JP6511917B2 - PHOTO-CURABLE RESIN COMPOSITION, CURED PRODUCT THEREOF, AND OPTICAL FILM - Google Patents

Description

  The present invention relates to a photocurable resin composition that can be suitably used in the fields of protective layer formation, adhesives, sealants, inkjet inks, optical three-dimensional modeling, etc., particularly for formation of protective layers on resin substrates, and It relates to the cured product. The present invention also relates to an optical film using the photocurable resin composition.

Photo-curable resins are currently used in many fields such as coating materials, paints, printing inks, adhesives and sealants because they have features such as energy saving and productivity improvement.
Photocurable resins are roughly classified into cationically polymerizable resins and radically polymerizable resins according to their polymerization mechanism. A photocurable epoxy resin, which is a type of cationically polymerizable photocurable resin, has well-balanced properties such as the excellent adhesion, high insulation, low shrinkage at curing, and good chemical resistance of the epoxy resin. However, they have the disadvantage of slow curing speed. On the other hand, photo-curable acrylate resin, which is a kind of radically polymerizable photo-curable resin, has the feature that the photo-curing rate is fast, but it has defects such as polymerization inhibition by oxygen and occurrence of remarkable curing shrinkage. doing.
In order to solve these drawbacks, hybrid type photocurable resins comprising cationically polymerizable compounds and radically polymerizable compounds are studied, and many fields such as protective layer formation, adhesives, inkjet inks, optical three-dimensional modeling, etc. Has been expanded. On the other hand, although a highly active antimony-containing cationic polymerization initiator may be used as a photopolymerization initiator to be used together with a photocurable resin, antimony is a toxic heavy metal, and from the viewpoint of environmental safety, antimony is used. It is desirable to use cationic polymerization initiators that do not contain it.

For example, in Patent Documents 1, 2 and 3, a protective layer for preventing damage to a resin substrate is formed using a hybrid photocurable resin composition in which a specific cationically polymerizable compound and a specific radically polymerizable compound are mixed. Then, it is described that it is possible to obtain a laminate having high hardness, less curling and less cracking of the coating.
However, in the examples of Patent Documents 1 and 2, the addition amount of the cationic polymerization initiator having phosphorus hexafluoride ion is large, and when such a photocured film is left under a high temperature and high humidity environment for a long time, the cationic polymerization initiator There is a problem that precipitates derived from the generated acid come to the film surface to be whitened or yellowed. On the other hand, when the combination of the cationic polymerization initiator UVI-6990 and the radical polymerization initiator described in the example of Patent Document 2 is used to reduce the amount of the cationic polymerization initiator in order to suppress precipitation and coloring. The problem is that the cationic polymerizability is lowered and the curling is deteriorated.

On the other hand, diphenyliodonium salt-based cationic polymerization initiators have high electron-donating properties generated by photoreaction of 1-hydroxy-cyclohexyl-phenyl-ketone and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide It is known that a radical reductively decomposes a diphenyliodonium salt to generate an acid (Non-patent Document 1). In this system, the radical polymerization initiator functions as a sensitizer during acid generation.
In Patent Document 3, a combination of diphenyliodonium salt and 1-hydroxy-cyclohexyl-phenyl-ketone is used in a specific cationically polymerizable compound and a specific radically polymerizable compound mixed system photocurable composition. Also in the combination, as shown in a comparative example described later, when the photo-cured film is left in a high temperature and high humidity environment for a long time, the precipitate derived from the acid generated from the cationic polymerization initiator comes out on the film surface and whitens Problems arise. Furthermore, the photocurable resin composition containing a diphenyl iodonium salt has a disadvantage that the stability as a composition is low and the viscosity increases with time.

  Further, in Patent Document 4, the radical initiator (A) generates an active species (H) by irradiation with an actinic ray, and the active species (H) react with the acid generator (B) to produce a new active species ( I) is formed to proceed with the polymerization reaction of the polymerizable substance (D) by the new active species (I), the active species (I) is an acid, and the acid generator It is described that the polymerization reaction of the polymerizable substance (D) proceeds with B) by the acid generated by the irradiation with the actinic ray. However, the main object of the patent document 4 is to provide a photosensitive composition which can be cured with a small amount of energy even when a substance such as a coloring agent which attenuates or shields the irradiated light is present at a high concentration. In order to use actinic radiation having a wavelength of 360 nm to 830 nm, a compound having absorption at a wavelength of 360 nm or more is used, and the resulting cured product has a composition obtained by removing the colorant and metal particles from the composition of the examples. Even there is a problem that yellowish.

Japanese Patent Application Laid-Open No. 8-73771 Japanese Patent Application Publication No. 2003-147017 Unexamined-Japanese-Patent No. 2007-237483 JP, 2012-167271, A

Polymer (2003), 44 (24), 7389-7396

  Although there is a protective layer of an optical film as one of the uses of a photocurable resin, in recent years, with the thinning of an image display device, the thinning of an optical film is also required. The film thickness of the conventional light transmitting base material is about 40 μm at most, but due to the recent progress of thin film technology of the base material, the base film thickness is 25 μm. Such thinning of the substrate reduces the hardness and hardness of the substrate itself, so that the conventional photocurable resin composition has insufficient hardness and curing shrinkage. That is, even when a thin film protective layer is formed on a thin film base, it has a certain hardness, and warpage (so-called curl) of the entire laminate due to curing shrinkage of protective layer components is suppressed Photocurable resin compositions are sought. The occurrence of the curl is particularly noticeable when the thickness of the light transmitting substrate is reduced.

The present invention has been made under the circumstances as described above, and the first object of the present invention is a highly toxic antimony-free composition, which is excellent in photocurability and durability under high temperature and high humidity environment. It is an object of the present invention to provide a photocurable resin composition and a cured product thereof, which are high in properties and capable of suppressing a whitening phenomenon and obtaining a cured product with less yellowing.
In addition, a second object of the present invention is a photocurable resin having a certain hardness even if it is a cured film of a thin film formed on a thin film base, and curling of a laminate is suppressed. An optical film comprising the composition, its cured product, and the cured product of the photocurable resin composition.

As a result of intensive studies to achieve the above object, the present inventors have identified a photoacid generator having a specific structure and a resin composition containing a cationically polymerizable compound and a radically polymerizable compound, and In combination with a radical polymerization initiator having the following structure, precipitation and whitening of precipitates are suppressed on the surface of the cured film under a high temperature and high humidity environment, and a cured product with less yellowish color is obtained, Furthermore, it was found that even a cured film of a thin film formed on a thin film base has a certain hardness, and a curling of the laminate is suppressed, resulting in a photocurable resin composition. .
The present invention has been completed based on such findings.

The photocurable resin composition according to the present invention is characterized by containing the following (A), (B) and (C).
(A) A photopolymerizable component which is at least one of the following (i) and (ii) (i) a compound having a cationically polymerizable group, and a compound having a radically polymerizable group (ii) a cationically polymerizable group and a radical Compound having a polymerizable group (B) Photoacid generator (C) represented by the following general formula (1) or general formula (1 ′) α-hydroxyacetophenone radical polymerization initiator, acylphosphine oxide radical polymerization Initiator, and at least one radical polymerization initiator selected from the group consisting of benzyl ketal radical polymerization initiators

(In the general formula (1) and the general formula (1 ′), R ¹ , R ² and R ³ each independently represent a substituent. A plurality of R ¹ , R ² or R ³ are each identical) Or may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom bond.
X ^- _{is, [P (R f) a} F 6-a] - a and, _{R f} represents an alkyl group in which at least 80% of the hydrogen atoms are substituted by fluorine atoms, is a = Less than six. The a number of Rf may be the same or different.
A is a chemical structure of n value, and n structures in parentheses are linked. n is an integer of 2 or more. Each of n pieces of X ⁻ , (R ¹ ) _{p ′} , (R ² ) _{q ′} and (R ³ ) _{r ′} may be the same or different.
p, q, p 'and q' are each independently an integer of 0-4.
r is an integer of 0-5, r 'is an integer of 0-4. )

  In the photocurable resin composition according to the present invention, the content of the anion in the photoacid generator (B) is 3 micromol / g to 50% of the total mass of the photopolymerizable component (A). It is preferable that it is micromol / g from the point from which a precipitate does not precipitate and whiten on a cured film surface under a high temperature and high humidity environment, and the hardened | cured material with little yellowishness is obtained.

  Further, in the photocurable resin composition according to the present invention, 50 mass of the compound having a radically polymerizable group in the molecule and not having a cationically polymerizable group in the total amount of the photopolymerizable component (A) It is preferable from the viewpoint that the hardness is improved to be contained in an amount of not less than 97% by mass. When the amount of radically polymerizable compound is large and the amount of cationically polymerizable compound is small, many photo acid generators are often required to promote cationic polymerization, but the specific photo acid generator of the present invention According to the combination of the above and the specific radical polymerization initiator, the cationic polymerization can be efficiently advanced with a small amount of photoacid generator. Therefore, precipitates are deposited on the surface of the cured film under a high temperature and high humidity environment while improving the hardness of the cured product with a content of a radical polymerizable group and a compound without a cationic polymerizable group as described above. It is possible to suppress the whitening.

  In the photocurable resin composition according to the present invention, the cationic polymerizable property is improved by containing a compound having at least a hydroxyl group and a radical polymerizable group in the molecule in the photopolymerizable component (A), It is preferable from the point which a curl inhibitory effect becomes high.

  In the photocurable resin composition according to the present invention, the photopolymerizable component (A) has 10 or more cationically polymerizable groups in one molecule, and the ratio of the molecular weight to the number of cationically polymerizable groups ( It is preferable that at least a compound having a molecular weight / number of cationically polymerizable groups) of 80 to 150 is contained to prevent precipitation and whitening on the surface of the cured film under a high temperature and high humidity environment.

  Further, in the photocurable resin composition according to the present invention, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] may be added to the radical polymerization initiator (C). It is preferable that the cured film in a high temperature and high humidity environment because at least containing phenyl} -2-methyl-propan-1-one is excellent in photocurability of the surface even when irradiated with UV in air, among others. It is preferable from the point which durability becomes high.

The present invention also provides a cured product of the photocurable resin composition according to the present invention.
Furthermore, the present invention also provides an optical film in which a protective layer containing a cured product of the photocurable resin composition according to the present invention is disposed on one side of a light transmitting substrate.

According to the present invention, it is a highly toxic antimony-free composition which is excellent in photocurability, highly durable in a high temperature and high humidity environment, suppressed in whitening phenomenon, and less in yellowing. A photocurable resin composition and a cured product thereof can be provided.
Further, according to the present invention, a photocurable resin composition which has a certain hardness even if it is a thin film cured film formed on a thin film substrate, and curling of a laminate is suppressed. And the optical film containing the hardened | cured material as well as the hardened | cured material of the said photocurable resin composition can be provided.

FIG. 1 is a schematic view showing an example of an optical film according to the present invention.

Hereinafter, the photocurable resin composition and the optical film according to the present invention will be described.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, (meth) acryloyl represents each of acryloyl and methacryloyl, and (meth) acrylate represents each of acrylate and methacrylate.

