JP4561977B2 - Photocurable resin composition and method for producing laminate using the same - Google Patents

Description

  The present invention relates to a photocurable resin composition and a laminate using the same, and more specifically, a photocurable resin composition that can be cured in a short time under mild conditions, and obtained from the composition. The present invention relates to a photocurable resin composition capable of forming a high refractive index film having a relatively low surface tension on a film without repelling or pinholes, a laminate using the same, and a method for producing the same.

  An antireflection function is cited as one of the required performances of the image display board. The general principle of the antireflection function is to provide a low refractive index layer on the surface of the high refractive index layer and use the difference in optical path between the light reflected by the high refractive index layer and the light reflected by the low refractive index layer. Thus, the reflected light is reduced by causing interference with each other.

  Conventionally, such an antireflection film is produced by using a dry coating method such as a vapor deposition method or a sputtering method. According to the dry coating method, it is possible to produce a uniform film, but there is a problem that the production cost is high because the production speed is low. For this reason, in recent years, as a method for producing an antireflection film at a lower cost, a functional layer (transfer) can be formed on a release substrate by a wet coating method that can be formed in a milder and shorter time than a dry coating method. Attention has been focused on a method of transferring a layer) onto the surface of a transfer material or a pressure-sensitive transfer (that is, a transfer method), and attempts have been made to use the transfer layer as an antireflection film.

  By the way, as a low refractive index material used for an antireflection film, a resin composition containing a fluorine compound is generally used in order to lower the refractive index. Such a resin composition contains a low molecular fluorine-containing compound having a reactive group (Patent Documents 1 and 2), an inert fluorine-containing polymer and a compound having a reactive group. The thing is proposed (patent document 3). Although not intended as a low-refractive index material, an acrylic elastomer having the same level of surface tension as a general low-refractive index material is a (meth) acrylic copolymer having a fluoroalkyl group and a reactive group. Coalescence has also been proposed (Patent Document 4).

Japanese Patent Laid-Open No. 4-272788 JP 2000-17099 A JP-A-6-136062 Japanese Patent Laid-Open No. 2-182712

  However, in the case of the resin compositions of Patent Document 1 and Patent Document 2, since the intermolecular force of the contained fluorine compound is weak, a toxic fluorine compound may volatilize when the resin composition is applied, In the case of the resin composition of Patent Document 3, although the possibility of volatilization of the inert fluorine-containing polymer after coating is reduced, a reactive group is obtained when attempting to obtain a film having a lower refractive index. There is a problem in that the amount of the compound having a relatively small amount is relatively reduced and the strength of the film itself is weakened. Moreover, when the acrylic elastomer of patent document 4 is used as a low refractive index film, it must be heated at the time of coating. Therefore, there is a risk of thermal deformation when the base material is plastic. Further, when a film is formed under mild conditions, it takes time, and thus productivity may be reduced.

  In addition, in the transfer method, the functional layer (transfer layer) is transferred collectively to the surface of the transfer target. Therefore, when the transfer layer is used as an antireflection film, a low refractive index layer is provided on the transfer material substrate. Although it is necessary to provide a high refractive index layer on a low refractive index layer, since a resin composition containing a compound containing a fluorine atom, such as Patent Document 1, generally exhibits water repellency and oil repellency, such a resin composition In many cases, it is difficult to laminate the film on the cured film.

  Thus, the present condition is that the resin composition which can be hardened | cured on mild conditions and for a short time, and can obtain the low refractive index film | membrane which can be coated on a base material is calculated | required widely.

  An object of the present invention is to provide a resin composition capable of obtaining a low refractive index film that can be cured under mild conditions and in a short time and can be laminated on a substrate, a laminate using the same, and a method for producing the same. Is to provide.

The present inventors have found that although clear reason is unknown, a fluorine-containing (meth) acrylic copolymer having no fluorine-containing (meth) acrylic copolymer having -CF 2 _H unit, in the molecule It has been found that the above object can be achieved by using a photocurable resin composition containing a photopolymerizable ethylenically unsaturated compound having at least one ethylenic double bond in a specific blending ratio. The present invention has been completed.

That is, the present invention includes the following components (A) and (B):
(A) A (meth) acrylic copolymer comprising structural units represented by the following chemical formulas (I) and (II)

(In the formula (I), X is .R ¹ represents a hydrogen atom or a methyl group represents a fluoroalkyl group having 1 to 15 carbon atoms. However, carbon atoms part of ^{R 1} has the -CF ₂ H unit 1 Represents -15 fluoroalkyl groups.)

(In the formula (II), X represents a hydrogen atom or a methyl group. R ² represents an alkyl group or a fluoroalkyl group having 1 to 20 carbon atoms and having at least one (meth) acryloyl group. Represents an integer of 1 to 5); and

(B) The compounding quantity in the solid content (including the component which becomes solid after hardening) of the component (A) including the photopolymerizable ethylenically unsaturated compound having at least one ethylene double bond in the molecule A photocurable resin composition that satisfies the relationship of the following formulas (1) and (2) when (part by mass) is (Awt) and the blending amount (part by mass) of component (B) is (Bwt): provide. It is preferable that the photocurable resin composition further contains a photopolymerization initiator as the component (C).

