TWI781263B - Curable resin composition, laminate, optical filter, and compound - Google Patents

Abstract

[R¹ ～R⁶ 分別獨立地為氫原子或甲基，X³ ～X¹⁰ 分別獨立地為具有脂環式烴基的碳數6～20的烴基，Y¹ ～Y⁴ 分別獨立地為具有脂環式烴基的碳數6～40的有機基，m為0～20的整數，n為0～20的整數]One embodiment of the present invention relates to a curable resin composition, a laminate, an optical filter, and a compound. The curable resin composition contains a compound selected from the following formula (A1) and the following formula (A2): At least one compound (A) and a polymerization initiator (D) among the compounds.

[R ¹ to R ⁶ are each independently a hydrogen atom or a methyl group, X ³ to X ¹⁰ are each independently a hydrocarbon group with 6 to 20 carbons having an alicyclic hydrocarbon group, and Y ¹ to Y ⁴ are each independently a hydrocarbon group having an alicyclic hydrocarbon group. An organic group with 6 to 40 carbon atoms of a cyclic hydrocarbon group, m is an integer of 0 to 20, and n is an integer of 0 to 20]

Description

Curable resin composition, laminate, optical filter and compound

One embodiment of the present invention relates to a curable resin composition, a laminate, an optical filter, and a compound.

In recent years, laminates in which a resin layer is provided on the surface of a substrate by coating a curable resin composition have been widely used in order to prevent film scratches or to improve the adhesion between the substrate and an upper layer provided thereon. Such laminates are used for display devices such as touch panels; surface materials for membrane switches and keypads; electrode substrates for liquid crystal cells that constitute liquid crystal display elements; retardation films, Optical films such as films with transparent electrodes for touch panels and films for near-infrared cut filters.

The resin layer of the laminate is required to be excellent in various properties such as scratch resistance, adhesion to the base material or upper layer, and hardness (for example, Patent Document 1 and Patent Document 2). [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 6041372 [Patent Document 2] Japanese Patent Laid-Open No. 2017-47683

In recent years, the development of a laminate formed with a base material/resin layer/inorganic film has progressed, and studies have been conducted on materials for lamination to obtain the laminate. For laminates used in optical components, etc., as one of the reliability evaluations, high adhesion at the interface of each layer after long-term storage in a high-temperature and high-humidity environment is required, but for the resin layer obtained by the conventional composition In other words, in order to meet the above requirements, there is still room for further improvement. In addition, if the surface hardness of the resin layer is low, scratches leading to defects will be generated. Therefore, the resin layer is desired to have a high hardness. However, the higher the hardness, the lower the adhesion, and it is difficult to achieve both hardness and adhesion.

One embodiment of the present invention provides a curable resin composition capable of forming a resin layer having high surface hardness and excellent adhesion, especially adhesion to an inorganic film.

As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems can be solved by the following configuration examples, and completed the present invention. Configuration examples of the present invention are as follows.

式（A1）中，R¹ 及R² 分別獨立地為氫原子或甲基，X³ ～X⁵ 分別獨立地為具有脂環式烴基的碳數6～20的烴基，Y¹ 及Y² 分別獨立地為具有脂環式烴基的碳數6～40的有機基，m為0～20的整數，在m為2以上的情況下，多個X⁴ 及Y¹ 既可分別相同，亦可不同； [化2]

式（A2）中，R³ ～R⁶ 分別獨立地為氫原子或甲基，X⁶ ～X¹⁰ 分別獨立地為具有脂環式烴基的碳數6～20的烴基，Y³ 及Y⁴ 分別獨立地為具有脂環式烴基的碳數6～40的有機基，n為0～20的整數，在n為2以上的情況下，多個X⁷ 、X¹⁰ 、Y⁴ 及R⁶ 既可分別相同，亦可不同。[1] A curable resin composition containing at least one compound (A) and a polymerization initiator (D) selected from the compounds represented by the following formula (A1) and the following formula (A2): 1]

In formula (A1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, X ³ to X ⁵ are each independently a hydrocarbon group with 6 to 20 carbons having an alicyclic hydrocarbon group, and Y ¹ and Y ² are respectively Independently an organic group having 6 to 40 carbon atoms having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and when m is 2 or more, a plurality of X ⁴ and Y ¹ may be the same or different ; [Chem 2]

In formula (A2), R ³ to R ⁶ are each independently a hydrogen atom or a methyl group, X ⁶ to X ¹⁰ are each independently a hydrocarbon group with 6 to 20 carbons having an alicyclic hydrocarbon group, and Y ³ and Y ⁴ are respectively Independently an organic group having 6 to 40 carbon atoms having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and when n is 2 or more, a plurality of X ⁷ , X ¹⁰ , Y ⁴ and R ⁶ may be used They are the same or different.