[Photo-curable resin composition]
The photocurable resin composition according to the present invention is characterized by containing the following (A), (B) and (C).
(A) A photopolymerizable component which is at least one of the following (i) and (ii) (i) a compound having a cationically polymerizable group, and a compound having a radically polymerizable group (ii) a cationically polymerizable group and a radical Compound having a polymerizable group (B) Photoacid generator (C) represented by the following general formula (1) or general formula (1 ′) α-hydroxyacetophenone radical polymerization initiator, acylphosphine oxide radical polymerization Initiator, and at least one radical polymerization initiator selected from the group consisting of benzyl ketal radical polymerization initiators

(In the general formula (1) and the general formula (1 ′), R ¹ , R ² and R ³ each independently represent a substituent. A plurality of R ¹ , R ² or R ³ are each identical) Or may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom bond.
X ^- _{is, [P (R f) a} F 6-a] - a and, _{R f} represents an alkyl group in which at least 80% of the hydrogen atoms are substituted by fluorine atoms, is a = Less than six. The a number of Rf may be the same or different.
A is a chemical structure of n value, and n structures in parentheses are linked. n is an integer of 2 or more. Each of n pieces of X ⁻ , (R ¹ ) _{p ′} , (R ² ) _{q ′} and (R ³ ) _{r ′} may be the same or different.
p, q, p 'and q' are each independently an integer of 0-4.
r is an integer of 0-5, r 'is an integer of 0-4. )

Since a compound having a radically polymerizable group (hereinafter sometimes simply referred to as "radically polymerizable compound") generally shrinks in volume during curing, the hardness tends to be high, but it is warped to a laminate of a substrate and a protective layer ( Positive curl) is easily generated and warps to the protective layer coated side (positive curl). On the other hand, among compounds having a cationically polymerizable group (hereinafter sometimes simply referred to as "cationically polymerizable compounds"), compounds having an epoxy group generally expand in volume upon curing, so the opposite side to the radically polymerizable compound Warpage (reverse curl) is likely to occur on the (substrate side), and it is difficult to achieve high hardness. In order to suppress the curling of the laminate of the base material and the protective layer, it is conceivable to use a resin composition containing a radically polymerizable compound that easily generates positive curl and a cationically polymerizable compound that easily generates reverse curl. . Further, in order to compensate for the disadvantages of the cationically polymerizable compound and the radically polymerizable compound as described above, resin compositions containing a cationically polymerizable compound and a radically polymerizable compound are required in many fields. However, a resin composition containing a conventionally disclosed cationically polymerizable compound and a radically polymerizable compound which does not contain highly toxic antimony is a white precipitate on the surface of the cured film when stored under a high temperature and high humidity environment. New problems have arisen (whitening phenomenon). The whitening phenomenon in which white precipitates are observed on the surface of the cured film under such a high temperature and high humidity environment is, as shown in Comparative Examples 1 and 2 described later, when only a radically polymerizable compound is used, or a cation When only the polymerizable compound was used, this phenomenon was not observed.
As a result of the inventor's examination, it turned out that the said white precipitate originates in the phosphorus component (anion part) of a cationic polymerization initiator. Such problems occur in a resin composition containing a cationically polymerizable compound and a radically polymerizable compound because the radical polymerization reaction is likely to proceed rapidly, and the progress of the cationic polymerization reaction is inhibited to form a densely crosslinked structure It is presumed that if the component derived from the acid generated from the cationic polymerization initiator is present in a large amount in the cured film, it will bleed on the surface of the cured film under a high temperature and high humidity environment.
On the other hand, in the present invention, in the resin composition containing a cationically polymerizable compound and a radically polymerizable compound, a photoacid generator having a specific thianthrene ring structure as a cationic polymerization initiator (B), and a specific one In combination with the radical polymerization initiator of
When a photoacid generator having a specific thianthrene ring structure is used in combination with a specific radical polymerization initiator, the conventional sulfonium salt-based photoacid generator or iodonium salt light photoacid generator similarly combined with the specific radical polymerization initiator Compared with the acid generator, the cationic polymerization is further advanced, and the photo-curing property is excellent, so the durability of the cured film under high temperature and high humidity environment becomes high, and curing when stored under high temperature and high humidity environment It becomes possible to suppress the precipitation of white precipitates on the film surface. Further, according to the combination of the photoacid generator having a specific thianthrene ring structure of the present invention and the specific radical polymerization initiator, the photoacid generator having a specific thianthrene ring structure is excellent because the photocurability is excellent Since a small amount may be added, adverse effects on the photoacid generator itself or a cured product derived from the photoacid generator or a decomposition product derived from the acid generator can be reduced. It is easy to suppress the generation of precipitates when stored in
A photoacid generator having a specific thianthrene ring structure is reductively reduced by a radical having a high electron-donating property generated by the photoreaction of the specific radical polymerization initiator, as compared to a conventional sulfonium salt photoacid generator. It is presumed that it is easy to be decomposed and to generate an acid more easily.
In addition, since the photoacid generator having a specific thianthrene ring structure absorbs more j-rays (313 nm) on the longer wavelength side than conventional iodonium salt photoacid generators, cationic polymerization can be used alone. Excellent in quality. Therefore, unlike the conventional iodonium salt photoacid generators, it is not necessary to use a sensitizer such as a thioxanthone sensitizer in combination, and the coloration of the cured film by the sensitizer can be suppressed.
From the above, according to the present invention, a highly toxic antimony-free composition is obtained, and a cured product having good photocurability, high durability in a high temperature and high humidity environment, and low yellowness is obtained. Be
When the photocurable resin composition of the present invention is used as a photocurable composition for forming a protective layer on a thin film substrate, both curl reduction and hardness after forming the protective layer can be achieved. Moreover, in the coating on a thin film substrate, a phenomenon that wrinkles harden by the heat generation at the time of radical polymerization reaction is apt to occur, but the photocurable resin composition of the present invention promotes cationic polymerization and causes radical polymerization. By the reaction being at an appropriate speed, a cured film in which the occurrence of wrinkles is suppressed can be obtained.
Furthermore, the photocurable resin composition of the present invention is difficult to thicken with time and is excellent in storage stability.

The photocurable resin composition of the present invention contains at least the above (A), (B), and (C), and further contains other components within the range not impairing the effects of the present invention. Is also good.
Hereinafter, although each component of the photocurable resin composition of such this invention is demonstrated, it demonstrates in order from the said (B) component characteristic to this invention.

((B) Photo acid generator)
The photoacid generator (B) used in the present invention is composed of an onium salt composed of an anion part and a cation part, as represented by the following general formula (1) or general formula (1 ′), and is irradiated with light Is a photoacid generator that generates an acid.

(In the general formula (1) and the general formula (1 ′), R ¹ , R ² and R ³ each independently represent a substituent. A plurality of R ¹ , R ² or R ³ are each identical) Or may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom bond.
X ^- _{is, [P (R f) a} F 6-a] - a and, _{R f} represents an alkyl group in which at least 80% of the hydrogen atoms are substituted by fluorine atoms, is a = Less than six. The a number of Rf may be the same or different.
A is a chemical structure of n value, and n structures in parentheses are linked. n is an integer of 2 or more. Each of n pieces of X ⁻ , (R ¹ ) _{p ′} , (R ² ) _{q ′} and (R ³ ) _{r ′} may be the same or different.
p, q, p 'and q' are each independently an integer of 0-4.
r is an integer of 0-5, r 'is an integer of 0-4. )

  The photoacid generator represented by the general formula (1 ') has two or more thianthrene ring structures in the parentheses due to the linking group A which is an n-valent chemical structure. The photoacid generator represented by the above general formula (1 ′) has solubility in organic solvents and affinity with the photopolymerizable component (A) etc. to be combined, by selecting a chemical structure that plays the role of a linking group. It can be improved.

In the general formula (1 ′), when the chemical structure A serving as a linking group is a direct bond, two structures in the parenthesis of the general formula (1 ′) are directly linked. Here, in the present invention, direct bonding means that there are no atoms in between. When the chemical structure A is n-valent, n structures in parentheses are linked. In the present invention, the valence of the chemical structure A does not include the valence when A has a substituent.
Examples of the general formula (1 ′) include compounds having the following structures.

(In the general formulas (1′-1) to (1′-4), R ¹ , R ² , R ³ , X ⁻ , p ′, q ′, r ′ and n are the same as the general formula (1 ′) A ₁ is a divalent chemical structure, A ₂ is a trivalent chemical structure, A ₃ is a tetravalent chemical structure, and A _n is a repeating unit of the polymer.)

The chemical structure A included in the general formula (1 ′) may have any chemical structure having a valence of 2 or more, and examples thereof include a hydrocarbon group, —COO—, —OCO—, —CO—, —O—, — _{S -, - S (= O} ) -, - S (= O) 2 -, - OS (= O) 2 -, - CONH -, - NHCOO-, amino bond, an imino bond (-N = C (-R -, -C (= NR)-: Here, R is a hydrogen atom or a monovalent hydrocarbon group) etc. are mentioned. Examples of the above-mentioned hydrocarbon group include linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof, and the like, with -COO-, -OCO -, - CO -, - O -, - S -, - S (= O) -, - S (= O) 2 -, - OS (= O) 2 -, - CONH -, - NHCOO-, Amino bond, imino bond (-N = C (-R)-, -C (= NR)-: wherein R is a hydrogen atom or a monovalent hydrocarbon group), and may have one or more bonds . In addition, examples of the chemical structure having a valence of 2 or more other than the hydrocarbon group include, for example, siloxane, silane, borazine and the like.

Chemical structure A is selected from among hydrocarbon groups, ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, and amino bonds, among others, in view of availability and ease of synthesis. Or a combination of two or more of these. Among the above hydrocarbon groups, aliphatic hydrocarbon groups such as alkylene groups are preferable, among them, from the viewpoints of price and availability, ease of synthesis, solubility, and heat resistance, and an ester bond is preferably contained therein. And those containing at least one of an ether bond are also preferred.
The hydrocarbon group is preferably a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and 6 to 20 carbon atoms, more preferably carbon atoms 6-10 aromatic hydrocarbon groups, as well as combinations thereof.
The hydrocarbon group contained in the chemical structure A may further have a substituent, and examples of the substituent include those similar to R ¹ described later.

  Specific structures of the compound represented by the above general formula (1 ') are illustrated, but the present invention is not limited thereto.

(X ⁻ is the same as in the general formula (1 ′). Here, n is an integer of 1 or more.)

The compound represented by the above general formula (1 ′) is, like the polymer containing the repeating unit represented by the general formula (1′-4), a table in the parenthesis of the general formula (1 ′) in the polymer skeleton It may be a structure having a plurality of the above-described structures in a pendant manner. In this case, the compound represented by the general formula (1 ′) may contain a repeating unit other than the repeating unit represented by the general formula (1′-4). Repeating units other than the repeating unit represented by 4) and n pieces of _{An form} an n-valent chemical structure X. In addition, n pieces of _An may be one kind or two or more kinds and may be different. Specifically, for A _n, for example, a structure derived from a monomer having an ethylenically unsaturated bond such as a (meth) acryloyl group, or a structure containing an ester bond, an ether bond, an amide bond, a urethane bond or the like Etc. The amount of the structure represented in the parenthesis of the general formula (1 ') in the polymer is appropriately determined in consideration of the photopolymerizable component used in combination and the physical properties of the final coating film, etc. You can choose
As a repeating unit represented by General formula (1'-4), the repeating unit represented by General formula (1'-5) as follows is used suitably, for example. In this case, as a repeating unit other than the repeating unit represented by the general formula (1′-5), an ester, an amide, an aromatic vinyl compound, etc. derived from (meth) acrylic acid, etc. are suitably ethylenically unsaturated It may be a copolymer containing a repeating unit derived from a monomer having a bond and a repeating unit represented by the general formula (1′-5).