Moreover, this invention is a manufacturing method of the laminated body by which the cured resin layer was laminated | stacked on the base material, Comprising: The following processes (a) and (b):
(A) a step of forming a film of the above-mentioned photocurable resin composition on a substrate; and (b) curing and curing the resulting photocurable resin composition film by irradiation with active energy rays. In a manufacturing method including a step of forming a resin layer, and as a specific embodiment thereof, in a manufacturing method of a transfer material having a release base film and a transfer layer including a cured resin layer provided thereon, the following steps (A ′) and (b ′):
(A ′) forming a film of the aforementioned photocurable resin composition on the surface of the release base film; and (b ′) irradiating the obtained photocurable resin composition film with active energy rays. To provide a method for producing a transfer material including a step of forming a cured resin layer.

  Further, the present invention is a laminate in which a cured resin layer is laminated on a substrate, and at least one of them is formed from the above-mentioned photocurable resin composition, and a specific embodiment thereof A transfer material having a release base film and a transfer layer provided thereon, wherein the transfer layer includes a cured resin layer made of the above-described photocurable resin composition. To do.

  The present invention also provides a transfer product characterized in that the transfer layer of the transfer material described above is transferred onto the surface of a transfer object.

The photocurable resin composition of the present invention comprises a fluorine-containing (meth) acrylic copolymer having a —CF ₂ H unit, a fluorine-containing (meth) acrylic copolymer not having, and at least one in the molecule. It contains a photopolymerizable ethylenically unsaturated compound having an ethylene double bond in a specific blending ratio, so it can be cured under mild conditions and in a short time, and can be laminated on a substrate. A cured resin film, for example, a low refractive index thin film (for example, a film having a thickness of about 0.01 to 10 μm) can be obtained.

  Hereinafter, the present invention will be described in detail. In this specification, the acryloyl group or methacryloyl group may be abbreviated as (meth) acrylate group, and acrylic acid or methacrylic acid may be abbreviated as (meth) acrylic acid.

The photocurable resin composition of the present invention includes the following components (A) and (B):
(A) A (meth) acrylic copolymer comprising structural units represented by the following chemical formulas (I) and (II)

(In the formula (I), X is .R ¹ represents a hydrogen atom or a methyl group represents a fluoroalkyl group having 1 to 15 carbon atoms. However, carbon atoms part of ^{R 1} has the -CF ₂ H unit 1 Represents -15 fluoroalkyl groups.)

(In the formula (II), X represents a hydrogen atom or a methyl group. R ² represents an alkyl group or a fluoroalkyl group having 1 to 20 carbon atoms and having at least one (meth) acryloyl group. Represents an integer of 1 to 5); and

(B) The compounding quantity in the solid content (including the component which becomes solid after hardening) of the component (A) including the photopolymerizable ethylenically unsaturated compound having at least one ethylene double bond in the molecule The relationship of the following formulas (1) and (2) is satisfied when the (part by mass) is (Awt) and the blending amount (part by mass) of the component (B) is (Bwt).

  In the above formula, when the value of “(Awt) / {(Awt) + (Bwt)}” is less than 0.5, the refractive index of the cured resin film obtained from the photocurable resin composition increases. A good antireflection function cannot be obtained, and if it exceeds 0.9, the content of the component (B) is relatively lowered, so that the film strength is lowered. In addition, when the value of “(Bwt) / {(Awt) + (Bwt)}” exceeds 0.50, the content of the component (A) is relatively lowered and the refractive index of the cured resin film is increased, which is favorable. Thus, the antireflection function cannot be obtained, and if it is less than 0.1, the film strength decreases.

  Moreover, from the viewpoint of the refractive index and the surface hardness of the cured resin layer, the photocurable resin composition preferably further satisfies the following expressions (1a) and (2a).

  The (meth) acrylic copolymer comprising the structural units represented by the chemical formulas (I) and (II) of the component (A) constituting the photocurable resin composition of the present invention is a low refractive index curing that can be laminated. It is a component for obtaining a resin film and increasing the film strength, and it is soluble in non-halogen solvents used in general paints.

The structural unit of the chemical formula (I) constituting the (meth) acrylic copolymer of the component (A) contributes particularly to lowering the refractive index of the cured resin film. Here, X in the chemical formula (I) is a hydrogen atom or a methyl group, but is preferably a methyl group in order to keep the film strength high. R ¹ is a fluoroalkyl group having 1 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. However, in order to improve the wettability of the surface of the cured resin film and obtain a cured film that can be laminated, a part of the fluoroalkyl group is a fluoroalkyl group having 1 to 15 carbon atoms having a —CF ₂ H unit. There is a need to. In this case, if the ratio of the “fluoroalkyl group having 1 to 15 carbon atoms having a —CF ₂ H unit” in the entire “fluoroalkyl group having 1 to 15 carbon atoms” of R ¹ is too low, the effect of improving wettability is obtained. If it is not sufficient and is too high, the refractive index is difficult to decrease, so it is preferably 30 to 100 mol%, more preferably 50 to 100 mol%.

Preferable specific examples of the monomer containing a —CF ₂ H unit necessary for constituting the structural unit represented by the chemical formula (I) include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H. , 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, and the like. Among them, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate is particularly preferred from the viewpoint of the strength of the resulting cured resin film. Is particularly preferred.

