a composition layer by applying the above-described photocurable resin composition of the present invention onto a substrate film (a composition layer containing a photocurable resin composition is applied to one side of the substrate film Step of forming), and (2) Step of curing the composition layer by exposing the composition layer (step of forming a cured film by exposing the composition layer to cure the composition layer) .

Process (1)
The substrate film may have transparency. The substrate film may be, for example, a film of polyester such as polyethylene terephthalate (PET), polycarbonate (PC), polyarylate (PAR), polyether sulfone (PES), or polyimide (PI). The substrate film may be a polyimide (PI) film in that the effects relating to the cured film can be particularly remarkably exhibited. The base film may also contain a material. When the substrate film contains an inorganic material, the content is in the range of more than 0% by weight and 60% by weight or less based on the substrate film, for example, in the range of 5 to 55% by weight, and in the range of 10 to 50% by weight May be there.
As an inorganic material, what was illustrated about the inorganic compound which may be contained in the base film in description of the above-mentioned laminated body can be used.

  The thickness of the substrate film may be 30 to 300 μm, or 50 to 200 μm. When the base film is thin, the strength of the laminate of the cured film and the base film tends to decrease. When the substrate film is thick, the transparency of the substrate film may be reduced or the flexibility may be reduced. The substrate film may contain various additives. Such additives include, for example, stabilizers, plasticizers, lubricants, and flame retardants.

  The substrate film may have an adhesive layer provided on the surface thereof. An adhesive layer is for sticking a cured film to a base film, and is formed in accordance with a conventional method. The adhesive for forming the adhesive layer is appropriately selected according to the material of the base film and the cured film, but, for example, acrylic adhesive (adhesive), silicone adhesive (adhesive), polyester adhesive Etc. can be used. When the adhesive layer is thin, it is difficult to obtain sufficient adhesive strength, and when the adhesive layer is too thick, the laminate of the cured film and the base film tends to be too hard and the flexibility as a film tends to decrease. Therefore, the thickness of the adhesive may be in the range of 0.1 to 1 μm.

  As a method of apply | coating a photocurable resin composition to a base film, the roll coat method, a spin coat method, the coil bar method, the dip coat method, the die coat method etc. are mentioned, for example. A method that can be applied continuously, such as a roll coating method, is particularly advantageous in terms of productivity and production cost.

When the composition layer (coated photocurable resin composition) contains a solvent, a step (1 ′) of removing the solvent from the composition layer may be provided. The removal of the solvent is performed, for example, by evaporating the solvent from the composition layer by heating means using a heating device such as a hot plate, pressure reducing means using a pressure reducing device, or a combination thereof. The conditions of the heating means and the pressure reducing means can be selected according to the type of solvent contained in the composition layer and the like. For example, in the case of a hot plate, the surface temperature of the hot plate can be set in the range of about 50 to 200 ° C. The pressure reducing means may be a suitable pressure reducing device, and the substrate film having the composition layer can be enclosed in the pressure reducing device. The pressure of the atmosphere formed by the pressure reducing means (the internal pressure of the pressure reducing device) may be, for example, about 1 to 1.0 × 10 ⁵ Pa. By removing the solvent from the composition layer, a composition layer substantially free of the solvent can be formed on the substrate film.

Process (2)
Exposure is usually performed by irradiation of ultraviolet light. At this time, the ultraviolet light includes light in the visible light range. The photopolymerization initiator develops photopolymerization initiation ability by light irradiation, and the composition layer obtained in the step (1) is cured. The ultraviolet light may have a wavelength of 200 to 450 nm. The photopolymerization initiator may have an absorption range at a wavelength of 220 to 450 nm of light. In general, the wavelength of ultraviolet light is shorter than 380 nm, and the wavelength of visible light is 380 to 780 nm.

  If the wavelength of the ultraviolet light is less than 200 nm, the ultraviolet light tends to be absorbed by the ultraviolet light absorber, and the photopolymerization initiation ability of the photopolymerization initiator is not sufficiently expressed, so that the curability of the composition layer tends to be reduced. When the wavelength of the ultraviolet light exceeds 450 nm, the function as the ultraviolet light tends to decrease. When the wavelength of light in the absorption region of the photopolymerization initiator is less than 220 nm, the ultraviolet absorber tends to easily absorb the ultraviolet light, and the photopolymerization initiation ability tends to decrease. There are few kinds of photopolymerization initiators in which the wavelength of light in the absorption region exceeds 450 nm, and such photopolymerization initiators may cause the expression of photopolymerization initiation ability by ultraviolet light to be insufficient.