(In the general formula (1′-5), R ¹ , R ² , R ³ , X ⁻ , p ′, q ′, r ′ and n are the same as in the general formula (1 ′). R ⁴ is hydrogen Represents an atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, L represents a divalent chemical structure)

In the general formula (1′-5), L represents a divalent chemical structure, and as L, an alkylene group, a cycloalkylene group, an arylene group, -COO-, -OCO-, -CO-, -O -, - S -, - S (= O) -, - S (= O) 2 -, - OS (= O) 2 -, - CONH-, and or any one selected from -NH- among them And groups in which two or more of them are combined. As L, among others, a group selected from -O-, -COO-, -CONH-, an alkylene group, and an arylene group or a combination of two or more of them is preferable.
R ⁴ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

  Although the specific structure in the case where it has two or more structures represented within the parenthesis of General formula (1 ') in a pendant form in a polymer frame is illustrated, it is not limited to these.

(R ¹ , R ² , R ³ , R ⁴ , X ⁻ , p ′, q ′, r ′ and n are the same as in general formula (1′-5).)

In the general formula (1) or the general formula (1 ′), R ¹ , R ² and R ³ each independently represent a substituent, and a plurality of R ¹ , R ² or R ³ are each identical Or may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom bond.
In the general formula (1) or the general formula (1 ′), the substituent is appropriately selected and used, for example, for the purpose of adjusting the light absorption wavelength, solubility in a solvent, and compatibility with a photopolymerizable component. Just do it.

The monovalent substituent in R ¹ , R ² and R ³ is not particularly limited, and examples thereof include a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group, and alkynyl Group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxy group Carbonyloxy, amino (including anilino), ammonio, acylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoylamino, alkyl and arylsulfonylamino, mercapto , Alkylthio, a Arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, arylazo group, heterocyclic ring Azo group, imide group, phosphino group, phosphinyl group, phosphinyl oxy group, phosphinyl amino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) 2), phosphato group (-OPO (OH) 2), sulfato group (-OSO 3 H), and a group in which any of the above substituents is further substituted on the hydrocarbon group contained in any of the above substituents, and other known substituents Are mentioned as an example.

The monovalent substituent is preferably a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a cyano group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an acylamino group. Group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group Or an alkoxycarbonyl group, a carbamoyl group, an imide group, a silyl group, a ureido group, or a group in which any of the above-mentioned substituents is further substituted on the hydrocarbon group contained in any of the above-mentioned substituents; Atoms, alkyl groups, aryl groups, cyano groups, hydroxy groups, alkoxy groups, acyloxy groups, acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, alkyl and arylsulfonylamino groups, alkylthio groups, sulfamoyl groups, alkyl and aryl A sulfonyl group, an alkoxycarbonyl group, a carbamoyl group, and a hydrocarbon group contained in any of the above-mentioned substituents are further substituted with any of the above-mentioned substituents.
The monovalent substituent is more preferably at least selected from the group consisting of an alkyl group, an aryl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, a hydroxyalkylthio group, and a hydroxyalkylsulfonyl group. It is one kind.
Moreover, carbon number 20 or less is preferable, and, as for the said monovalent substituent, carbon number 15 or less is more preferable.

In addition, a plurality of R ^{1 's} , a plurality of R ^{2' s} , or a plurality of R ^{3 's} may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom bond It is a thing. The cyclic structure includes an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring, and may be a polycyclic fused ring. Specific examples of the cyclic structure include, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring , Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, dibenzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, Quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring, Xanthone ring, and the like. Moreover, as in the following structure, the case where a dicarboximide group forms a cyclic structure to be substituted on the benzene ring of a thianthrene ring and the benzene ring is phthalimide is mentioned.

(R ¹ , R ³ , X ⁻ , p and r are the same as in the general formula (1).)

Among them, by bonding adjacent R ³ together, the structure forming a dibenzothiophene ring, or thioxanthone ring, are preferably used from the viewpoint of sensitivity to actinic rays in the long wavelength region.
Further, among R ¹ adjacent, or R ² together are bonded, structures the dicarboximide group is substituted to form a cyclic structure, sensitivity to the long wavelength region of the i-line (wavelength 365 nm), in a solvent It is preferably used in view of solubility and compatibility with the resin.

In addition, a plurality of R ^{1 's} , a plurality of R ^{2' s} , or a plurality of R ³ 's may further have a substituent in the cyclic structure bonded to each other, and such a further substituent The specific example is the same as the specific example of the above-mentioned monovalent substituent.

p, q, p ', and q' are respectively independently an integer of 0-4, and 0-2 are preferable. Moreover, r is an integer of 0-5, r 'is an integer of 0-4, and 0-2 are preferable.
Although the following structures are mentioned as an example of a substituent of the cation part in the parenthesis of General formula (1) or General formula (1 '), for example, it is not limited to these.

(X ⁻ is the same as in the general formula (1).)

  The cation moiety in the parenthesis of the general formula (1) or the general formula (1 ') may be appropriately prepared by a known method. For example, it can be prepared with reference to the methods described in JP 2005-501040, JP 2006-518322, WO 03/002557, JP 2011-523971, JP 2012-48075, and the like.

X ^- _{is, [P (R f) a} F 6-a] - a and, _{R f} represents an alkyl group in which at least 80% of the hydrogen atoms are substituted by fluorine atoms, is a = Less than six. The a number of Rf may be the same or different.
X ^- it is, PF ₆ ^-, or a fluorinated alkyl fluorophosphate anion a = 1 to 6. In the fluorinated alkyl fluorophosphate anion, R _f represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl and cyclopentyl And a cycloalkyl group such as cyclohexyl, and 80% or more of the hydrogen atoms of the alkyl group are substituted with a fluorine atom. The proportion of substitution by a fluorine atom is 80% or more, preferably 90% or more, and more preferably 100%. If the substitution rate of the fluorine atom is less than 80%, the cationic polymerization initiation ability is reduced.

Particularly preferable Rf is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a 100% substitution of a fluorine atom, and specific examples thereof include CF ₃ , CF ₃ CF ₂ , (CF _{3 ) 2 CF, CF 3 CF 2} CF 2, CF 3 CF 2 CF 2 CF, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, include (CF _{3) 3} C.

The number a of Rf is an integer of 0 to 6, but is preferably an integer of 0 to 4. When a is 1 or more, because they contain always fluorinated alkyl group in the anion portion, PF ₆ ^- hydrophobic becomes higher than that, and increases the molecular weight, even under high temperature and high humidity environment, curing It becomes difficult to bleed out on the film surface, and the precipitates become more difficult to deposit. On the other hand, when the number of Rf is too large, the molecular weight is too large, and it is difficult for the cationic polymerization reaction to proceed, which may make it difficult to exhibit the curl suppression effect. The number a of Rf is more preferably 0 to 3, and particularly preferably 0 to 2. The a number of Rf may be the same or different.

[(CF ₃ ) ₂ PF ₄ ] ⁻ , [(CF ₃ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [[CF ₃ ) ₂ PF ₄ ] ⁻ , [] (CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [(CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂₎ ) ₂ PF _4] ^-, and _{[(CF 3 CF 2 CF 2} ) 3PF 3] - , and the like. Among these, at least one selected from the group consisting of [(CF ₃ ) ₃ PF ₃ ] ⁻ , (CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , and [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ Is particularly preferred.

  In the photoacid generator (B), the anion part preferably has a molecular weight of 140 to 800, and more preferably 140 to 450. In the hybrid type photocurable composition comprising the cationically polymerizable compound and the radically polymerizable compound of the present invention, the reaction of the radically polymerizable group is faster in the polymerization of the radically polymerizable group, and the acid in the film where the crosslinking of the radically polymerizable group has progressed. Move to promote cationic polymerization. When the molecular weight of the anion portion of the photoacid generator is too high, the molecular weight of the generated acid is high, and there is a possibility that it will be difficult to move in the crosslinked film.

  The fluorinated alkyl fluorophosphate anion in which a is 1 to 6 may also be suitably prepared by a known method. For example, it can be prepared with reference to the method described in WO 2005/116038.

When the photoacid generator (B) is not a polymer, the molecular weight is not particularly limited, but is usually 5000 or less.
On the other hand, when the photoacid generator (B) is a polymer, the number average molecular weight is preferably 1,500 to 40,000, and further preferably 2,000 to 20,000, solubility in a solvent and photopolymerization described later It is preferable from the point of compatibility with the component (A).

  In the photocurable resin composition according to the present invention, the content of the anion in the photoacid generator (B) is 3 μmol / g or more based on the total mass of the photopolymerizable component (A) described later It is preferable from the viewpoint of suppressing curling that the amount is 5 micromoles / g or more, further 10 micromoles / g or more, and particularly 20 micromoles / g or more. On the other hand, the content of the anion in the photoacid generator (B) is 50 micromol / g or less, further 41 micromol / g or less, based on the total mass of the photopolymerizable component (A) described later. Furthermore, it is preferable that it is 25 micromol / g or less from the point which precipitates do not precipitate and whiten on the cured film surface under high temperature and high humidity environment, and the hardened | cured material with little yellowishness is obtained.

The (B) component used by this invention can be used 1 type or in mixture of 2 or more types.
It is preferable that 0.5-4 mass% is contained in solid content of a photocurable resin composition, and, as for (B) component used by this invention, it is more preferable that 0.5-2 mass% is contained. When the content of the component (B) is less than the lower limit value, the progress of the curing reaction of the cationically polymerizable compound may be insufficient, and the curl suppressing effect may be reduced. On the other hand, when the content of the component (B) is more than the upper limit value, there is a possibility that precipitates may be deposited on the surface of the cured film under high temperature and high humidity environment.

((A) photopolymerizable component)
The photopolymerizable component (A) used in the present invention is a photopolymerizable component which is at least one of the following (i) and (ii).
(I) Compound having cationically polymerizable group, and compound having radically polymerizable group (ii) Compound having cationically polymerizable group and radically polymerizable group Here, the compound having cationically polymerizable group in (i) is Represents a compound (i-1) having a cationically polymerizable group but not having a radically polymerizable group, and the compound having a radically polymerizable group in (i) has a radically polymerizable group, but the cationically polymerizable group And a compound (i-2) having no
The photopolymerizable component (A) used in the present invention may be at least one of the above (i) and (ii), and includes the following embodiments (1) to (5).
(1) Compound (i-1) having a cationically polymerizable group, and compound (i-2) having a radically polymerizable group
(2) Compound having cationically polymerizable group and radically polymerizable group (ii)
(3) Compound (i-1) having a cationically polymerizable group, and compound (ii) having a cationically polymerizable group and a radically polymerizable group
(4) Compound (i-2) having a radically polymerizable group, and compound having a cationically polymerizable group and a radically polymerizable group (ii)
(5) Compound (i-1) having a cationically polymerizable group, compound (i-2) having a radically polymerizable group, and compound having a cationically polymerizable group and a radically polymerizable group (ii)
Among them, the above (1), (4) or (5) is preferably used.