Specific examples of monomers that do not contain a —CF ₂ H unit that can be used as necessary to constitute the structural unit represented by the chemical formula (I) include 2,2,2-trifluoroethyl ( (Meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2-trifluoromethyl-3,3,3-trifluoropropyl (meth) acrylate, 1-methyl-2,2, 3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 1-methyl-2,2,3,3,4, 4,4-heptafluorobutyl (meth) acrylate, 3-trifluoromethyl-4,4,4-trifluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,5,5- Nonafluoropentyl ( ) Acrylate, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl (meth) acrylate, 3,3,4,4,5,5,6,6 , 6-Nonafluorohexyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl (meth) acrylate, 5-trifluoro Methyl-3,3,4,4,5,6,6,6-octafluorohexyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7 , 8,8,8-pentadecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate 7-trifluoromethyl-3,3,4,4,5,6,6,7,8,8,8-undecafluorooctyl ( (Meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl (meth) acrylate 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) acrylate, 9-trifluoromethyl- 3,3,4,4,5,6,6,7,8,8,9,10,10,10-tetradecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5 6,6,7,7,8,8,9,9,10,10,11,11,11-nonadecafluorodecyl (meth) acrylate and other fluoroalkyl groups having a trifluoromethyl group at the terminal thereof ( (Meth) acrylate; 2,2,3,3,4,4-hexafluorocyclobutyl (meth) a Relate, 2,2,3,3,4,4,5,5-octafluorocyclopentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6-decafluorocyclohexyl ( (Meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorocycloheptyl (meth) acrylate, 2,2,3,3,4,4,5 , 5,6,6,7,7,8,8-tetradecafluorocyclooctyl (meth) acrylate and the like; 2-trifluoromethylcyclobutyl (meth) acrylate, 3-trifluoro Methylcyclobutyl (meth) acrylate, 2-trifluoromethylcyclopentyl (meth) acrylate, 3-trifluoromethylcyclopentyl (meth) acrylate, 2-trifluoromethyl Cyclohexyl (meth) acrylate, 3-trifluoromethylcyclohexyl (meth) acrylate, 4-trifluoromethylcyclohexyl (meth) acrylate, 2-trifluoromethylcycloheptyl (meth) acrylate, 3-trifluoromethylcycloheptyl (meth) Examples thereof include trifluoromethylcycloalkyl (meth) acrylate such as acrylate.

On the other hand, the structural unit of the chemical formula (II) contributes to improving the cross-linking density of the cured resin film and improving the film strength. Here, X in the chemical formula (II) is a hydrogen atom or a methyl group, but is preferably a methyl group in order to keep the film strength high. R ² is an alkyl group or fluoroalkyl having 1 to 20 carbon atoms, preferably 5 to 20, more preferably 5 to 15 and having at least one, preferably 1 to 3 (meth) acryloyl groups. Represents a group. Although n is an integer of 1-5, Preferably it is an integer of 1-3.

  The structural unit represented by the chemical formula (II) is, for example, a copolymer of a monomer having a (meth) acryloyl group and an isocyanate group and a monomer for constituting the structural unit represented by the above chemical formula (I). It can be easily obtained by urethanizing the compound with a compound having a (meth) acryloyl group and a hydroxyl group.

  Specific examples of the monomer having a (meth) acryloyl group and an isocyanate group include (meth) acryloyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate. 2-Methacryloyloxyethyl isocyanate is preferred from the viewpoints of handleability, toxicity, and film strength.

  The compound having a (meth) acryloyl group and a hydroxyl group is a compound capable of urethanation reaction with the monomer having the (meth) acryloyl group and isocyanate group described above, and has a (meth) acryloyl group and one hydroxyl group in the molecule. If it is a compound which has the alkyl group or fluoroalkyl group to contain, there will be no restriction | limiting in particular. Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate, 2-hydroxy-3- ( (Meth) acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-4,4,5,5,6,6,7,7,7, -nonafluoroheptyl (meth) acrylate, 2 -Hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl (meth) acrylate, 2-hydroxy-4,4,5,5, 6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorounenyl (meth) acrylate, 2-hydroxy-6-to Fluoromethyl-4,4,5,5,6,7,7,7-dodecafluoroheptyl (meth) acrylate, 2-hydroxy-8-trifluoromethyl-4,4,5,5,6,6,7 , 7,8,9,9,9-dodecafluorononyl (meth) acrylate, 2-hydroxy-10-trifluoromethyl-4,4,5,5,6,6,7,7,8,9,9 , 10, 11, 11, 11-pentadecafluorounenyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-par Fluorohexyl-2-hydroxypropyl acrylate is preferred because of its high reactivity during curing. When it is desired to lower the refractive index of the cured film, a compound having a fluoroalkyl group such as 2-hydroxy-4,4,5,5,6,6,7,7,7-nonafluoroheptyl (meth) acrylate is used. preferable.

Preferred structural units of the chemical formula (II) include the following chemical formula (III) from the viewpoint of productivity of the cured resin film or (IV) from the viewpoint of the antireflection function of the cured resin film. However, in (IV), X represents a hydrogen atom or a methyl group. R ³ represents a fluoroalkyl group having 1 to 14 carbon atoms, preferably a perfluoroalkyl group having 3 to 10 carbon atoms.

The proportion of the structural units represented by the chemical formulas (I) and (II) in the (meth) acrylic copolymer of the component (A) is the structural unit represented by the chemical formula (I) (a mol). When the structural unit represented by (II) is (b mol), it is preferable to satisfy the relationship of the following formulas (3) and (4).