[2] The curable resin composition according to [1], wherein at least one of the X ³ to X ⁵ and at least one of the X ⁶ to X ¹⁰ each independently have an adamantane ring. A hydrocarbon group with 10-20 carbons.

[3] The curable resin composition according to [1] or [2], wherein at least one of Y ¹ to Y ² and at least one of Y ³ to Y ⁴ are independently the following: The base represented by any one of the above (y1)~the following (y5):

In formula (y1)~formula (y4), the two * respectively represent the bonding position with the N forming the urethane bond in formula (A1) or formula (A2), and the E in formula (y5) Among the two *, one of them represents the bonding position with the N of the isocyanurate ring, and the other represents the bond with the N forming the urethane bond in formula (A1) or formula (A2) Location.

式（B）中，R¹⁰ 為氫原子或甲基，L為具有碳數6～20的脂環式烴基的有機基。[4] The curable resin composition according to any one of [1] to [3], which has a compound (B) represented by the following formula (B): [Chem. 4]

In the formula (B), R ¹⁰ is a hydrogen atom or a methyl group, and L is an organic group having an alicyclic hydrocarbon group having 6 to 20 carbon atoms.

[5] The curable resin composition according to [4], wherein the content ratio of the compound (A) to the compound (B) in the curable resin composition (mass of compound (A) : the mass of compound (B)) is 1:99~99:1.

[6] The curable resin composition according to any one of [1] to [5], wherein the compound (A) has a molecular weight of 500 to 5,000. [7] The curable resin composition according to [4] or [5], wherein the molecular weight of the compound (B) is 180-600.

[8] A laminate comprising a substrate and a resin layer formed of the curable resin composition according to any one of [1] to [7]. [9] The laminate according to [8], wherein at least one of the base material and the resin layer contains a pigment.

[10] An optical filter comprising the laminate described in [8] or [9] and a dielectric multilayer film.

式（a）中，Y''為具有脂環式烴基的碳數6～40的有機基，X''獨立地為具有脂環式烴基的碳數6～20的烴基，R''獨立地為氫原子或甲基，p為2或3，多個X''及R''既可分別相同，亦可不同。[11] A compound represented by the following formula (a): [Chem. 5]

In formula (a), Y'' is an organic group with 6 to 40 carbons having an alicyclic hydrocarbon group, X'' is independently a hydrocarbon group with 6 to 20 carbons having an alicyclic hydrocarbon group, and R'' is independently is a hydrogen atom or a methyl group, p is 2 or 3, and a plurality of X'' and R'' may be the same or different.

[12] The compound according to [11], wherein at least one of the X'' is an adamantanediyl group.

式（y1）～式（y4）中，兩個*分別表示與式（a）中的構成胺基甲酸酯鍵的N的鍵結位置，式（y5）中的E的兩個*中，其中一個表示與異氰脲環的N進行鍵結的鍵結位置，另一個表示與式（a）中的構成胺基甲酸酯鍵的N的鍵結位置。[13] The compound as described in [11] or [12], wherein the Y'' is a group represented by any one of the following (y1) to the following (y5): [Chemical 6]

In the formulas (y1) to (y4), the two * respectively represent the bonding position with the N constituting the urethane bond in the formula (a), and in the two * of the E in the formula (y5), One of them represents a bonding position to N of the isocyanurate ring, and the other represents a bonding position to N constituting a urethane bond in formula (a).

According to one embodiment of the present invention, there is provided a curable resin composition capable of forming a resin layer having high surface hardness, excellent adhesion, especially adhesion to an inorganic film, and a low haze value. Furthermore, according to one embodiment of the present invention, it is possible to provide a laminate and an optical filter which are excellent in heat-and-moisture resistance and have few defects.