<Compound (i-1) having a cationically polymerizable group>
The compound (i-1) having a cationically polymerizable group is a compound having one or more cationically polymerizable groups in one molecule but having no radically polymerizable group. The cationically polymerizable group is not particularly limited as long as it is a functional group capable of causing a cationic polymerization reaction, and examples thereof include an epoxy group, an oxetanyl group, and a vinyl ether group. When the compound (i-1) having a cationically polymerizable group has two or more cationically polymerizable groups, these cationically polymerizable groups may be identical to or different from each other. Among them, at least one of an epoxy group and an oxetanyl group is preferable as the cationically polymerizable group from the viewpoint of the degree of reverse curl and the degree of reactivity. From the viewpoint of reverse curl, epoxy groups are particularly preferred.

  As a compound having an epoxy group, an epoxy compound having one or more alicyclic structure (aliphatic ring structure) and one or more epoxy group in one molecule from the viewpoint of curing speed and heat resistance of cured product ( “Alicyclic epoxy compounds” are preferred. Specifically as the above-mentioned alicyclic epoxy compound, for example, an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms constituting an (i-1-a) alicyclic ring and an oxygen atom And compounds having an epoxy group directly bonded to the (i-1-b) alicyclic ring by a single bond.

  The compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms constituting the above (i-1-a) alicyclic ring and an oxygen atom is arbitrarily selected from known compounds. Can be used. Among them, as the above-mentioned alicyclic epoxy group, a group (cyclohexene oxide group) constituted by two adjacent carbon atoms constituting a cyclohexane ring and an oxygen atom is preferable.

  Examples of the compound in which an epoxy group is directly bonded to the above (i-1-b) alicyclic ring by a single bond include a compound represented by the following general formula (I).

(In general formula (I), R ′ is a group (residue) obtained by removing p —OH from p-valent alcohol, and p and n each represent a natural number.)

Examples of the p-valent alcohol [R ′-(OH) p] include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol, aromatic alcohols such as benzyl alcohol, ethylene glycol , Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, neopentyl hydroxypivalate Glycol esters, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane (2,2-bis (hydroxymethyl) -1-butanol), tri Chiroruetan, pentaerythritol, and polyhydric alcohols such as polyhydric alcohols such as dipentaerythritol. The number of carbon atoms of the polyhydric alcohol is preferably 4 to 15, and more preferably 4 to 10.
p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in {} may be the same or different.

Specific examples of the compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol.
As a commercial item of the epoxy resin represented by the said general formula (I) used for this invention, Daicel Chemical Industries, Ltd. make, EHPE3150 (sum of n is an average of 15) is mentioned as a suitable thing.

In the present invention, a compound having four or more cationically polymerizable groups in one molecule is preferably contained.
Compounds having four or more cationically polymerizable groups in one molecule are compounds having a cationically polymerizable group (i-- from the viewpoint of curl suppressing effect, hardness, adhesion, and whitening suppression under high temperature and high humidity environment). The total amount of 1) and the compound (ii) having a cationically polymerizable group and a radically polymerizable group is preferably 70% by mass or more, and more preferably 80% by mass or more.
In addition, a compound having four or more cationically polymerizable groups in one molecule is a compound having a cationically polymerizable group (from a point of curl suppression effect, hardness, adhesion, and whitening suppression under high temperature and high humidity environment) In i-1), the content is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass. .

Examples of the compound having four or more cationically polymerizable groups in one molecule include sorbitol polyglycidyl ether (Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622: Nagase Polyglycidyl ethers of aliphatic polyhydric alcohols having four or more hydroxyl groups in one molecule, such as Chemtech), pentaerythritol polyglycidyl ether (Denacol EX-411: Nagase Chemtech), etc .; 4 in one molecule Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols having one or more hydroxyl groups; phenols having four or more hydroxyl groups in one molecule Add alkylene oxide Polyglycidyl ethers of polyether alcohols obtained Te;
Butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone (Epolide GT-401: made by Daicel), ethanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl), etc. in 4 molecules per molecule An aliphatic polyvalent carboxylic acid derivative having one or more carboxy groups, which is a compound having one or more epoxy groups or oxetanyl groups;
Condensation reaction product of 3-ethyl-3-oxetane methanol and silane tetraol polycondensate (Aron oxetane OXT-191 (average condensation degree of silane tetraol polycondensate 5): manufactured by Toagosei Kogyo Co., Ltd.), Silanetriols or silanetetraols or their polycondensate derivatives, such as A), which have one or more epoxy groups or oxetanyl groups;
The above general formula such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EHPE 3150: manufactured by Daicel, average number of epoxy groups in one molecule: 15) Among the compounds represented by (I), compounds in which the sum of n is 4 or more; and polymers having a cationic polymerizable group in the repeating unit, and the like can be mentioned.

  As a polymer which contains a cationic polymerizable group in the said repeating unit, the polymer containing the repeating unit represented by the following general formula (II) is mentioned, for example.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, P ¹ is a monovalent group containing a cationically polymerizable group, and L ¹ is a single bond or a divalent linking group.)

L ¹ is a single bond or a divalent linking group, preferably a single bond, -O-, an alkylene group, an arylene group, -COO-, -CONH-, -OCO- or -NHCO-. P ¹ is a monovalent group containing a cationically polymerizable group such as an epoxy group, an oxetanyl group and a vinyl ether group.

The polymer containing the repeating unit represented by the general formula (II) of the present invention is preferably synthesized by polymerizing a corresponding monomer. As the polymerization reaction in this case, radical polymerization is most convenient and preferable. Preferred specific examples of the repeating unit represented by Formula (II) are shown below, but the present invention is not limited thereto. In addition, R < ¹ > in the following general formula (II-1)-(II-6) is the same as general formula (II).

  Among the repeating units represented by the general formula (II) of the present invention, more preferable examples are repeating units derived from (meth) acrylate having an epoxy group, and among them, glycidyl (meth) acrylate or 3, Particularly preferred is a structural unit derived from 4-epoxycyclohexylmethyl (meth) acrylate. In addition, the polymer containing the repeating unit represented by the general formula (I) of the present invention may be a copolymer composed of a plurality of repeating units represented by the general formula (II), and among them, glycidyl is particularly preferable. The curing shrinkage can be reduced more effectively by using a copolymer composed of structural units derived from (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate.

  The polymer containing the repeating unit represented by the general formula (II) of the present invention may be a copolymer containing repeating units other than the general formula (II). For example, when it is desired to control the Tg or the hydrophilicity or hydrophobicity of a polymer, or in order to control the content of cationically polymerizable groups in the polymer, a copolymer containing repeating units other than the general formula (II) can be used. The method for introducing a repeating unit other than the general formula (II) is preferably a method in which the corresponding monomer is copolymerized and introduced.

  When a repeating unit other than the general formula (II) is introduced by copolymerizing a corresponding vinyl monomer, preferred monomers to be used include esters or amides derived from (meth) acrylic acids (for example, methyl (Meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc. Ni-propylacrylamide etc.), (meth) acrylic acids ((meth) acrylic acid, itaconic acid etc.), vinyl esters (eg vinyl acetate), esters derived from maleic acid or fumaric acid (dimethyl maleate) , Maleic acid Butyl, diethyl fumarate etc), maleimides (N-cyclohexyl maleimide, N-phenyl maleimide etc), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (eg butadiene, Cyclopentadiene, isoprene), aromatic vinyl compounds (eg, styrene, sodium styrene sulfonate), vinyl alkyl ethers (eg, methyl vinyl ether), ethylene, propylene, 1-butene, isobutene and the like. These vinyl monomers may be used in combination of two or more. Among them, esters derived from (meth) acrylic acid, and amides, maleimides and aromatic vinyl compounds are particularly preferably used as the monomer for inducing a repeating unit other than the general formula (I).

  Repeating units having reactive groups other than cationically polymerizable groups can also be introduced as repeating units other than the general formula (I). In particular, when it is desired to increase the hardness of the protective layer or to improve the adhesion, a method of using a copolymer containing a reactive group other than the cationically polymerizable group is preferable. As a method of introducing a repeating unit having a reactive group other than a cationically polymerizable group, a method of copolymerizing a corresponding monomer is simple and preferred.

Although the preferable specific example of the monomer which has reactive groups other than a cationically polymerizable group below is shown below, this invention is not limited to these.
Hydroxyl group-containing vinyl monomer (eg, hydroxyethyl (meth) acrylate, allyl alcohol etc.), isocyanate group-containing vinyl monomer (eg, isocyanatoethyl (meth) acrylate etc.), N-methylol group-containing vinyl monomer (eg, N-methylol group) Methylol (meth) acrylamide etc., carboxyl group-containing vinyl monomer (eg (meth) acrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate etc.), alkyl halide-containing vinyl monomer (eg chloromethylstyrene, 2-hydroxy-3) Chloropropyl methacrylate etc.), acid anhydride containing vinyl monomers (eg maleic anhydride etc.), formyl group containing vinyl monomers (eg acrolein, methacrolein etc.), active methylene containing vinyl mo Monomers (eg acetoacetoxyethyl methacrylate etc.), acid chloride containing monomers (eg (meth) acrylic acid chloride etc), amino group containing monomers (eg allylamine), alkoxysilyl group containing monomers (eg (meth) acryloyloxypropyltrimethoxysilane Etc.).

  The proportion of the repeating unit represented by the general formula (II) in the polymer containing the repeating unit represented by the general formula (II) of the present invention is 30% by mass or more and 100% by mass or less, preferably 50% by mass The content is 100% by mass or less, particularly preferably 70% by mass to 100% by mass. If the repeating unit other than the general formula (II) does not have a reactive group, the hardness decreases if the content is too large, and if it has a reactive group, the hardness may sometimes be maintained, but the cure shrinkage is large And brittleness may deteriorate. In particular, when the molecular weight reduction such as dehydration or dealcoholation is accompanied during the crosslinking reaction as in the case of using a copolymer of an alkoxysilyl group-containing monomer and a repeating unit represented by the general formula (II), the cure shrinkage tends to be large . When a repeating unit having a reactive group which causes a crosslinking reaction to proceed with such molecular weight reduction is introduced into a polymer containing the repeating unit represented by the general formula (II) of the present invention, a table of the general formula (II) The preferable ratio in which the repeating unit is contained is 70% by mass to 99% by mass, more preferably 80% by mass to 99% by mass, and particularly preferably 90% by mass to 99% by mass.

  Among them, polyglycidyl methacrylate and poly (3,4-epoxycyclohexylmethyl methacrylate) are preferably used as the polymer containing the repeating unit represented by the general formula (II) of the present invention.

  The preferred molecular weight range of the polymer containing the repeating unit represented by the general formula (II) is 1,000 or more and 1,000,000 or less, more preferably 3,000 or more, and 200,000 or less in weight average molecular weight. Most preferably, it is 5,000 or more and 100,000 or less.