  In the above formula, when the value of “(a mol) / {(a mol) + (b mol)}” is less than 0.40, the refractive index of the cured resin film of the photocurable resin composition is lowered. There is a possibility that the hardness of the cured resin film is lowered. If the value of “(b mol) / {(b mol) + (b mol)}” is smaller than 0.01, the hardness of the cured resin film may be lowered. There is a possibility that the refractive index of the film cannot be lowered.

  Further, from the viewpoint of the refractive index and surface hardness of the cured resin layer, the abundance of the structural units represented by the chemical formulas (I) and (II) in the (meth) acrylic copolymer of the component (A) is It is preferable to satisfy the relationship of the formulas (3a) and (4a).

  The (meth) acrylic copolymer of component (A) containing the structural units represented by chemical formulas (I) and (II) is obtained by copolymerizing the above monomers corresponding to the respective structural units. Can do.

  The photocurable resin composition of the present invention contains a photopolymerizable ethylenically unsaturated compound having at least one, preferably two ethylene double bonds in the molecule as component (B). Here, “photopolymerizable” means that polymerization is possible by irradiation with active energy rays (for example, ultraviolet rays, visible light, electron beams, X-rays, etc.). In addition, the component (B) may be the same as the compound having a (meth) acryloyl group and a hydroxyl group used for forming the structural unit of the chemical formula (II) constituting the component (A). Specific examples of such photopolymerizable ethylenically unsaturated compounds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopenteno Xylethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (Meth) acrylate, biphenoxyethyl (meth) acrylate, biphenoxyethoxyethyl (meth) acrylate, norbornyl (meth) acrylate, phenylepoxy (meth) acrylate, (meth) acryloylmorpholine, diacetone acrylamide, N- [2- (Meth) acryloylethyl] -1,2-cyclohexanedicarboximide, N- [2- (meth) acryloylethyl] -1,2-cyclohexanedicarbomido-1-ene, -Monofunctional (meth) acrylate monomers such as [2- (meth) acryloylethyl] -1,2-cyclohexanedicarbomido-4-ene; N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam, Vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meta ) Acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol pivalic acid ester di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Reethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol-A-diglycidyl ether di (meth) acrylate, ethylene oxide modified diacrylate of 1,4-cyclohexanedimethanol, ethylene oxide modified tetrabromobisphenol- A bifunctional (meth) acrylate such as A-di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate , Pentaerythritol hexa (meth) acrylate, tri (meth) acrylate of ethylene oxide-added trimethylolpropane, ethyl Tetra (meth) acrylate of oxide-added ditrimethylolpropane, tri (meth) acrylate of propylene oxide-added trimethylolpropane, ethylene oxide-modified isocyanuric acid tri (meth) acrylate, tetra (meth) acrylate of propylene oxide-added ditrimethylolpropane, Tetra (meth) acrylate of ethylene oxide-added pentaerythritol, tetra (meth) acrylate of propylene oxide-added pentaerythritol, penta (meth) acrylate of ethylene oxide-added dipentaerythritol, penta (meth) acrylate of propylene oxide-added dipentaerythritol, Hexa (meth) acrylate of ethylene oxide-added dipentaerythritol, propylene Polyfunctional monomer such as hexa (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl formal, 1,3,5-triacryloylhexahydro-s-hydrazine of xide-added dipentaerythritol; ethylene oxide modified Bisphenol-A-divinyl ether, ethylene oxide-modified bisphenol-F-divinyl ether, ethylene oxide-modified catechol divinyl ether, ethylene oxide-modified resorcinol divinyl ether, ethylene oxide-modified hydroquinone divinyl ether, ethylene oxide-modified 1,3,5, benzenetriol Vinyl ether monomers such as trivinyl ether; oligomer acrylates such as urethane acrylate and ester acrylate And the like. These may be used alone or in combination. Of these, polyfunctional monomers having two or more functions are preferably used.

  In addition to the photopolymerizable ethylenically unsaturated compound, the photocurable resin composition can contain a photopolymerizable epoxy compound or oxetane compound, if necessary.

  Epoxy compounds include 1,2-epoxycyclohexane, 1,4-butanediol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, trimethylolpropane diglycidyl ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, glycidyl ether of phenol novolac, bisphenol A diglycidyl ether, oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) ) Oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and the like.

In addition, the photocurable resin composition preferably contains a photopolymerization initiator as the component (C) in order to polymerize by irradiation with active energy rays. In addition, it is preferable to contain one or more photocatalytic compounds such as a photosensitizer and a photo accelerator. As a photocatalyst compound, it can select from a well-known photocatalyst compound suitably, and can be used.

  As a photoinitiator of a component (C), it can select suitably according to the kind (ultraviolet ray, visible light, an electron beam, etc.) of the active energy ray which is a hardening means.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4-diaminobenzophenone, Benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-thioxanthone, camphorquinone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one and the like. Further, a photopolymerization initiator having at least one (meth) acryloyl group in the molecule such as N-acryloyloxyethylmaleimide can also be used.

  The blending amount of the photopolymerization initiator is preferably based on 100 parts by mass of the solid content of the photocurable resin composition excluding the diluent described later (the total of components already solid before curing and solid components after curing). Is 0.1 to 10 parts by mass, more preferably 3 to 5 parts by mass.

  Specific examples of photosensitizers that can be used together with a photopolymerization initiator to promote photopolymerization include 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. Specific examples of the photo-accelerating agent that can be used together with the photo-polymerization initiator for promoting photo-polymerization include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid 2-n. -Butoxyethyl, 2-dimethylaminoethyl benzoate and the like can be mentioned.