"Curable Resin Compositions and Compounds" The curable resin composition (hereinafter, also referred to as "this composition") according to one embodiment of the present invention contains at least one compound selected from the compounds represented by the above formula (A1) and the above formula (A2) (A) and a polymerization initiator (D). Furthermore, the compound (hereinafter also referred to as "compound (a)") of one embodiment of the present invention is represented by the formula (a).

Since this composition contains the compound (A), and by using the compound (a), it is easy to obtain high surface hardness, a small haze value, and excellent adhesion to substrates and inorganic films, especially when hot and humid. It is also a resin layer excellent in adhesion to an inorganic film because, for example, hygroscopicity can be suppressed. Furthermore, since the resin layer is easy to recover elastically and exhibit toughness, it can be expected to improve the scratch resistance of the film-formed film and improve the yield due to the suppression of micro cracks during wafer stamping, etc. The interaction between the urethane bond and the inorganic film and the effect of improving the adhesion to the base material or the inorganic film by stress relaxation can be recognized. Conventional polyfunctional urethane compounds are easy to absorb moisture, and their adhesion to substrates or inorganic films decreases when they are wet and hot. Furthermore, they tend to cause curing shrinkage due to multifunctionalization to achieve high hardness. , the adhesiveness with the substrate or the inorganic film decreases. On the other hand, by using compounds (A) and (a) having a large amount of alicyclic structure, a hydrophobic resin layer that is less likely to shrink when hardened and has high hardness can be formed, and it can be compatible with hardening or wet heat. Adhesiveness and high hardness of substrate or inorganic film. Moreover, compounds (A) and (a) having urethane bonds are easier to synthesize than compounds having ester bonds. Therefore, the present invention related to the compounds (A) and (a) can also be described as a development of materials. Medium and high practicality. This composition and compound (a) can be suitably used for an optical member, especially an optical filter, and further a near-infrared cut filter.

<Compound (A)> The compound (A) is at least one compound selected from the compounds represented by the following formula (A1) and the following formula (A2). A compound represented by the following formula (A1) is more preferable in terms of easily obtaining a resin layer having better adhesion to the base material and adhesion to the inorganic film during wet heat and less curing shrinkage.

[式（A1）中，R¹ 及R² 分別獨立地為氫原子或甲基，X³ ～X⁵ 分別獨立地為具有脂環式烴基的碳數6～20的烴基，Y¹ 及Y² 分別獨立地為具有脂環式烴基的碳數6～40的有機基，m為0～20的整數，在m為2以上的情況下，多個X⁴ 及Y¹ 既可分別相同，亦可不同][chemical 7]

[In formula (A1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, X ³ to X ⁵ are each independently a hydrocarbon group with 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y ¹ and Y ² Each independently is an organic group having 6 to 40 carbon atoms having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and when m is 2 or more, a plurality of X ⁴ and Y ¹ may be the same or may be different]

[式（A2）中，R³ ～R⁶ 分別獨立地為氫原子或甲基，X⁶ ～X¹⁰ 分別獨立地為具有脂環式烴基的碳數6～20的烴基，Y³ 及Y⁴ 分別獨立地為具有脂環式烴基的碳數6～40的有機基，n為0～20的整數，在n為2以上的情況下，多個X⁷ 、X¹⁰ 、Y⁴ 及R⁶ 既可分別相同，亦可不同][chemical 8]

[In formula (A2), R ³ to R ⁶ are each independently a hydrogen atom or a methyl group, X ⁶ to X ¹⁰ are each independently a hydrocarbon group with 6 to 20 carbons having an alicyclic hydrocarbon group, Y ³ and Y ⁴ Each independently is an organic group having 6 to 40 carbon atoms having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and when n is 2 or more, a plurality of X ⁷ , X ¹⁰ , Y ⁴ and R ⁶ Can be the same or different]

X ³ to X ¹⁰ are each independently a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, preferably a group including an alicyclic hydrocarbon group. The carbon number of the hydrocarbon group in X ³ to X ¹⁰ is 6 or more, preferably 8 or more, more preferably 10 or more, and 20 or less, preferably 17 or less, more preferably 12 or less.