As the compound (i-1) having a cationically polymerizable group used in the present invention, from the viewpoint of curl suppressing effect, hardness, adhesion, and whitening suppression under high temperature and high humidity environment, functional group of cationically polymerizable group The group equivalent is not particularly limited, but is preferably 350 or less, more preferably 300 or less, and still more preferably 250 or less. If the functional group equivalent exceeds 350, the hardness of the protective layer may decrease or curling may be significant.
As the compound (i-1) having a cationically polymerizable group used in the present invention, a cationically polymerizable compound is preferred among them from the viewpoints of the curl suppressing effect, hardness, adhesion, and whitening suppression under high temperature and high humidity environment. It is preferable that at least one compound has at least 10 cationically polymerizable groups in one molecule, and the functional equivalent of the cationically polymerizable groups is 250 or less.
The functional group equivalent of the cationically polymerizable group of the compound (i-1) having a cationically polymerizable group can be calculated by the following formula.
[Functional group equivalent of cationically polymerizable group] = [molecular weight of compound (i-1) having cationically polymerizable group] / [number of cationically polymerizable groups possessed by compound (i-1) having cationically polymerizable group]

<Compound Having Radically Polymerizable Group (i-2)>
The compound (i-2) having a radically polymerizable group is a compound having one or more radically polymerizable groups in one molecule but not having a cationically polymerizable group. The radically polymerizable group is not particularly limited as long as it is a functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond, and more specifically, a vinyl group And (meth) acryloyl groups. When the compound (i-2) having a radically polymerizable group has two or more radically polymerizable groups, these radically polymerizable groups may be identical to or different from each other.

  The number of radically polymerizable groups that the compound (i-2) having a radically polymerizable group has in one molecule is preferably 2 or more, and more preferably 3 or more. Among them, compounds having a (meth) acryloyl group are preferable, and compounds called polyfunctional acrylate monomers having 2 to 6 (meth) acryloyl groups in the molecule, urethane (meth) acrylate, polyester (meth) acrylate, Oligomers having a molecular weight of several hundred to several thousand having several (meth) acryloyl groups in a molecule called epoxy (meth) acrylate can be preferably used.

  Specific examples of the compound (i-2) having a radically polymerizable group include vinyl compounds such as divinylbenzene; ethylene glycol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, and 9,9-bis [4- (2- (Meth) acryloyloxyethoxy) phenyl] fluorene, alkylene oxide modified bisphenol A di (meth) acrylate (eg, ethoxylated (ethylene oxide modified) bisphenol A di (meth) acrylate, etc.), trimethylolpropane Tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, Polyol polyacrylates such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diacrylate of bisphenol A diglycidyl ether, diacrylate of hexanediol diglycidyl ether And epoxy acrylates, urethane acrylate obtained by the reaction of polyisocyanate and hydroxyl group-containing acrylate such as hydroxyethyl acrylate, and the like.

  Moreover, you may use the polymer which contains a radically polymerizable group in a repeating unit, and as such a polymer, the polymer containing the repeating unit represented by the following general formula (III) is mentioned, for example.

(In the formula, R ² represents a hydrogen atom or a methyl group, P ² is a monovalent group containing a radical polymerizable group, and L ² is a single bond or a divalent linking group.)

L ² is a single bond or a divalent linking group, and specifically, those similar to the aforementioned L ¹ can be mentioned.
P ² is a monovalent group containing a radical polymerizable group such as a vinyl group and a (meth) acryloyl group. Specific examples of the combination of L ² and P ² of the repeating unit represented by General Formula (III) will be shown below, but the present invention is not limited thereto. As other repeating units, the repeating units described in paragraphs 0034 to 0038 of JP-A No. 2003-147017 can be mentioned, and the preparation of a polymer containing such repeating units is It can be prepared with reference to paragraphs 0039 to 0050 and the like.

As a combination of L ² and P ² ,
-COOCH ₂ CH = CH _{2
-COOCH 2 CH 2 OC (= O} ) CH = CH 2
_{-COOCH 2 CH 2 OC (= O} ) C (CH 3) = CH 2
_{-CONHCH 2 CH 2 OC (= O} ) CH = CH 2
_{-CONHCH 2 CH 2 OC (= O} ) C (CH 3) = CH 2
_{-COOCH 2 CH 2 OC (= O} ) Ph-CH = CH 2 (Ph = phenylene)
_{-COOCH 2 CH (OH) CH 2} OC (= O) CH = CH 2
_{-COOCH 2 CH (OH) CH 2} OC (= O) C (CH 3) = CH 2
—COOCH ₂ CH ₂ OCH ₂ NHC (= O) CH = CH ₂

  In the polymer containing the repeating unit represented by the general formula (III) of the present invention, from the viewpoint of increasing the hardness, the preferable ratio in which the repeating unit represented by the general formula (III) is included is 30% by mass or more and 100% % Or less, more preferably 50% by mass or more and 100% by mass or less, particularly preferably 70% by mass or more and 100% by mass or less.

  The preferred molecular weight range of the crosslinkable polymer containing the repeating unit represented by the general formula (III) of the present invention is 1,000 to 1,000,000, more preferably 3,000 to 200,000, in terms of weight average molecular weight. Most preferably, it is 5,000 or more and 100,000 or less.

As the compound (i-2) having a radically polymerizable group used in the present invention, from the viewpoint of curl suppressing effect, hardness, adhesion, and whitening suppression under high temperature and high humidity environment, functional group of radically polymerizable group The group equivalent is not particularly limited, but is preferably 300 or less, more preferably 275 or less, and still more preferably 250 or less. If the functional group equivalent exceeds 300, the hardness of the protective layer may decrease.
As the compound (i-2) having a radically polymerizable group to be used in the present invention, a radically polymerizable compound is particularly preferred in view of the curling suppressing effect, hardness, adhesion, and whitening suppression under high temperature and high humidity environment It is preferable to include at least a compound having three or more radically polymerizable groups in one molecule and having a functional group equivalent of 90 to 120 of the radically polymerizable groups.
The functional group equivalent of the radically polymerizable group of the compound (i-2) having a radically polymerizable group can be calculated by the following formula.
[Functional group equivalent of radically polymerizable group] = [molecular weight of compound (i-2) having radically polymerizable group] / [number of radically polymerizable groups possessed by compound (i-2) having radically polymerizable group]

  In the photocurable resin composition, when coexistence of low curlability and hardness is required in a thin film substrate, the compound (i-2) having a radically polymerizable group has one or more hydroxyl groups in one molecule. It is preferable to include at least a compound having three or more (meth) acryloyl groups and having a molecular weight / number of (meth) acryloyl groups of 120 or less. The hydroxyl group accelerates the reaction of the cationically polymerizable group and reacts with the cationically polymerizable group to decrease the shrinkage rate, thereby reducing the curl and also because the density of the (meth) acryloyl group is high, it is highly crosslinked by radical polymerization. The hardness is maintained because of the density film. Examples of the compound include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

<Compound having cationically polymerizable group and radically polymerizable group (ii)>
The compound (ii) having a cationically polymerizable group and a radically polymerizable group is a compound having one or more cationically polymerizable groups and one or more radically polymerizable groups in one molecule. As the cationically polymerizable group and the radically polymerizable group, the same functional groups as exemplified for the compound (i) can be used. When the compound (ii) having a cationically polymerizable group and a radically polymerizable group has two or more cationically polymerizable groups or two or more radically polymerizable groups, these cationically polymerizable groups or radically polymerizable groups Each may be the same or different.

  As the compound (ii) having a cationically polymerizable group and a radically polymerizable group, a polymer containing a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (III) is a cured film Are preferably used in view of the hardness and durability of the In the polymer, the mass ratio of the repeating unit represented by the general formula (I) to the repeating unit represented by the general formula (III) is the curl of the protective layer after curing while improving the hardness of the protective layer. It is preferable that it is 50: 50-5: 95 from the point which a suppression effect becomes high, and it is further more preferable that it is 20: 80-10: 90.

  The polymer containing the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (III) is, for example, a copolymer having the repeating unit represented by the general formula (I) A compound having a functional group (for example, a hydroxyl group or a carboxy group) capable of reacting with a cationically polymerizable group contained in the repeating unit represented by the general formula (I), and a compound having a radically polymerizable group, which is synthesized It is possible to prepare by reacting with a cationically polymerizable group. For example, by reacting methacrylic acid with a part of the epoxy group of poly (glycidyl methacrylate), a copolymer containing a repeating unit having an epoxy group and a repeating unit having a methacryloyl group can be obtained.

  Alternatively, even if the polymer is not a polymer having a repeating unit represented by the above general formula (I), for example, (meth) acrylic acid or the like in part of the epoxy group of the polyfunctional epoxy compound having multiple epoxy groups in the molecule A compound having a compound having a cationically polymerizable group and a radically polymerizable group can be prepared by reacting a compound having a carboxy group and a radically polymerizable group. Thus, when a compound having a carboxyl group such as (meth) acrylic acid and a radically polymerizable group is reacted with a part of the epoxy group, for example, a hydroxyl group is generated after the reaction. That is, since a compound having a hydroxyl group, a radically polymerizable group, and a cationically polymerizable group in one molecule can be obtained, the reaction of the cationically polymerizable group can be promoted, and it is suitably used in the present invention.

  A polymer comprising the repeating unit represented by the above general formula (I) and the repeating unit represented by the above general formula (III), or two or more radically polymerizable groups in one molecule The compound having a cationically polymerizable group of the above is suitably used even in an embodiment using only the compound (ii) having a cationically polymerizable group and a radically polymerizable group as the photopolymerizable component (A).

On the other hand, as a compound (ii) having a cationically polymerizable group and a radically polymerizable group used together with the above compound (i) as the photopolymerizable component (A), one radically polymerizable group and one radically polymerizable group are included Alternatively, a compound having two cationically polymerizable groups is also suitably used.
As such a compound having one radically polymerizable group and one or two cationically polymerizable groups in one molecule, for example, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl etc. are mentioned.
Among them, a compound having an oxetanyl group as a cationically polymerizable group and having a group containing an ethylenically unsaturated bond as a radically polymerizable group is effective in suppressing the curling of the protective layer after curing while improving the hardness of the protective layer. And the adhesion after the light resistance test is preferred from the viewpoint that the improvement effect is high.
As a compound (ii) which has a cationically polymerizable group and a radically polymerizable group, the compound represented by the following general formula (IV-1), (IV-2), and (IV-3) is mentioned, for example.

(In the general formula (IV-1), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X ¹ represents an alkylene group having 1 to 20 carbon atoms. And X ² represents an alkylene group having 1 to 5 carbon atoms or a phenylene group, m is an integer of 0 to 6)

(In formula (IV-2), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group. R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. And each of X ³ and X ⁴ independently represents an alkylene group having 1 to 5 carbon atoms.)

(In General Formula (IV-3), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, and X ⁵ and X ⁶ each independently represent an alkylene group having 1 to 5 carbon atoms.)

In the general formula (IV-1) or (IV-2), examples of the alkyl group having 1 to 6 carbon atoms as R ⁴ , R ⁷ and R ⁸ include linear alkyls such as methyl, ethyl and n-propyl. And linear or branched C1 to C6, preferably C1 to C3 alkyl groups such as branched alkyl groups such as isopropyl, isobutyl and t-butyl. Among them, a methyl group or an ethyl group is preferable as R ⁴ , R ⁷ and R ⁸ in the present invention.

In General Formula (IV-1), X ¹ represents an alkylene group having 1 to 20 carbon atoms, but the alkylene group may be linear or branched. It is preferable that it is a linear alkylene group from the point which the curl inhibitory effect of the protective layer after hardening becomes high, improving hardness of a protective layer, and it is a C1-C5 linear alkylene group especially Is preferred.