  Moreover, in order to improve the coating property, a diluent can be added to the photocurable resin composition. The addition amount of the diluent can be appropriately determined according to the thickness of the cured layer to be formed. For example, when the thickness of the hardened layer is about 0.1 μm, it is preferable that the coating is applied at a wet film thickness of 1.9 μm with a diluent of 94.75% by mass with respect to a solid content of 5.25% by mass.

  As the diluent, a diluent used in a general resin coating solution can be used. Specifically, for example, ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone; methyl acetate, ethyl acetate, acetic acid Ester compounds such as butyl, ethyl lactate and methoxyethyl acetate; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve and dioxane; aromatic compounds such as toluene and xylene; pentane and hexane Aliphatic compounds; halogen-based hydrocarbons such as methylene chloride, chlorobenzene and chloroform; alcohol compounds such as methanol, ethanol, normal propanol and isopropanol. As the diluent, water and lower alcohols (for example, methanol, ethanol, propanol, etc.) having high affinity with the solid photopolymerizable substance can be preferably used.

  If necessary, the photocurable resin composition of the present invention may further include an inorganic filler, a polymerization inhibitor, a color pigment, a dye, an antifoaming agent, a leveling agent, a dispersing agent, a light diffusing agent, a plasticizer, and an antistatic agent. An agent, a surfactant, a non-reactive polymer, a near-infrared absorber, and the like can be added as long as the effects of the present invention are not impaired.

  In addition, the photocurable resin composition of the present invention comprises components (A) and (B) described above and other components including component (C) blended as necessary according to a conventional method. It can be prepared by mixing uniformly.

  The photocurable resin composition of the present invention can be formed on a substrate and photocured to form a laminate comprising a substrate and a cured resin layer. Such a laminate includes the type, thickness, and physical properties of the substrate used, and the physical properties and thickness of a cured resin layer made of a photocurable resin composition, and an additional thermoplastic layer that is laminated as necessary. It can be used in a wide range according to the kind and properties (for example, adhesive layer) of the thermosetting layer or the photocurable layer. For example, it can be used as a transfer material, an antireflection material, or the like.

  The substrate of such a laminate is not particularly limited as long as it is plate-like or film-like, such as a metal substrate such as iron or aluminum, a glass substrate, a ceramic substrate, an acrylic resin, a polyester resin, or a polycarbonate. A resin base material etc. can be mentioned.

  Such a laminate can be manufactured by a manufacturing method including the following steps (a) and (b). Hereinafter, it demonstrates for every process.

Step (a)
First, a film of the photocurable resin composition of the present invention is formed on a substrate. As a film forming method, a known method such as an impregnation method, a relief printing method, a flat printing method, a coating method using a roll used in intaglio printing, a spray method of spraying on a substrate, a curtain flow coat, or the like is used. Can be used. When a diluent is contained in the photocurable resin composition, the coating film is preferably heated and dried in a heating furnace, a far infrared furnace, or a super far infrared furnace.

  As the base material, a plate-like or film-like metal (iron, aluminum, etc.) substrate, a ceramic substrate including a glass substrate, a plastic substrate such as acrylic resin, PET, polycarbonate, a thermosetting resin substrate, etc. may be used. it can.

Step (b)
The photocurable film obtained in the step (a) is cured by irradiating with active energy rays such as ultraviolet rays, visible light, laser, electron beam, X-rays, etc. to form a cured resin layer. Thereby, the laminated body by which the cured resin layer which consists of a photocurable resin composition of this invention on the base material was laminated | stacked is obtained. In addition, as a light source when using an ultraviolet-ray, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp etc. are mentioned.

  The laminate obtained in this way is not limited to a two-layer structure of a base material and a cured resin layer, and a layer of a thermoplastic, thermosetting, or photocurable material may be provided in advance, or a cured layer You may provide again after formation.

  As described above, the photocurable resin composition of the present invention, the laminate having a cured resin layer comprising the photocurable resin composition, and the production method thereof have been described. However, as an example of preferred specific embodiments of these laminates and production methods, a transfer material and its The manufacturing method is shown below. In addition, the meaning of the term in them is as having already demonstrated.

  The transfer layer of the transfer material of the present invention has at least one cured resin layer composed of the above-described photocurable resin composition, and therefore may be a cured resin layer alone, but other low refractive index layers. Further, it may be a multilayer structure of two or more layers including a high refractive index layer, a polymer layer and the like.

  For example, the transfer layer can be used as an antireflection layer in combination with other low refractive index layers, high refractive index layers, or the like, depending on the intended use of the transfer material. It may also include a hard coat layer such as an acrylic or silicon type, a functional layer such as an antibacterial layer, a decorative layer such as a printing layer or a colored layer, a vapor deposition layer (conductive layer) made of a metal or a metal compound, a primer layer, or the like. it can.

  Specific examples of the layer structure of the transfer layer include a cured resin layer, a low refractive index layer / cured resin layer, a low refractive index layer / high refractive index layer / cured resin layer, a low refractive index layer / a high refractive index layer / vapor deposition. Layer / primer layer / cured resin layer, low refractive index layer / high refractive index layer / primer layer / evaporation layer / primer layer / cured resin layer, low refractive index layer / high refractive index layer / primer layer / cured resin layer, hard Examples thereof include a coat layer / cured resin layer, a printed layer / cured resin layer, and a decorative layer / cured resin layer.