Other Steps In addition to the above steps (1) and (2), the method for producing a laminate having a cured film can further include an optional step such as a thermal curing or annealing step.

  Hereinafter, the embodiment will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the scope of the examples.

  Each physical property was measured as follows in each of the following Examples and Comparative Examples.

[Adhesiveness]
It measured based on JISK5600-5-6.
Make a scratch in a grid of 10 squares × 10 squares at 2 mm intervals, stick an adhesive tape (made by Nichiban), and count the number of squares left after peeling off in the direction of about 60 ° to the surface did.

[Lightfastness]
The above adhesion test was performed after the QUV test. The QUV test used UVCON (lamp: UVB 313 nm) manufactured by Atlas, was set so that the coated surface was irradiated with light, and was subjected to a 24 hr irradiation test.

[Pencil hardness]
The pencil hardness of the surface of the cured film was measured in accordance with JIS K 5600-5-4: 1999. The load was 1 kg.

[Flexibility]
The bending test was performed in accordance with JIS K 5600-5-1: 1999. The laminate of the cured film and the base film was cut into 1 cm × 8 cm to obtain a measurement sample. The measurement sample was wound on a roll with a diameter of 6 mm or 2 mm, respectively, with the direction of the cured film being inside or outside.
Flexibility was determined as follows based on the presence or absence of the occurrence of cracking in the cured film.
(Judgment of flexibility)
:: no cracks occurred ○: 1 to 4 cracks occurred △: 5 or more cracks occurred ×: material failure of the measurement sample

[Weight average molecular weight]
"Weight average molecular weight" means a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC). The measurement conditions were SHODEX GPC-104, column KF-602, mobile phase THF, flow rate 0.5 ml / min, temperature 40 ° C. The value used was a converted value from a polystyrene standard substance.

[Glass transition point]
About 10 mg of a dried sample of the poly (meth) acrylate solution is weighed into an aluminum pan, set in a DSC (DSC 3100 manufactured by MAC Science), cooled to -100 ° C. with liquid nitrogen, and then 10 ° C./min. The glass transition temperature was determined from the DSC chart obtained by raising the temperature in the above.

[Double bond equivalent]
The double bond equivalent was determined according to the following formula.
Double bond equivalent (g / mol) = feed amount of total monomer (g) / single amount of monomer used for double bond (mol)

Example 1
"Synthesis of hydroxyl group-containing (meth) acrylic polymer A"
In a flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 300 g of methyl isobutyl ketone is charged, the temperature is raised to 110 ° C. under a nitrogen stream, methyl methacrylate 245 g, 2-hydroxyethyl methacrylate 55 g, polypropylene glycol monoacrylate 100 g A mixed solution of 50 g of methyl isobutyl ketone and 3 g of azobisisobutyronitrile was charged into a dropping funnel, dropped at equal speed over 2 hours, and then aged at the same temperature for 1 hour. Next, 2 g of azobisisobutyronitrile and 100 g of methyl isobutyl ketone were charged into a dropping funnel and dropped at equal speed over 2 hours. Then, it was aged for 3 hours and diluted with 150 g of methyl isobutyl ketone to synthesize a hydroxyl group-containing (meth) acrylic polymer A. As a result of measuring the molecular weight of the obtained polymer, it was 71000 by weight average molecular weight, and the heating residue was 39.9%. The glass transition point (Tg) measured using a differential scanning calorimeter was about 30 ° C.

"Synthesis of (meth) acrylic urethane oligomer B"
In a flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 500 g of methyl isobutyl ketone, 318 g of isophorone diisocyanate (IPDI), 0.5 g of methoquinone, 0.05 g of dioctyltin are charged and 80 ° C. under a mixed gas of nitrogen and oxygen. The temperature rose to the end. Then, 182 g of 2-hydroxyethyl acrylate was charged into the dropping funnel and dropped at a constant speed over 3 hours. Then, it was aged at 80 ° C. for 5 hours, and the reaction was completed when NCO% was 6 to 8%. A (meth) acrylic urethane oligomer B having an isocyanate group at one end and an acrylate group at the other end was synthesized. As a result of measuring the molecular weight of the obtained oligomer, it was about 400 in weight average molecular weight, and the heating residue was 50.1%.