In General Formula (IV-1), X ² represents an alkylene group having 1 to 5 carbon atoms or a phenylene group, but the alkylene group may be linear or branched. m is an integer of 0 to 6, and when m is 2 or more, two or more X ^{2 s} may be the same or different.
At least one of X ² is preferably a linear alkylene group from the viewpoint of improving the hardness of the protective layer and enhancing the curl suppression effect of the protective layer after curing, and in particular, a straight chain having 1 to 5 carbon atoms It is preferably a chain alkylene group.
Further, m is preferably 3 or less, and more preferably 1 or less from the viewpoint of the hardness of the cured film.

In General Formula (IV-2), X ³ and X ⁴ and X ⁵ and X ⁶ in General Formula (IV-3) each independently represent an alkylene group having 1 to 5 carbon atoms, The group may be linear or branched. It is preferable that it is a linear alkylene group from the point which the curl inhibitory effect of the protective layer after hardening becomes high, improving hardness of a protective layer, and it is a C1-C2 linear alkylene group especially Is preferred.

Among the compounds represented by the general formula (IV-1), (IV-2) or (IV-3), the point at which the curl suppression effect of the protective layer after curing becomes high while improving the hardness of the protective layer It is preferable to use (3-ethyl oxetan-3-yl) methyl (meth) acrylate.
The compounds represented by the general formula (IV-1), (IV-2) or (IV-3) may be commercially available products, and may be JP-A-2011-168561 or JP-A-2013-14076. It is possible to prepare the description of the publication as a reference. As a commercial item of the compound represented by general formula (IV-1), (IV-2) or (IV-3), OXE-10, OXE-30 (Osaka organic chemical industry corporation make) etc. are mentioned, for example It can be mentioned.

  In the photopolymerizable component (A) used in the present invention, the total amount of the component (A) preferably contains 50% by mass or more of a compound having at least a radically polymerizable group. Among them, from the viewpoint of improving the hardness, the compound having at least a radically polymerizable group is preferably contained in an amount of 70% by mass or more in the total amount of the component (A), and more preferably 80% by mass or more. On the other hand, from the viewpoint of curl suppression, the compound having at least a radically polymerizable group is preferably contained in an amount of 95% by mass or less in the total amount of component (A), and is further contained in an amount of 90% by mass or less in the total amount of component (A) Is preferred.

  Among them, the compound (i-2) having a radically polymerizable group but not having a cationically polymerizable group is preferable from the viewpoint of improving the hardness of the cured film when forming the cured film of the thin film on a thin film substrate The total amount of the component A) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 85% by mass or more. On the other hand, the compound (i-2) having a radically polymerizable group but not having a cationically polymerizable group is preferably contained in an amount of 97% by mass or less in the total amount of the component (A). It is preferable to be contained by mass% or less, and it is more preferable to further contain 90 mass% or less in the total amount of component (A).

  In the photopolymerizable component (A) used in the present invention, the compound (ii) having a cationically polymerizable group and a radically polymerizable group used together with the compound (i) improves the hardness of the cured film of the thin film. However, it is preferably contained in an amount of 1% by mass or more, and further 2% by mass or more in the total amount of the component (A) from the viewpoint that the curl suppression effect of the laminate after curing is enhanced and the adhesion after light resistance test is improved. Is preferred.

In addition, the photopolymerizable component (A) used in the present invention has a cationically polymerizable group from the viewpoint that the curl suppression effect of the laminate after curing is enhanced while the hardness of the cured film of the thin film is improved. The total amount of the compound (i-1) having no polymerizable group and the compound (ii) having a cationically polymerizable group and a radically polymerizable group is preferably 40% by mass or less in the total amount of component (A), The content is further preferably 30% by mass or less, and still more preferably 25% by mass or less.
Among them, a cationically polymerizable group is possessed but it has a radically polymerizable group, from the viewpoint that the curl suppression effect of the laminate after curing is enhanced while the hardness of the cured film of the thin film is improved and the adhesion after light resistance test is improved. The mass ratio ((ii) / (i-1)) of the compound (ii) having a cationically polymerizable group and a radically polymerizable group to the compound (i-1) not to be mixed is preferably 0.05 or more, and more preferably It is preferable that it is 0.1 or more. If the mass ratio is too small, adhesion after the light resistance test may be insufficient.

  The component (A) used in the present invention can be used alone or in combination of two or more as described above. The content of the component (A) used in the present invention may be appropriately selected in consideration of the balance with other components, and is not particularly limited. The component (A) used in the present invention is preferably contained in an amount of 30 to 98.9% by mass, more preferably 50 to 98.5% by mass, in the solid content of the photocurable resin composition. In addition, solid content here means all the components except a solvent, and a liquid monomer is also contained. Moreover, it is preferable that 80-98.9 mass% is contained with respect to the total amount of (A), (B), and (C) component, and (A) component used by this invention is 90-98 preferably. It is preferable that 0.5 mass% be included.

<(C) Radical polymerization initiator>
The radical polymerization initiator used in the present invention is at least one selected from the group consisting of an α-hydroxyacetophenone radical polymerization initiator, an acyl phosphine oxide radical polymerization initiator, and a benzyl ketal radical polymerization initiator. It is a radical polymerization initiator.
In the present invention, the photoacid generator (B) having the specific thianthrene ring structure is combined with such a specific radical polymerization initiator to produce an electron generated by the photoreaction of the specific radical polymerization initiator. The photoacid generator (B) having the specific thianthrene ring structure is likely to be reductively decomposed by the radical having high donating ability, thereby more easily generating an acid, and the effect of the present invention as described above can be obtained. It is estimated that

  Specific examples of the α-hydroxyacetophenone type radical polymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] Phenyl} -2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy 2-Methyl-1- {4- (1-methylvinyl) phenyl} propanone], 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-1- (4- (4) And-(2-hydroxy-3,5,2-methylpropionyl) -benzyl) -phenyl) -2-methylpropan-1-one and the like.

Specific examples of the acylphosphine oxide radical polymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. .
Moreover, a 2, 2- dimethoxy- 1, 2- diphenyl ethane 1-one etc. are mentioned as a specific example of a benzyl ketal type radical polymerization initiator.
(C) As a radical polymerization initiator, it can be used individually or in combination of 2 or more types.

Among the radical polymerization initiators used in the present invention, the sensitization action during acid generation is particularly high, it is easy to promote cationic polymerization, the radical polymerization initiation ability is also high, and the photocurability is excellent. Among them, it is preferable to use at least one of α-hydroxyacetophenone-based radical polymerization initiators.
Among them, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one may be added to the radical polymerization initiator (C). It is preferable from the viewpoint that the durability of the cured film in a high temperature and high humidity environment becomes high, because at least containing at least the cationic polymerization proceeds, the inhibition of the radical polymerization by the presence of oxygen is small, and the photocurability is excellent. . The radical polymerization initiator (C) is at least 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one. In the case where a relatively large amount of the photoacid generator (B) is used and the photocurable reaction is performed by light irradiation in air, the whitening phenomenon tends to occur in the cured film under a high temperature and high humidity environment. Also in the situation, the whitening phenomenon can be suppressed.

The (C) component used by this invention can be used 1 type or in mixture of 2 or more types.
The component (C) used in the present invention is preferably contained in an amount of 1 to 5% by mass, and more preferably 1 to 3% by mass, in the solid content of the photocurable resin composition. If the content of the component (C) is less than the lower limit value, the progress of the curing reaction of the radically polymerizable compound may be insufficient to lower the hardness. On the other hand, when the content of the component (C) is more than the upper limit value, only the radical polymerization reaction preferentially proceeds, and curl may be remarkable.

<Other ingredients>
If necessary, other components may be contained as long as the effects of the present invention are not impaired. For example, those comprising an antistatic agent, an antiglare agent and an antifouling agent are preferable from the viewpoint of being able to further impart antistatic properties, antiglare properties and antifouling properties. Furthermore, in order to increase the hardness, fine particles of silica, fine particles of resin, reactive or non-reactive leveling agents, various sensitizers, etc. may be mixed. As these additives, known materials can be appropriately selected and used.

The photocurable resin composition of the present invention may further contain a solvent. As the solvent, a solvent which dissolves the component (A), the component (B) and the component (C) may be appropriately selected and used. For example, ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone may be mentioned.
The photocurable resin composition of the present invention is stirred while the above-mentioned component (A), component (B), component (C), and, if necessary, a solvent are used, for example, while eliminating air bubbles under vacuum. , Prepared by mixing. The temperature at the time of stirring and mixing is, for example, about 10 to 60 ° C. For stirring and mixing, known devices such as, for example, a rotation-revolution type mixer, a single-shaft or multi-shaft extruder, a planetary mixer, a kneader, and a dissolver can be used.

  The photocurable resin composition of the present invention is preferably adjusted in viscosity as appropriate depending on the use. For example, in order to form a cured film such as a protective layer of a thin film, the viscosity measured at 25 ° C. is preferably 0.5 to 10 mPa · s, and more preferably 1 to 5 mPa · s. The viscosity here can be measured by a B-type viscometer.

  Even if it is a cured film of the thin film formed on the base material of a thin film, the photocurable resin composition of this invention has fixed hardness, and the curl of a laminated body is suppressed. Furthermore, in the coating on a thin film substrate, a phenomenon in which wrinkles cure on the substrate due to heat generation during radical polymerization reaction is likely to occur, but the photocurable resin composition of the present invention promotes cationic polymerization and radical By setting the reaction rate of polymerization to an appropriate rate, a cured film in which the generation of wrinkles is suppressed can be obtained. Furthermore, in the cured film of the photocurable resin composition of the present invention, precipitation and precipitation on the surface of the cured film in a high temperature and high humidity environment are suppressed. Therefore, among them, it is suitable for forming a protective layer having a thickness of 20 μm or less, and can be suitably used even for a protective layer having a thickness of 10 μm or less.

[Optical film]
The optical film according to the present invention is an optical film in which a layer containing the cured product of the photocurable resin composition according to the present invention is disposed on one side of a light transmitting substrate.
FIG. 1 is a cross-sectional view schematically showing an example of the layer configuration of the optical film according to the present invention. In the cross-sectional view shown in FIG. 1, the scale in the thickness direction (vertical direction in the figure) is greatly enlarged and exaggerated than the scale in the lateral direction (horizontal direction in the figure) for ease of explanation. is there.
The optical film 1 is provided with a layer 20 containing a cured product of the photocurable resin composition according to the present invention on one side of the light transmitting substrate 10. The layer 20 containing the cured product of the photocurable resin composition according to the present invention functions as various functional layers such as an antistatic layer, an antiglare layer, an antifouling layer, as well as a protective layer.

The optical film according to the present invention has a thin film thickness since the layer containing the cured product of the photocurable resin composition according to the present invention is disposed on one side of the light transmitting substrate. Even if a layer containing the cured product of a thin film is formed on a substrate, a cured film having a certain hardness, suppressing curling, and suppressing the occurrence of wrinkles is obtained, and a high temperature and high humidity environment is obtained. Since precipitates do not precipitate on the surface of the cured film and cause whitening, an optical film of a thin film is obtained, which is suitable for thinning of a display.
Hereinafter, each layer which comprises the optical film of this invention is demonstrated in order.

<Light transmitting base material>
The light transmitting substrate may be transparent, semitransparent, colorless or colored as long as it transmits light, but the average light transmittance in the visible light range of 380 to 780 nm is 50% or more, preferably 70% or more. More preferably, it is 85% or more. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corp. make UV-3100PC).