Examples of the alicyclic hydrocarbon group contained in X ³ to X ¹⁰ include: cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctane Diyl, cyclopropenediyl, cyclobutenediyl, cyclopentenediyl, cyclohexenediyl, cycloheptenediyl, cyclooctenediyl, bicyclo[2.2.1]heptanediyl, three Methylbicyclo[2.2.1]heptanediyl, bicyclo[2.2.2]octanediyl, adamantanediyl, bicyclo[2.2.1]heptenediyl, bicyclo[2.2.2]octenediyl , cyclohexane dimethyl, tricyclodecane dimethyl, pentacyclodecane dimethyl, etc. Among them, cyclohexanedimethyl and adamantanediyl groups are preferable because a resin layer with high hardness can be easily obtained even if the crosslinking group concentration is low, and a combination of high hardness and low curing shrinkage can be easily obtained. The adamantanediyl group is particularly preferable in terms of a resin layer having a better balance between them. That is, preferably at least one of X ³ to X ⁵ and at least one of X ⁶ to X ¹⁰ , wherein preferably X ³ to X ¹⁰ are each independently a hydrocarbon group having an adamantane ring with 10 to 20 carbons , especially preferably adamantanediyl.

The carbon number of the organic group in Y ¹ to Y ⁴ is 6 or more, preferably 8 or more, more preferably 10 or more, and 40 or less, preferably 30 or less, more preferably 20 or less.

Examples of the alicyclic hydrocarbon group contained in Y ¹ to Y ⁴ include the same groups as those exemplified as the alicyclic hydrocarbon group contained in X ³ to X ¹⁰ .

In terms of being able to easily obtain a resin layer having better adhesion to the base material and the inorganic film, especially even when wet and hot, the resin layer having better adhesion to the inorganic film is preferred among ^Y1 to ^Y2 . At least one and at least one of Y ³ ~ Y ⁴ , wherein preferably Y ¹ ~ Y ⁴ are each independently a hydrocarbon group with 6 to 20 carbons having an alicyclic hydrocarbon group or containing an alicyclic hydrocarbon group and isocyanuric acid The organic group having 15 to 40 carbon atoms in the ester ring is more preferably a group containing a cyclohexane ring or a norbornane ring, and is further preferably formed by any one of the following (y1) to the following (y5). base of representation.

[chemical 9]

In the formulas (y1) to (y4), the two * respectively represent the bonding position with the N forming the urethane bond in the formula (A1) or the formula (A2), and the E in the formula (y5) Among the two *, one of them represents the bonding position with the N of the isocyanure ring, and the other represents the bonding with the N forming the urethane bond in formula (A1) or formula (A2) Location. The position of -CH ₂ -* in the formula (y3) is preferably the meta-position or para-position of *-CH ₂ -Cy (Cy is a cyclohexane ring).

m is preferably 0 to 5, and is more preferably 0 in consideration of the ease of synthesis of the compound (A), the yield during synthesis, and the like. n is preferably 0 to 5, and is more preferably 0 in consideration of the ease of synthesis of the compound (A), the yield during synthesis, and the like.

In particular, the compound (A) is preferably represented by the following formula (a) in terms of easily obtaining a resin layer having high surface hardness, a small haze value, and excellent adhesion to the substrate and the inorganic film. indicated compound.

[chemical 10]

In formula (a), Y'' is an organic group having 6 to 40 carbon atoms having an alicyclic hydrocarbon group, and examples thereof include the same groups as Y ¹ to Y ⁴ , and preferred groups are also the same. X'' is independently a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, examples of which include the same groups as X ³ to X ¹⁰ , and preferred groups are also the same. R'' is independently a hydrogen atom or a methyl group, and p is 2 or 3. A plurality of X'' and R'' may be the same or different.

The molecular weight of the compound (A) is preferably 500-5000, more preferably 500-2000.

The synthesis method of the compound (A) is not particularly limited, and it can be synthesized by a previously known method, but it is preferable to combine the compound represented by the following formula (a1) with the compound represented by the following formula (a2) The way the compound reacts. In addition, a compound represented by the following formula (a3) can also be used when performing the reaction.

（式（a1）中，R及X¹ 分別與所述R¹ 及X³ 含義相同）[chemical 11]

(In formula (a1), R and X ¹ have the same meaning as R ¹ and X ³ respectively)

（式（a2）中，Y與所述Y¹ 含義相同，q為2或3）[chemical 12]

(In the formula (a2), Y has the same meaning as ^Y1 , and q is 2 or 3)

（式（a3）中，X² 與所述X³ 含義相同）[chemical 13]

(In formula (a3), X ² has the same meaning as X ³ above)

The reaction is preferably performed in the presence of a catalyst, a solvent, and the like previously used in the reaction of a hydroxyl group and an isocyanate group. Moreover, the reaction is preferably carried out under heating, and the reaction temperature is preferably 50°C to 90°C.