  Although there is no restriction | limiting in particular in the film thickness of the said cured resin layer, Usually, it selects suitably from the range of about 0.5-20 micrometers. Further, the film thicknesses of the other layers are not particularly limited, but are usually appropriately selected from the range of about 0.1 to 10 μm.

  In order to form a cured resin layer from the photocurable resin composition, the film of the formed photocurable resin composition is subjected to ultraviolet light, visible light, α according to a known photocuring technique of a photopolymerizable resin. A wide range of active energy rays such as rays, β rays, γ rays, electron rays, and lasers can be used. Among these, it is preferable to use ultraviolet rays. Any light source such as a point light source, a line light source, and a surface light source can be used, but a line light source is generally used from the viewpoint of practicality. For example, an ultraviolet lamp is generally used as an ultraviolet ray generation source in terms of practicality and economy, and specific examples include a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, and a metal halide lamp. In addition, what is necessary is just to scan suitably so that predetermined | prescribed light can be irradiated to the layer which consists of a photocurable resin composition, when using a point light source or a line light source.

  Since the transfer material has a release base film and the above-described transfer layer thereon, specific examples of the layer structure of the transfer material include a release base film / cured resin layer, a release base film / Low refractive index layer / cured resin layer, release base film / low refractive index layer / high refractive index layer / cured resin layer, release base film / low refractive index layer / high refractive index layer / vapor deposition layer / primer layer / curing Resin layer, release base film / low refractive index layer / high refractive index layer / primer layer / evaporation layer / primer layer / cured resin layer, release base film / low refractive index layer / high refractive index layer / primer layer / curing Examples thereof include a resin layer, a release base film / hard coat layer / cured resin layer, a release base film / printing layer / cured resin layer, and a release base film / decoration layer / cured resin layer.

  The releasable base film used for the transfer material of the present invention is not particularly limited. For example, the releasable base film has a releasability that exhibits a surface tension of 40 dyn / cm or less at 20 ° C., and has a sufficient self-holding property. Any film can be used as long as it is a film used for an ordinary transfer material. Specific examples of the release base film according to the present invention include polyester films such as polyethylene terephthalate films, polyolefin films such as polyethylene films and polypropylene films, polycarbonate films, polyvinylidene fluoride films, polyvinyl fluoride films, polyhexafluoropropylene films, Fluorine-based resin films such as poly (heptafluoroisopropyl (meth) acrylate film), silicon-containing polymer films such as polyoxydimethylsilylene, polyoxymethylsilylene, polyoxydimethylsilylene-α, ω-dibutanoic acid, and polyoxyvinylsilylene , Polystyrene film, polyamide film, polyamideimide film, polyvinyl chloride film, cellulose acetate film, etc. Resin films, paper such as cellophane paper, glassine paper, Japanese paper, composite films of these, and those subjected to release treatment.

  The thickness of the releasable base film is not particularly limited, but is usually preferably in the range of 4 to 150 μm, more preferably in the range of 12 to 100 μm, in order to suppress the occurrence of wrinkles and cracks, More preferably, it is in the range of 30-100 μm.

  When the mold release property of the mold release base film is insufficient, a mold release treatment can be further performed on at least one surface of the mold release base film. Such a release treatment can be performed by a known method by appropriately selecting a release polymer or wax. Examples of the treatment agent used for the release treatment include release waxes such as paraffin wax; release resins such as silicone resins, melamine resins, urea resins, urea-melamine resins, cellulose resins, and benzoguanamine resins. Molding resin; various surfactants, etc., alone or mixed with a solvent, etc., applied onto a releasable base film according to a normal printing method such as gravure printing, screen printing, or offset printing, and dried Furthermore, it can be formed by curing (heating, ultraviolet irradiation, electron beam irradiation, radiation irradiation) as necessary.

  As described above, the transfer material of the present invention can be provided with a primer layer between layers in a transfer layer having a multilayer structure. Such a primer layer is a coating layer of a composition mainly composed of a polymer component having good adhesion to both the layers in the transfer material of the present invention, and the thickness is preferably in the range of about 0.5 to 5 μm. Specific examples of the primer layer include layers of acrylic resin, vinyl acetate resin, melamine resin, polyester resin, urethane resin, and the like. These layers can be formed by, for example, dissolving the resin in a solvent, applying the resin by the printing method, and drying.

  The transfer material of the present invention can be produced according to a production method including steps (a ′) and (b ′) as described below.

Step (a ′)
On the release base film, the above-mentioned photocurable resin composition of the present invention is applied to form a film of the photocurable resin composition. The release base film and the photocurable resin composition are as described above.

Step (b ′)
The film of the photocurable resin composition obtained in the step (a ′) is irradiated with active energy rays as described above. Thereby, the film | membrane of a photocurable resin composition hardens | cures and becomes a cured resin layer. Thereby, the transfer material which has the cured resin layer which consists of a photocurable resin composition of this invention is obtained.

  The transfer material thus obtained is not limited to the two-layer structure of the release base film and the cured resin layer, and may be provided with a layer of thermoplastic, thermosetting, or photocurable material in advance, or You may provide again after hardened layer formation.