Further, in the present invention, since the adhesion is good even when formed on the light transmitting resin base and curling of the protective layer is suppressed, the light transmitting resin base is preferably used.
In the present invention, it is preferable to select the light transmitting resin substrate depending on the mode in which the optical film is used. For example, in the case where optical isotropy is required for the target optical film, it is possible to use triacetate cellulose (TAC), diacetyl cellulose, acetate propionate cellulose, acetate butyrate cellulose, etc. as the light transmitting resin substrate. Of cellulose ester, polynorbornene type transparent resin product name Artton (made by JSR), cyclic polyolefin such as Zeonor (made by Nippon Zeon), etc., polyester resin, acrylic resin, PET easily treated with polyether resin etc. Preferably it is used.
Among the above, a base film selected from a triacetyl cellulose film, a polyester film, and an acrylic film is preferable. From the viewpoint of mechanical strength and dimensional stability, polyesters (polyethylene terephthalate, polyethylene naphthalate) that are drawn, especially uniaxially or biaxially drawn, are preferable, and TAC and acrylic are light transmissive and optically isotropic. It is suitable from the viewpoint.

  In the present invention, the light-transmitting substrate may be subjected to surface treatment (eg, saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment), primer layer (adhesive) Layer) may be formed.

  The thickness of the light transmitting substrate is usually about 20 μm to 200 μm. In the present invention, since the anti-curl property is particularly excellent, the anti-curl property can be achieved even if the thickness of the light transmitting resin substrate is thin, and a thickness of about 20 μm or more and less than 40 μm is preferable. It can be used for

<Layer Containing Cured Product of Photocurable Resin Composition According to the Present Invention>
In the optical film, the layer containing the cured product of the photocurable resin composition according to the present invention is usually formed as a layer comprising the cured product of the photocurable resin composition according to the present invention.
The cured product of the photocurable resin composition according to the present invention contains the polymer of the photopolymerizable component (A).

The photocurable resin composition according to the present invention is applied onto the light transmitting substrate to form a coating film.
The application method is not particularly limited as long as it is a method capable of uniformly applying the photocurable resin composition according to the present invention to the surface of the light transmitting substrate, and a spin coating method, a dip method, a spray Various methods such as a method, a slide coating method, a bar coating method, a roll coater method, a meniscus coater method, a flexo printing method, a screen printing method, and a peel coater method can be used.
The hardened | cured material of this invention can be manufactured by irradiating an ultraviolet-ray to the coating film of the said photocurable resin composition. When the photocurable resin composition is irradiated with light, the curing reaction (radical polymerization reaction and cationic polymerization reaction) is promoted to form a cured product.

  For light irradiation, for example, light having a wavelength of about 250 to 400 nm is used, and the irradiation amount is, for example, about 0.1 to 100 J / cm 2. After the light irradiation, if necessary, heat treatment may be performed, for example, at a temperature of about 50 to 200 ° C. (preferably 100 to 200 ° C.) for about 0.5 to 5 hours (post-baking treatment). By performing the post-baking treatment, the polymerization reaction further proceeds, and a cured product with further improved hardness can be formed.

  The curing reaction may be carried out under normal pressure, under reduced pressure or under pressure. The reaction atmosphere for the curing reaction is not particularly limited as long as the curing reaction is not inhibited. For example, any of an air atmosphere, a nitrogen atmosphere, and an argon atmosphere may be used.

  The layer containing the cured product according to the present invention has a certain hardness even if it is a thin film, has good adhesion, and suppresses curling of the laminate, among which a film of 20 μm or less It is suitable for thickness, and can also be suitably used as a layer having a thickness of 10 μm or less. It is preferable that the film thickness of the said layer is 3 micrometers or more from the point of hardness.

  In the layer containing the cured product of the photocurable resin composition according to the present invention, various additives may be further added according to the function to be imparted. Specifically, examples thereof include an antistatic agent in the case of an antistatic layer, an antiglare agent in the case of an antiglare layer, and an antifouling agent in the case of an antifouling layer.

The optical film according to the present invention further comprises an antistatic layer different from the layer containing the cured product of the photocurable resin composition according to the present invention, an antiglare layer, an antifouling layer, and an antireflective layer. At least one selected layer may be disposed. For these layers, conventionally known constitutions can be appropriately adopted as long as the effects of the present invention are not impaired.
Among them, from the viewpoint of reducing the reflection on the display surface, the optical film preferably further has an antireflective layer. In this case, the optical film has a light transmitting substrate, a protective layer made of a cured product of the photocurable resin composition according to the present invention, and an antireflective layer in this order, and the outermost surface has an antireflective layer. The structure which has is preferable.

  The antireflective layer may have a single layer structure composed of a layer having a refractive index lower than that of the protective layer. In addition, it may have a multilayer structure in which a high refractive index layer and a low refractive index layer are provided in order from the protective layer side, the outermost layer is a low refractive index layer, and the thickness d of each layer satisfies d = mλ / 4n. Here, m represents a positive odd number, n represents a refractive index of the low refractive index layer, and λ represents a wavelength. m is preferably 1. λ is preferably 450 to 700 nm, more preferably 500 to 600 nm.

The low refractive index layer and the high refractive index layer can also be formed by vacuum evaporation, sputtering, or the like using, for example, low refractive index particles or high refractive index particles. As low refractive index fine particles, for example, SiO ₂ (refractive index n = 1.45), MgF ₂ (refractive index n = 1.38), LiF (refractive index n = 1.36), NaF (refractive index n = 1) .33), CaF ₂ (refractive index n = 1.44), 3NaF · AlF ₃ (refractive index n = 1.4), AlF ₃ (refractive index n = 1.37), Na ₃ AlF ₆ (refractive index n And fine particles of metal oxides such as = 1.33), and the above-mentioned hollow particles. Moreover, as high refractive index fine particles, Al ₂ O ₃ (refractive index n = 1.63), La ₂ O ₃ (refractive index n = 1.95), ZrO ₂ (refractive index n = 2.05), Y ₂ Fine particles of metal oxides such as O ₃ (refractive index n = 1.87) can be mentioned.
Also, for example, the low refractive index layer has two or more reactive functional groups in one molecule, fluorine-containing compounds such as the above-mentioned low refractive index fine particles, vinylidene fluoride copolymer, silicone-containing vinylidene fluoride copolymer, etc. For example, it may be formed using a curable resin composition which preferably contains a fluorine-containing monomer having a pentaerythritol skeleton.

Hereinafter, the present invention will be specifically described by way of examples. These descriptions do not limit the present invention.
The weight average molecular weight was determined by GPC as a standard polystyrene equivalent value. The measurement was performed using HLC-8220GPC manufactured by Tosoh Corp., using THF as an eluent and TSKgel Super HZM-M manufactured by Tosoh Corp. as a measurement column.

Synthesis Example 1
(Synthesis of 3,4-epoxycyclohexylmethyl methacrylate homopolymer)
In a four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 48 parts of 3,4-epoxycyclohexylmethyl methacrylate, 50 parts of methyl isobutyl ketone (MIBK), 0 azobisisobutyronitrile (AIBN) .48 parts and 0.49 parts of dodecyl mercaptan were added, and the mixture was heated to 85 ° C. with stirring under a nitrogen atmosphere and reacted for 3 hours. The non-volatile content of the resulting poly (3,4-epoxycyclohexylmethyl methacrylate) solution was 50%, and the poly (3,4-epoxycyclohexylmethyl methacrylate) had a weight average molecular weight of 15,000.

(Composition example 2)
In a 4-neck flask equipped with a nitrogen inlet, stirrer, condenser and thermometer, 48 parts of glycidyl methacrylate, 70 parts of methyl ethyl ketone, 0.48 parts of azobisisobutyronitrile (AIBN), 0.49 parts of dodecyl mercaptan The reaction was carried out for 5 hours by heating to 75 ° C. while stirring under a nitrogen atmosphere. Thereafter, the reaction system is cooled to 50 ° C., the nitrogen introducing pipe is replaced with an air introducing pipe, 9.7 parts of methacrylic acid, 0.1 part of methoquinone and 0.2 parts of triphenylphosphine are charged and mixed, and then air The reaction mixture was heated to 75.degree. C. and reacted for 10 hours. The methyl ethyl ketone was added so that the non-volatile content became 35% by cooling, and an epoxy group- and methacryloyl group-containing polymer solution was prepared. The weight average molecular weight of the epoxy group- and methacryloyl group-containing polymer was 25,000, and the molar ratio of epoxy group / methacryloyl group was 67/33.

Example 1
(1) Preparation of photocurable resin composition The photocurable resin composition of the composition shown below was prepared.
<Photocurable resin composition 1>
· Cationic polymerizable compound (polyfunctional epoxy, EHPE 3150, manufactured by Daicel): 10 parts by mass · Radical polymerizable compound (polyfunctional acrylate (2), trade name Aronix M-403, manufactured by Toagosei, dipentaerythritol hexaacrylate / di Pentaerythritol pentaacrylate (containing hydroxyl group) mixture, main component is dipentaerythritol pentaacrylate: 45 parts by mass Radically polymerizable compound (polyfunctional acrylate (3), trade name KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd. , Pentaerythritol triacrylate (hydroxyl group-containing / pentaerythritol tetraacrylate mixture): 45 parts by mass · Radical polymerization initiator (α-hydroxyacetophenone type (1), 1-hydroxy-cyclohexyl-phenyl-ketone, trade name: IL Gacure 184, manufactured by BASF: 4 parts by mass Photoacid generator (photoacid generator (1) represented by the above general formula (1), photoacid generator represented by the following chemical formula (B), trade name Esacure 1187, manufactured by Lamberti, active ingredient 75% by mass propylene carbonate solution): 1.33 parts by mass, leveling agent: Megafac F 477: 0.1 parts by mass, solvent: methyl ethyl ketone: 75 parts by mass, solvent: methyl isobutyl ketone: 75 parts Department

(2) Production of Optical Film A 25 μm cellulose triacetate film (Fuji Photo Film Co., Ltd.) is used as a light transmitting substrate, and the film thickness after curing of the photocurable resin composition 1 is on the substrate It applied so that it might be set to 6 micrometers. It was dried at 70 ° C. for 60 seconds, and was irradiated with ultraviolet light 150 mJ / cm ² under a nitrogen atmosphere to produce an optical film.

(Examples 2 to 17 and Comparative Examples 1 to 8)
(1) Preparation of Photocurable Resin Composition The photocurable resin compositions of Examples 2 to 17 of the compositions shown in the following Table 1 and the photocurable resin compositions of Comparative Examples 1 to 8 were prepared.
Abbreviations in Table 1 other than the compounds used in Example 1 are as follows. In addition, the amount of the cationically polymerizable compound, the cationically polymerizable radically polymerizable compound, and the photoacid generator in Table 1 describes the amount of the active ingredient.