"Synthesis of (meth) acrylic urethane polymer C"
In a flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 265 g of methyl isobutyl ketone 300 g PTMG 650 manufactured by Mitsubishi Chemical Corporation, 190 g of hexamethylenediisonate and 0.05 g of dioctyl tin are mixed under a mixed nitrogen and oxygen stream The reaction mixture was heated to 80 ° C. and allowed to react for 5 hours to obtain a urethane oligomer containing isocyanate groups having both ends. Next, 0.5 g of methoquinone was added, and 45 g of 2-hydroxyethyl acrylate was charged into the dropping funnel and dropped at a constant speed over 1 hour. After dropping, the reaction was further carried out for 3 hours, and the reaction was diluted with 200 g of methyl isobutyl ketone to synthesize a (meth) acrylic urethane polymer C having an isocyanate group at one end and an acrylic group at the other end. As a result of measuring the molecular weight of the obtained polymer, it was about 7300 by weight average molecular weight, and the heating residue was 50.2%.

"Synthesis of Reactive Polymer E"
In a flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 700 g of a hydroxyl group-containing (meth) acrylic polymer A, 140 g of a (meth) acrylic urethane oligomer B, 100 g of a (meth) acrylic urethane polymer C, 0.5 g of methoquinone, The mixture was heated to 90 ° C. in a mixed stream of nitrogen and oxygen and allowed to react for 8 hours, and then 50 g of isocyanate group-containing alkoxysilane D (3-isocyanatopropyltriethoxysilane) was added and reacted for 3 hours. It was confirmed by FT-IR that the peak of the isocyanate group disappeared and diluted with 135 g of methyl isobutyl ketone to complete the reaction. Reactive polymer E was synthesized. As a result of measuring the molecular weight of the obtained polymer, it was 86000 in weight average molecular weight, and the heating residue was 40.2%. The double bond equivalent was 1812.

[Production of Photocurable Resin Composition]
30 parts by mass of tetrafunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) 30 parts by mass of trifunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMPT) 40 parts by mass of reactive polymer E 3 parts by mass of an absorbent (BASF, TINUVIN (registered trademark) 479), 5 parts by mass of a photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd., IRGACURE (registered trademark) 184), a photopolymerization initiator (Cibas Specialty Chemicals) 3 parts by mass of IRGACURE (registered trademark) 819, manufactured by Co., Ltd., 0.6 parts by mass of a leveling agent (by BYK-Chemie Japan Co., Ltd., BYK-350), 30 parts by mass of methyl ethyl ketone are stirred and mixed to obtain a photocurable resin The composition was obtained.

[Production of laminate]
As a transparent base film, a resin base containing a polyimide having a thickness of 80 μm and silica particles in accordance with known documents (for example, US Pat. No. 8,207,256) (silica particle content: 60% by mass) Was produced. Using the transparent polyimide film, the photocurable resin composition was coated by a bar coater so as to have a dry film thickness of 5 μm. Thereafter, drying was performed in an oven at 60 ° C. for 5 minutes, and ultraviolet rays were irradiated and cured at an energy of 500 mj / cm ² to obtain a laminate of a cured film and a substrate. The adhesion of the obtained laminate before and after the QUV test was measured as described above.
The results are shown in Table 1. Moreover, the obtained laminate had a pencil hardness of 2H, and the bendability with respect to the diameters of 6 mm and 2 mm was ◎ on the inside and the outside of the cured film, respectively.

Examples 2 to 14 and Comparative Example 1
In Example 1, the isocyanate group-containing alkoxysilane D was blended so as to have the ethoxysilane group content described in Tables 1 to 3 and that aluminum hydroxide and smectite were used at the contents described in Table 3 A laminate of the cured film and the base was obtained in the same manner as Example 1 except for the above. The results of measuring the adhesion between the obtained photocurable film and the substrate are shown in Tables 1 to 3. Further, the laminates obtained in Examples 2 to 8 and Comparative Example 1 had a pencil hardness of 2H, and the bendability for diameters of 6 mm and 2 mm was ◎ on the inside and the outside of the cured film, respectively. The laminates obtained in Examples 9 to 14 had a pencil hardness of 3 H, and the bendability for diameters of 6 mm and 2 mm was ◎ on the inside and the outside of the cured film, respectively.