  The transfer material according to the present invention is capable of thermally transferring the transfer layer to the transfer material by heating the outermost surface layer in close contact with the transfer material. The shape and the like of the material to be transferred are not particularly limited, but preferred examples include commercially available resin sheets, films, glass plates, and the like. Moreover, when using for a display screen protection board etc., it is preferable that it is a resin sheet as a to-be-transferred material. Specific examples of such resins are not particularly limited as long as they are transparent at visible light wavelengths, but methacrylic resins such as polymethyl methacrylate (PMMA), polycarbonate resins, methyl methacrylate-styrene copolymers (MS resins) and the like are preferable. Used.

  The transfer material of the present invention can easily transfer a transfer layer to a surface of a transfer target such as an image display device or a helmet shield with good transfer efficiency at low cost. Accordingly, the obtained transfer product is a transfer product having a good appearance.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this.

Reference Example 1 (Production of polymer for low refractive index resin)
Into a 100 mL three-necked flask in which the internal air was replaced with nitrogen, 50 mL of toluene, 8FM, 17FM and / or MOI shown in Table 1, and 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (Product name: Perocta O, manufactured by NOF Corporation) 30 mg was added, and the mixture was stirred at 80 ° C. for 6 hours. Furthermore, 10 mg of N, N-dimethyl-p-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred for 30 minutes, and then HEA or R1633 and N-nitrosophenylhydroxylamine aluminum (Wako Pure Chemical Industries, Ltd.) shown in Table 1 were used. (Company) 5 mg was added, and the mixture was further stirred for 3 hours. Thereafter, the polymerization solution was cooled and then poured into hexane, and the resulting precipitate was collected by filtration and vacuum dried for 10 hours to obtain a polymer for low refractive index resin.

(Table 1 note)
* 1: 1H, 1H, 5H-octafluoropentyl methacrylate (trade name: Biscoat 8FM, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
* 2: 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (trade name: Biscoat 17FM, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
* 3: 2-Methacryloyloxyethyl isocyanate (trade name: Karenz MOI Showa Denko KK)
* 4: 2-hydroxyethyl acrylate (Wako Pure Chemical Industries, Ltd.)
* 5: 3-perfluorohexyl-2-hydroxypropyl acrylate, (3- (1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl) -2-Hydroxypropyl acrylate (trade name: R1633, manufactured by Daikin Fine Chemical Co., Ltd.)
6: Represents isolated yield 7: Represents NMR value * 8: Polystyrene equivalent molecular weight by GPC

Reference Example 2 (Production Method of High Refractive Index Resin Composition)
Titanium fine particles (trade name HIT, manufactured by Nissan Chemical Co., Ltd.) 1.8% by mass, dipentaerythritol hexaacrylate (trade name: DPCA-60 manufactured by Nippon Kayaku Co., Ltd.) 1.2% by mass, photopolymerization initiator (trade name) : Irgacure 184 Ciba Specialty Chemicals Co., Ltd.) 0.15% by mass and 96.85% by mass of isopropanol were mixed to obtain a high refractive index resin composition.

Reference Example 3 (Method for producing hard coat resin composition)
Dipentaerythritol hexaacrylate (trade name: DPCA-60 manufactured by Nippon Kayaku Co., Ltd.) 10% by mass, ethylene oxide modified bisphenol A diacrylate (trade name biscoat # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 14% by mass, poly Methyl methacrylate (trade name: Parapet HR-L, manufactured by Kuraray Co., Ltd.) 6 mass%, photopolymerization initiator (trade name: Irgacure 184 Ciba Specialty Chemicals Co., Ltd.) 1.5 mass%, methyl isobutyl ketone 68.5 mass% Were mixed to obtain a hard coat resin composition for transfer film.

Examples 1-5, Comparative Examples 1-3
In a ratio of 3% by mass of the photocurable resin composition shown in Table 2, 0.15% by mass of a photopolymerization initiator (trade name: Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), and 96.85% by mass of methyl isobutyl ketone. A low refractive index resin composition was obtained by mixing. The obtained low refractive index resin composition was applied on a 50 μm thick polyester film so as to have a dry thickness of 1 μm, dried at 130 ° C. for 30 seconds, and further irradiated with ultraviolet rays (80 w high pressure mercury lamp, speed 1 m). / Min, 1 pass). Thereby, a low refractive index layer was formed.

  Subsequently, on this low refractive index layer, the high refractive index resin composition shown in Reference Example 2 was applied so as to have a dry thickness of 1 μm, dried at 130 ° C. for 30 seconds and irradiated with ultraviolet rays (80 w high pressure). Mercury lamp, speed 1 m / min, 1 pass). Thereby, a high refractive index layer was formed.

  On this high refractive index layer, the hard coat resin composition shown in Reference Example 3 was applied at a film thickness of 10 μm, dried at 130 ° C. for 30 seconds and irradiated with ultraviolet rays (80 w high pressure mercury lamp, speed 1 m / min, 1 pass). Went. Thereby, a hard coat was formed, and a transfer film was obtained.

  The obtained transfer film was thermally transferred to a 2 mm thick polymethyl methacrylate plate (roll speed 1 m / min, roll temperature 160 ° C.), and the polyester film was peeled off to obtain a laminate. The obtained laminate was evaluated for scratch resistance and reflectance of the transfer layer as described below. The results are shown in Table 2.

Scratch resistance A stack of 12 cheesecloths is attached to the tip of a metal rod with a diameter of 0.6 mm, and it is brought into contact with the transfer layer of the laminated plate under a load of 1.6 kg. When the surface was reciprocated 150 times, it was visually confirmed whether or not the transfer layer was peeled off from the laminate.