The content ratio of the compound (A) in the present composition is preferably 1 mass % or more, more preferably at least 10 mass %, especially preferably at least 30 mass %, and preferably at most 90 mass %, more preferably at most 80 mass %, especially preferably at most 70 mass %.

＜Polymerization initiator (D)＞ This composition contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound capable of polymerizing the compound (A) and the following compound (B) or compound (C). The polymerization initiator (D) contained in this composition may be one type or two or more types.

As a polymerization initiator (D), a well-known photoinitiator can be used, and a thermal polymerization initiator can also be used together as needed.

As a polymerization initiator (D), the photoinitiator described in Unexamined-Japanese-Patent No. 2008-276194 and Unexamined-Japanese-Patent No. 2003-241372 is mentioned, for example.

Examples of the polymerization initiator (D) include alkylphenone compounds, acylphosphine oxide compounds, biimidazole compounds, triazine compounds, oxime ester compounds, benzoin compounds, and benzophenone compounds.

Examples of alkylphenone compounds include: 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2- Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propane Acyl)-benzyl]phenyl}-2-methyl-propan-1-one and other α-hydroxyalkylphenones; 2-methyl-1-(4-methylthiophenyl)-2- Morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(2-methylbenzyl) -2-Dimethylamino-1-(4-morpholinylphenyl)butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholinyl Phenyl)butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-(2-ethylbenzyl)- 2-Dimethylamino-1-(4-morpholinophenyl) butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl) Base) butanone and 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl) butanone and other α-aminoalkylphenones; 2,2 - Dialkoxyacetophenones such as dimethoxy-1,2-diphenylethan-1-one and 2,2-diethoxyacetophenone.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)benzene Phosphine oxides.

As the biimidazole compound, for example, 2,2'-bis(2,4-dichlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dimethylphenyl )-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-methylphenyl)-4,5,4',5'-tetra Phenyl-1,2'-biimidazole and 2,2'-diphenyl-4,5,4',5'-tetraphenyl-1,2'-biimidazole.

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine .

Examples of oxime ester compounds include N-benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-ethoxycarbonyloxy- 1-Phenylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-ethyl Acyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxazol-3-yl]ethane-1-imine and N-acetyloxy-1 -[9-Ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxocyclopentylmethyloxy)benzoyl}-9H- Xazol-3-yl]ethane-1-imine.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of benzophenone compounds include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylthio ether, 3,3',4,4'-bis(diethylamino)benzophenone, 4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and 2,4, 6-Trimethylbenzophenone.

Among these, an acylphosphine oxide compound and an alkylphenone compound are preferable, and an alkylphenone compound is more preferable at the point that a resin layer more excellent in curability and transparency can be easily obtained.

The content ratio of the polymerization initiator (D) in this composition is relative to It is preferably at least 0.5 parts by mass, more preferably at least 1 part by mass, and preferably at most 15 parts by mass, based on 100 parts by mass of the compound (A) and the following compound (B) and compound (C) in total. , more preferably 8 parts by mass or less.

＜Compound (B)＞ The present composition may contain a compound represented by the following formula (B) other than the above-mentioned compound (A) from the viewpoint of easily obtaining a resin layer having better adhesion to the substrate and the inorganic film, etc. (B). The compound (B) contained in this composition may be one type, or may be two or more types.

[chemical 14]

In formula (B), R ¹⁰ is a hydrogen atom or a methyl group. L is an organic group having an alicyclic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom of the alicyclic structure may be substituted with a group or atom other than a (meth)acryl group such as a hydroxyl group, a hydrocarbon group or a halogen atom. Examples of the alicyclic hydrocarbon group in L include the same groups as those exemplified for ^X3 , and the like. The carbon number of the organic group in L is preferably 8 or more, more preferably 10 or more, and is preferably 15 or less, more preferably 12 or less.