・ Cationically polymerizable compound (epoxy group-containing polymer (1), merproof G-01100 (glycidyl methacrylate unit-containing polymer), manufactured by NOF Corporation)
・ Cationically polymerizable compound (epoxy group-containing polymer (2), poly (3,4-epoxycyclohexylmethyl methacrylate) of Synthesis Example 1)
・ Cationically polymerizable radically polymerizable compound (epoxy group and methacryloyl group-containing polymer, polymer of Synthesis Example 2)
・ Cationically polymerizable radically polymerizable compound (oxetanyl group-containing (meth) acrylate, (3-ethyl oxetan-3-yl) methyl methacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Radically polymerizable compound (polyfunctional acrylate (1), trade name: Alonix M-405, manufactured by Toagosei, dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (containing hydroxyl group) mixture, main component is dipentaerythritol hexaacrylate)
· Photoacid generators (photoacid generators (2) represented by the above general formula (1), photoacid generators represented by the following chemical formula (C), specification of WO 2005-116038, and JP 2005- It synthesize | combined according to the method as described in 146001 gazette.)
-Sulfonium salt-based photoacid generator (1) (trade name CPI-100P, manufactured by San Apro, 50 mass% propylene carbonate solution of active ingredient)
· Sulfonium salt-based photoacid generator (2) (bis (diphenylsulfonio) sulfide, a mixture of bis (hexafluorophosphate) and [(phenylthio) phenyl] diphenylsulfonium hexafluorophosphate, trade name AT-6992 Manufactured by ACETO, 42 mass% propylene carbonate solution of active ingredient)
-Iodonium salt photoacid generator (iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] hexafluorophosphate (1-),) trade name Irg 250, manufactured by BASF, 75 mass of active ingredient % Propylene carbonate solution)
・ Radical polymerization initiator (α-hydroxyacetophenone type (2), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane- 1-ON, trade name Irgacure 127, manufactured by BASF
· Radical polymerization initiator (α-hydroxyacetophenone type (3), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, trade name Irgacure 2959 , Made by BASF)
Radical polymerization initiator (α-hydroxyacetophenone type (4), oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone], trade name Esacure One, manufactured by Lamberti)
Radical polymerization initiator (acyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, trade name Lucirin TPO, manufactured by BASF)
Radical polymerization initiators (benzyl ketals, 2,2-dimethoxy-1,2-diphenylethan-1-one, trade name Irgacure 651, manufactured by BASF)
・ Radical polymerization initiator (α-aminoalkylphenone type, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, trade name Irgacure 907, manufactured by BASF)
Sensitizer (2,4-diethylthioxanthone Product name: KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.)

(2) Production of Optical Film In the production of the optical film of Example 1, the photocurable resin composition of Example 1 was compared with the photocurable resin compositions of Examples 2 to 17 and Comparative Examples 1 to 8, respectively An optical film was produced in the same manner as in Example 1 except that the photocurable resin composition was changed.

[Evaluation method]
The optical films of Examples 1 to 17 and Comparative Examples 1 to 8 were evaluated for curl width, pencil hardness, coloring, and whitening in a high temperature and high humidity environment. Moreover, the storage stability was evaluated about the photocurable resin composition of Examples 1-17 and Comparative Examples 1-8. The results for Examples 1 to 17 and Comparative Examples 1 to 8 are shown in Table 2.
(1) Curl Width The produced optical film was cut out to 100 mm × 100 mm, placed on a horizontal place with the protective layer surface up, and the distance between both ends of the film was measured by a ruler. The curl width was measured one day after preparation of the optical film.
When it was warped to the protective layer coated side (normal curl), it was not displayed, and when it was warped to the substrate side (reverse curl), it was displayed as "(reverse)".
<Evaluation criteria>
Evaluation ○: 70 mm or more Evaluation △: 50 mm or more and less than 70 mm Evaluation ×: less than 50 mm

(2) Pencil Hardness The prepared optical film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, and then the hardness was evaluated by a pencil hardness test in accordance with JIS K5600-5-4.

(3) Coloring Evaluation The prepared optical film was measured for b * at five locations by a transmission method using a spectroscope (“UVPC2450” manufactured by Shimadzu Corporation), and the value was determined from the average value.
<Evaluation criteria>
Evaluation ○: The average value of b * is 0.7 or less ×: The average value of b * exceeds 0.7

(4) Whitening under high temperature and high humidity environment After leaving the produced optical film for 24 hours under high temperature and high humidity environment (80 ° C., 90% humidity), the surface of the protective layer is visually observed to precipitate precipitates on the surface It was evaluated whether it was whitening or not.
<Evaluation criteria>
Evaluation ○: No precipitates deposited on the surface of the protective layer and not whitening Evaluation ×: Deposits deposited on the surface of the protective layer and whitened

(5) Evaluation of storage stability of the composition The viscosities of the photocurable resin composition immediately after preparation and after storage at 40 ° C for 7 days were measured at 25 ° C, and storage stability was judged from the degree of thickening. The smaller the rate of viscosity increase, the better the storage stability of the composition.
<Evaluation criteria>
Evaluation ○: Viscosity change is less than 1.3 times Evaluation ×: Viscosity change is 1.3 times or more

(Summary of results)
The photoacid generator represented by (B) the general formula (1) or the general formula (1 ′) of the present invention, (C) α-hydroxyacetophenone type radical polymerization initiator, acylphosphine oxide type radical polymerization initiation A photocurable resin composition containing a combination of at least one radical polymerization initiator selected from the group consisting of a curing agent and a benzyl ketal radical polymerization initiator does not contain highly toxic antimony, and is photocurable It was revealed that the curling is suppressed, the whitening of the surface of the cured film in a high temperature and high humidity environment is suppressed, and a cured product with less yellowing is obtained.
On the other hand, the photocurable resin compositions of Comparative Example 3 and Comparative Example 6, which contain a sulfonium-based photoacid generator and an α-hydroxyacetophenone-based radical polymerization initiator in combination, cure in a high temperature and high humidity environment. It was revealed that white precipitates were observed on the surface of the membrane and were whitened.
In the photocurable resin composition of Comparative Example 7 in which the amount of the active ingredient was reduced using a sulfonium salt-based photoacid generator, ultraviolet light was irradiated in a nitrogen atmosphere to produce an optical film, so curing under a high temperature and high humidity environment Although the whitening of the film surface was suppressed, the curl was aggravated.
The photocurable resin compositions of Comparative Example 4 and Comparative Example 5 containing an iodonium-based photoacid generator and an acylphosphine oxide-based radical polymerization initiator in combination have a cured film surface under high temperature and high humidity conditions. It was revealed that a white precipitate was seen and whitened. Furthermore, it was revealed that the photocurable resin compositions of Comparative Example 4 and Comparative Example 5 were inferior in storage stability. Moreover, in the photocurable resin composition of Comparative Example 5 in which a sensitizer was further added to Comparative Example 4, although curling was suppressed, a colored cured product was obtained.
Furthermore, the photoacid generator represented by the general formula (1) or the general formula (1 ′) used in the present invention is combined with an α-aminoalkylphenone-based radical polymerization initiator different from the present invention. In the photocurable resin composition of Comparative Example 8, the curl was significantly deteriorated.
Further, according to Comparative Examples 1 and 2, the whitening phenomenon in which white precipitates are observed on the surface of the cured film under a high temperature and high humidity environment is observed when only the radically polymerizable compound is used or when only the cationically polymerizable compound is used. Was not seen.

(Example 18)
A 25 μm cellulose triacetate film (manufactured by Fuji Photo Film Co., Ltd.) is used as a light transmitting substrate, and the film thickness after curing of the photocurable resin composition 3 obtained in Example 3 is 6 μm on the substrate. It applied so that it might become. The layer is dried at 70 ° C. for 60 seconds, irradiated with ultraviolet light 150 mJ / cm 2 in air, and a layer (protective layer) containing the cured product of the photocurable resin composition on one side of the light transmitting substrate A placed optical film was produced.

(Comparative example 9)
An optical film was produced in the same manner as in Example 18 except that in the production of the optical film of Example 18, the photocurable resin composition was changed to the comparative photocurable resin composition 7 obtained in Comparative Example 7. .

[Evaluation]
With respect to the optical films of Example 18 and Comparative Example 9, the whitening evaluation in a high temperature and high humidity environment was performed in the same manner as in Example 1.
[Evaluation results]
In Example 18 in which the photocurable resin composition of Example 3 was used, even when ultraviolet light was irradiated in the air to produce an optical film, the precipitates were not deposited on the surface of the protective layer as in Example 3. , Did not whiten. On the other hand, in the optical film of Comparative Example 7 in which ultraviolet irradiation was performed in a nitrogen atmosphere, whitening did not occur, but in Comparative Example 9 in which ultraviolet irradiation was performed in air using the same curable resin composition of Comparative Example 7 Precipitates were deposited on the surface of the protective layer to cause whitening.
When a sulfonium salt photoacid generator is used, when the optical film is produced by reducing the amount of the active ingredient and irradiating ultraviolet light in a nitrogen atmosphere, whitening in a high temperature and high humidity environment is suppressed (however, curling occurs Similarly, when the amount of the active ingredient was reduced and ultraviolet light was irradiated in air to produce an optical film, it was revealed that whitening occurs in a high temperature and high humidity environment. On the other hand, when the photoacid generator represented by the formula (1) used in the present invention is used, even if the ultraviolet irradiation is performed in the air with the same amount of the active ingredient as the comparative example to produce an optical film, It has been clarified that whitening is suppressed under high humidity environment.

1 optical film 10 light transmitting substrate 20 layer containing cured product of photocurable resin composition according to the present invention

Claims (6)

The photocurable resin composition containing following (A), (B), and (C).
(A) A photopolymerizable component which is at least one of the following (i) and (ii), and has at least a hydroxyl group and a radically polymerizable group in the molecule as at least one of the following (i) and (ii) Compound (i) Compound Having a Cationic Polymerizable Group, and Compound Having a Radical Polymerizable Group (ii) Compound Having a Cationic Polymerizable Group and a Radical Polymerizable Group (B) The Following Formula (1) or Formula Photoacid generator (C) represented by (1 ′) is selected from the group consisting of α-hydroxyacetophenone type radical polymerization initiator, acyl phosphine oxide type radical polymerization initiator, and benzyl ketal type radical polymerization initiator At least one radical polymerization initiator
(In the general formula (1) and the general formula (1 ′), R ¹ , R ² and R ³ each independently represent a substituent. A plurality of R ¹ , R ² or R ³ are each identical) Or may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom bond.
X ^- _{is, [P (R f) a} F 6-a] - a and, _{R f} represents an alkyl group in which at least 80% of the hydrogen atoms are substituted by fluorine atoms, is a = Less than six. The a number of Rf may be the same or different.
A is a chemical structure of n value, and n structures in parentheses are linked. n is an integer of 2 or more. Each of n pieces of X ⁻ , (R ¹ ) _{p ′} , (R ² ) _{q ′} and (R ³ ) _{r ′} may be the same or different.
p, q, p 'and q' are each independently an integer of 0-4.
r is an integer of 0-5, r 'is an integer of 0-4. )   The content of the anion in the said photo-acid generator (B) is 3 micromol / g-50 micromol / g with respect to the total mass of the said photopolymerizable component (A). Photocurable resin composition.   The compound having a radically polymerizable group in the molecule and not having a cationically polymerizable group is contained in an amount of 50% by mass or more and 97% by mass or less in the total amount of the photopolymerizable component (A). The photocurable resin composition as described. The radical polymerization initiator (C) is at least 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one. The photocurable resin composition according to any one of claims 1 to 3 , comprising. A cured product of the photocurable resin composition according to any one of claims 1 to 4 . The optical film by which the layer containing the hardened | cured material of the photocurable resin composition of any one of Claims 1-4 is arrange | positioned at one surface side of a transparent substrate.