Comparative example 2
"Synthesis of hydroxyl group-containing (meth) acrylic polymer A2"
In a flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 300 g of methyl isobutyl ketone is charged, the temperature is raised to 110 ° C. under a nitrogen stream, and 260 g of methyl methacrylate, 140 g of 2-hydroxyethyl methacrylate, 50 g of methyl isobutyl ketone A mixed solution of 3 g of azobisisobutyronitrile was charged into a dropping funnel, dropped at a constant speed over 2 hours, and then aged for 1 hour at the same temperature. Next, 2 g of azobisisobutyronitrile and 100 g of methyl isobutyl ketone were charged into a dropping funnel and dropped at equal speed over 2 hours. Then, it was aged for 3 hours and diluted with 150 g of methyl isobutyl ketone to synthesize a hydroxyl group-containing (meth) acrylic polymer A. As a result of measuring the molecular weight of the obtained polymer, it was 86,000 in weight average molecular weight, and the heating residue was 40.1%. The glass transition point (Tg) measured using a differential scanning calorimeter was about 70 ° C.

"Synthesis of Reactive Polymer E2"
700 g of hydroxyl group-containing (meth) acrylic polymer A2, 140 g of (meth) acrylic urethane oligomer B, 100 g of (meth) acrylic urethane polymer C, 0.5 g of methoquinone, 0.5 g of dioctyltin in a flask equipped with a stirrer, dropping funnel, condenser and thermometer After charging 0.05 g, the temperature was raised to 90 ° C. under a mixed flow of nitrogen and oxygen, and reacted for 8 hours, then 100 g of an alkoxy group-containing alkoxysilane D was added and reacted for 3 hours. It was confirmed by FT-IR that the peak of the isocyanate group disappeared and diluted with 210 g of methyl isobutyl ketone to complete the reaction. The reactive polymer E2 of Comparative Example 2 was synthesized. As a result of measuring the molecular weight of the obtained polymer, it was 195,000 in weight average molecular weight, and the heating residue was 40.6%. The double bond equivalent was 1933.

[Production of Photocurable Resin Composition and Laminate]
Regarding the preparation of the photocurable resin composition of Example 1, a photocurable resin composition and a photocurable resin composition in the same manner as in Example 1 except that the reactive polymer E2 was used in place of the reactive polymer E, and A laminate was produced. The results of measuring the adhesion are shown in Table 1. Moreover, the obtained laminate had a pencil hardness of 2H, and the bendability with respect to the diameters of 6 mm and 2 mm was ◎ on the inside and the outside of the cured film, respectively.

  The reactive polymer, the photocurable resin composition and the laminate of the present invention may be used, for example, as a hard coat film provided on a display screen of an electronic image display device such as a plasma display (PD) or liquid crystal display (LCD). it can.

Claims (15)

  Reactive polymer having an alkoxysilane group and a (meth) acrylate group in a side chain.   The main chain comprising a (meth) acrylate polymer, and the (meth) acrylate group as the side chain are attached to the terminal of the urethane polymer and / or urethane oligomer bonded to the main chain. Reactive polymers.   The reactive polymer according to claim 1, wherein a weight average molecular weight of the reactive polymer is 10,000 to 250,000.   The reactive polymer according to any one of claims 1 to 3, wherein a double bond equivalent of the reactive polymer is 800 to 125,000.   The reactive polymer according to claim 2, wherein the glass transition point (Tg) of the (meth) acrylate polymer is 0 to 70 ° C.   The reactive polymer according to any one of claims 1 to 5, wherein the alkoxysilane group is an ethoxysilane group.   The photocurable resin composition containing a polyfunctional (meth) acrylate monomer, the reactive polymer in any one of Claims 1-6, a photoinitiator, and a ultraviolet absorber.   The photocurable resin composition according to claim 7, wherein the content of the reactive polymer is 5 to 60 parts by mass with respect to a total of 100 parts by mass of the polyfunctional (meth) acrylate monomer and the reactive polymer.   The photocurable resin composition according to claim 7 or 8, wherein the content of the alkoxysilane group in the reactive polymer is more than 0% by mass and less than 40% by mass based on the reactive polymer.   The photocurable resin composition according to any one of claims 7 to 9, further comprising an inorganic compound.   The photocurable resin composition according to claim 10, comprising at least one inorganic compound selected from the group consisting of columnar, plate-like and layered inorganic compounds.   The laminated body which has a base film and the cured film which is a hardened | cured material of the photocurable resin composition in any one of Claims 7-11 laminated | stacked on the at least single side | surface side of the said base film.   The laminate according to claim 12, wherein the substrate film is a substrate film made of polyimide. A method of manufacturing a laminate,
A process for obtaining a composition layer by applying the photocurable resin composition according to any one of claims 7 to 11 onto a substrate, and (2) the composition by exposing the composition layer Curing the object layer.   15. The method of claim 14, wherein the substrate is a polyimide.

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