Examples of the alicyclic hydrocarbon group contained in L include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropenyl, cyclobutenyl, and cyclopentenyl. , cyclohexenyl, cycloheptenyl, cyclooctenyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, tricyclo[3.3.1.1 ^3,7 ]decyl, Bicyclo[2.2.1]heptenyl, bicyclo[2.2.2]octenyl, etc. Among them, a tricyclo[3.3.1.1 ^3,7 ]decyl group is particularly preferable in that a resin layer having a better balance between high hardness and low curing shrinkage can be easily obtained.

The compound (B) is not particularly limited, and examples include: cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, dicyclopentenyl (methyl) ) acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, tricyclic Decanedimethanol (meth)acrylate, isobornyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (methyl) ) acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate, 3-phenylaminoformyl-1-adamantyl (meth)acrylate, and the like.

The molecular weight of the compound (B) is preferably 180 or more, more preferably 200 or more, preferably 600 or less, more preferably 400 or less.

When the compound (B) is included in this composition, it is possible to easily obtain a resin layer having high surface hardness, a small haze value, and better adhesion to substrates and inorganic films. The content ratio of the compound (B) in is preferably from 1 mass % to 50 mass %, more preferably from 1 mass % to 30 mass %. Furthermore, the content ratio of the compound (A) to the compound (B) in this composition (the mass of the compound (A) : the mass of the compound (B)) is preferable for the same reason as described above. 1:99 to 99:1, more preferably 80:20 to 50:50.

＜Other ingredients＞ The present composition may contain previously known components other than the above-mentioned compound (A) and compound (B) and the polymerization initiator (D). Examples of the other components include polyfunctional (meth)acrylic monomers other than compound (A) and compound (B) (hereinafter also referred to as "compound (C)"), compounds other than compound (B) Monofunctional (meth)acrylic monomers, solvents, antioxidants, UV absorbers, pigments, antireflective agents, hard coating agents, antistatic agents, metal complex compounds, leveling agents, defoaming agents, coupling agents . Each of these other components may be one type, or two or more types.

The compound (C) is not particularly limited, and examples thereof include poly(meth)acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Specifically, : Trimethylolpropane di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Trimethylolpropane oxide modified tri(meth)acrylate, Pentaerythritol tri(meth)acrylate ) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. In addition, tricyclodecane dimethanol di(meth)acrylate, alkanediol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, isocyanurate skeleton-containing Di- or tri(meth)acrylate, di(meth)acrylate having a bisphenol A skeleton, and the like.

In terms of easily obtaining a resin layer with high surface hardness, low haze value, and better adhesion with the substrate and the inorganic film, the content ratio of the compound (C) in the composition is preferably 5% by mass. % or more, more preferably 15 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less. Furthermore, the ratio of the compound (C) in the present composition to the total of 100% by mass of the compound (A) to the compound (C) is preferably 10% by mass for the same reason as described above. % or more, more preferably 20 mass % or more, and preferably 55 mass % or less, more preferably 45 mass % or less.

The pigment is not particularly limited, and may be an inorganic compound or an organic compound, but is preferably an organic compound. Furthermore, the dye may be appropriately selected from conventionally known dyes according to the intended use of the composition, but when the composition is used for a near-infrared cut filter, it is preferable to use a near-infrared absorbing dye .

Examples of such near-infrared absorbing dyes include squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, dithiol-based compounds, diimonium-based compounds, porphyrin-based compounds, Ke ketonium (croconium) series compounds.

The maximum absorption wavelength of the near-infrared absorbing pigment is preferably at least 600 nm, more preferably at least 620 nm, particularly preferably at least 650 nm, and more preferably at most 800 nm, further preferably at most 760 nm, most preferably at most 740 nm . When the maximum absorption wavelength is within such a wavelength range, sufficient near-infrared absorption characteristics and visible light transmittance can be achieved at the same time. As a near-infrared absorbing dye satisfying such absorption characteristics, squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, and crotonium-based compounds are particularly preferable.

In terms of excellent visible light transmittance and ability to absorb light of a desired wavelength, the content of the pigment in the composition is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and more preferably 20% by mass. or less, more preferably 10% by mass or less.

"Layers" The resin layer formed from this composition may be used alone as a resin film, but it is preferably used as a laminate with a base material. The base material and the resin layer contained in this laminated body may each be one layer (sheet), or may be two or more layers (sheet). Moreover, the resin layer may exist only in one surface of a base material, and may exist in both surfaces.