Reflectance (minimum value)
The 5 ° regular reflectance of the transfer layer of the laminate was measured, and the minimum reflectance at 400 nm to 700 nm was measured.

(Table 2 Note)
* 9: See Reference Example 1 * 10: 1H, 1H, 5H-octafluoropentyl methacrylate (trade name: Biscoat 8FM, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
* 11: Bisphenol-A-diglycidyl ether di (meth) acrylate (trade name: Biscote # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
* 12: Ethylene oxide modified isocyanuric acid tri (meth) acrylate (trade name M315, manufactured by Toagosei Co., Ltd.)
13: Pentaerythritol hexa (meth) acrylate (trade name DCPA60, manufactured by Nippon Kayaku Co., Ltd.)
14: Product name MEK-ST, manufactured by Nissan Chemical Industries, Ltd.

  From Table 2, it can be seen that satisfactory results were obtained for both the scratch resistance and the reflectance of the transfer layer of the transfer products prepared from the transfer films of Examples 1 to 5. On the other hand, it can be seen that Comparative Examples 1 and 2 have a problem with the scratch resistance of the transfer layer, and Comparative Example 3 has a problem with the reflectance of the transfer layer.

The photocurable resin composition of the present invention comprises a fluorine-containing (meth) acrylic copolymer having a —CF ₂ H unit, a fluorine-containing (meth) acrylic copolymer not having, and at least one in the molecule. It contains a photopolymerizable ethylenically unsaturated compound having an ethylene double bond in a specific blending ratio, so it can be cured under mild conditions and in a short time, and can be laminated on a substrate. A cured resin film, for example, a low refractive index thin film (for example, a film having a thickness of about 0.01 to 10 μm) can be obtained. Therefore, the cured resin film produced from the photocurable resin composition of the present invention can be applied as an antireflection film, and can be advantageously used for articles such as a laminate foil, an image display screen protection plate, and a helmet shield. it can.

Claims (7)

And the release base film, the transfer material and a transfer layer provided thereon, viewed including the cured resin layer transfer layer is made of a photocurable resin composition, the components of the photocurable resin composition is less (A) and (B):
(A) A (meth) acrylic copolymer comprising structural units represented by the following chemical formulas (I) and (II)

(In the formula (I), X is .R ¹ represents a hydrogen atom or a methyl group represents a fluoroalkyl group having 1 to 15 carbon atoms. However, carbon atoms part of ^{R 1} has the -CF ₂ H unit 1 Represents -15 fluoroalkyl groups.)

(In the formula (II), X represents a hydrogen atom or a methyl group. R ² represents an alkyl group or a fluoroalkyl group having 1 to 20 carbon atoms and having at least one (meth) acryloyl group). Represents an integer of 1 to 5);
(B) A photopolymerizable ethylenically unsaturated compound having at least one ethylenic double bond in the molecule
The blending amount (parts by mass) in the solid content of the component (A) (including the component that becomes solid after curing) is (Awt), and the blending amount (parts by mass) of the component (B) is (Bwt) When the following formulas (1) and (2)

A transfer material , which is a photocurable resin composition that satisfies the above relationship . The transfer material according to claim 1, wherein the structural unit of the chemical formula (I) is a structural unit derived from 1H, 1H, 5H-octafluoropentyl methacrylate. The structural unit of the chemical formula (II) is represented by the following chemical formula (III)

The transfer material according to claim 1, wherein the transfer material is a structural unit represented by: The structural unit of chemical formula (II) is represented by the following chemical formula (IV)

(In the formula (IV), X represents a hydrogen atom or a methyl group. R ³ represents a C 1-14 fluoroalkyl group.)
The transfer material according to claim 1, wherein the transfer material is a structural unit represented by: The transfer material according to claim 1, wherein the photocurable resin composition further contains a photopolymerization initiator as the component (C). In a method for producing a transfer material having a release base film and a transfer layer including a cured resin layer provided thereon, the following steps (a ′) and (b ′):
Curing by irradiation with an active energy ray film; 'and (b step of forming a film of the photocurable resin composition to a release base film plane) obtained photocurable resin composition (a)' are allowed, it sees contains a step of forming a cured resin layer, step photocurable resin composition of the following components used in (a ') (a) and (B):
(A) A (meth) acrylic copolymer comprising structural units represented by the following chemical formulas (I) and (II)

(In the formula (I), X is .R ¹ represents a hydrogen atom or a methyl group represents a fluoroalkyl group having 1 to 15 carbon atoms. However, carbon atoms part of ^{R 1} has the -CF ₂ H unit 1 Represents -15 fluoroalkyl groups.)

(In the formula (II), X represents a hydrogen atom or a methyl group. R ² represents an alkyl group or a fluoroalkyl group having 1 to 20 carbon atoms and having at least one (meth) acryloyl group). Represents an integer of 1 to 5);
(B) A photopolymerizable ethylenically unsaturated compound having at least one ethylenic double bond in the molecule
The blending amount (parts by mass) in the solid content of the component (A) (including the component that becomes solid after curing) is (Awt), and the blending amount (parts by mass) of the component (B) is (Bwt) When the following formulas (1) and (2)

A photocurable resin composition that satisfies the above relationship . A transfer product, wherein a transfer layer of the transfer material according to claim 1 is transferred onto the surface of a transfer object.