The thickness of the resin layer (one layer) can be appropriately selected according to the desired application, but it is preferably at least 0.1 μm, more preferably at least 0.5 μm, particularly preferably at least 0.7 μm, and preferably at most 20 μm, and further Preferably, it is 10 μm or less, especially preferably 5 μm or less.

The base material is preferably a transparent plate-shaped body with an average light transmittance of 85% or more in the wavelength region of 400 nm to 700 nm, and is preferably formed of a material that transmits visible light, for example, resin-based materials, glass substrates. Among them, the resin substrate is preferable because it is excellent in processability and has excellent adhesion to the resin layer.

Examples of resin base materials include polycarbonate resins, acrylic resins, polyester resins, polyether resins, polyolefin resins, epoxy resins, alkyd resins, melamine resins, poly Base materials for urethane-based resins, polyimide-based resins, polyamide-based resins, norbornene-based resins, etc.

Examples of glass substrates include soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, chemically strengthened glass, physically strengthened glass, copper-containing Substrates for phosphate glass, copper-containing fluorophosphate glass, etc.

At least one of the base material and the resin layer preferably contains a pigment. In particular, when the laminate is used for a near-infrared cut filter, it is preferable to use a near-infrared absorbing dye. Examples of the near-infrared absorbing dye include the same dyes as described above, and the content of the dye in the base material or the resin layer also includes the same range as the content ratio of the dye in the above-mentioned composition.

The thickness of these substrates can be appropriately selected according to the desired application, preferably 10 μm or more, more preferably 20 μm or more, especially preferably 25 μm or more, and preferably 100 mm or less, more preferably 50 mm below, preferably below 10 mm.

The method for producing the laminate is not particularly limited. After forming a resin layer (film) from this composition on a support, the support can be peeled off, and the obtained resin layer (film) can be laminated with a substrate. Preferably, the present composition is coated on a substrate and cured to form a laminate.

As the coating method, known methods can be appropriately selected. For example, wire bar coating method, dip coating method, cast coating method, spray coating method, spinner coating method, bead coating method, knife coating method, roll coating method, curtain coating method, slot coating method, etc. Film coater method, gravure coater method, slit reverse coater method, microgravure method, comma coater method, screen printing method, flexographic printing printing method.

After coating this composition on a base material, before hardening mentioned later, you may dry the coated this composition, for example.

The curing method is not particularly limited, and there are a method of curing by heating, a method of irradiating light, etc., and a method of irradiating light is particularly preferable. The light to be irradiated is preferably light with a wavelength of 200 nm to 500 nm. Curing can also be accelerated by heating during or after light irradiation. The temperature condition at the time of light irradiation is preferably at least 0°C, more preferably at least 10°C, and is preferably at most 100°C, more preferably at most 60°C. The environment when light is irradiated may be under the atmosphere, but an inert gas environment is preferable in terms of reducing the influence of oxygen barrier and the like. Nitrogen, argon, etc. are mentioned as an inert gas. The amount of light exposure (cumulative light amount) can be selected from, for example, a range of about 50 mJ/cm ² to 20000 mJ/cm ² , and in the case of a nitrogen environment, it is preferably 100 mJ/cm ² or more, more preferably 200 mJ/cm ² or more, and preferably 10000 mJ/cm ² or less, more preferably 8000 mJ/cm ² or less.

The laminate may further have an inorganic film. This inorganic film may be formed on the substrate, but it is preferably formed on the resin layer in terms of further exerting the effect of providing the resin layer. Examples of the inorganic film include: dielectric multilayer films, conductive films such as indium tin oxide (Indium Tin Oxide, ITO) films; films of metals such as gold, platinum, and copper, oxides thereof, or alloys containing these metals; .

The laminate can be suitably used for display devices such as touch panels; surface materials for membrane switches, keypads, etc.; electrode substrates for liquid crystal cells constituting liquid crystal display elements; retardation films, tapes for touch panels, etc. Films for transparent electrodes, optical films such as films for near-infrared cut filters, etc., are particularly preferably used for near-infrared cut filters (films).

"Optical Filter" An optical filter according to one embodiment of the present invention preferably has the above-mentioned laminate and a dielectric multilayer film. The dielectric multilayer film may be formed directly on the substrate, but it is preferably formed on the resin layer in terms of further exerting the effect of providing the resin layer. The optical filter is not particularly limited, but is preferably a near-infrared cut filter.

The dielectric multilayer film is preferably a film capable of reflecting near infrared rays. The dielectric multilayer film may be provided on one side or both sides of the laminate. When provided on one side, an optical filter with excellent manufacturing cost and ease of manufacture can be obtained, and when provided on both sides, an optical filter with high strength and less warpage can be obtained.

Examples of the dielectric multilayer film include films in which high-refractive-index material layers and low-refractive-index material layers are alternately laminated.

As a material constituting the high-refractive index material layer, a material having a refractive index of 1.7 or higher can be used, and a material whose refractive index ranges generally from 1.7 to 2.5 can be selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as the main component, and a small amount (for example, relative to the main component) 0% to 10%) containing titanium oxide, tin oxide and/or cerium oxide, etc.

As a material constituting the low-refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material whose refractive index ranges generally from 1.2 to 1.6 can be selected. Examples of such materials include silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The method of laminating the high-refractive-index material layer and the low-refractive-index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, on the laminated body, directly by chemical vapor deposition (chemical vapor deposition, CVD) method, sputtering method, vacuum evaporation method, ion-assisted evaporation method or ion plating method, etc., to form alternate laminated layers. Dielectric multilayer film of high refractive index material layer and low refractive index material layer. In addition, at this time, the surface of the resin layer may be surface treated by corona treatment, plasma treatment, or the like.

If the wavelength to be shielded is λ (nm), the thickness of each of the high-refractive index material layer and the low-refractive index material layer is usually preferably a thickness of 0.1 λ to 0.5 λ. If the thickness of each layer of the high refractive index material layer and the low refractive index material layer is within the above range, the optical film thickness calculated by the product (n×d) of the refractive index (n) and the film thickness (d) becomes equal to Values of λ/4 being substantially the same tend to allow easy control of shielding and transmission of specific wavelengths in terms of the relationship between the optical characteristics of reflection and refraction. The value of λ (nm) is, for example, 700 nm or more, preferably 750 nm or more, and for example, 1400 nm or less, preferably 1300 nm or less.

The total number of laminated layers of the high-refractive-index material layer and the low-refractive-index material layer in the dielectric multilayer film is preferably 5 or more layers, more preferably 10 or more layers, and preferably 60 layers in terms of the optical filter as a whole Below, more preferably below 50 layers.

If warpage occurs in the optical filter when the dielectric multilayer film is formed, in order to eliminate the warp, the dielectric multilayer film can be formed on both sides of the laminate, or the laminate can be formed. A method in which the surface on which the dielectric multilayer film is formed is irradiated with electromagnetic waves such as ultraviolet rays. In addition, when irradiating electromagnetic waves, the irradiation may be performed during the formation of the dielectric multilayer film, or may be irradiated separately after formation.

For the above-mentioned optical filter, within the scope of not impairing the effect of the present invention, for the purpose of improving the surface hardness of the base material or the dielectric multilayer film, improving chemical resistance, antistatic, and eliminating damage, etc., in On the surface of the laminate on the opposite side to the surface on which the dielectric multilayer film is provided, or on the surface of the dielectric multilayer film on the opposite side to the surface on which the laminate is provided, an antireflection film or hard coating is appropriately provided. Coating film, anti-static film and other functional films. [Example]

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

[Determination of molecular weight] The molecular weights of the compounds synthesized in the following synthesis examples were obtained by using GPC columns (G2000HXL 2, G3000HXL 1, and G4000HXL 1) manufactured by Tosoh Co., Ltd. under the following measurement conditions. Permeation chromatography (Gel Permeation Chromatography, GPC) to determine. GPC determination conditions: Dissolution solvent: tetrahydrofuran ·Flow rate: 1.0 mL/min ・Sample concentration: 1.0% by mass ・Sample injection volume: 100 μL ·Column temperature: 40℃ Detector: differential refractometer ・Standard material: monodisperse polystyrene

[Synthesis Example 1] Synthesis of Compound (A-1) In a reaction vessel with a stirring device, a thermometer and a condenser, 0.0194 g of 2,6-di-tert-butyl-4-methylphenol was prepared at room temperature , 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222), 27.047 g (0.12 mol), and isophorone diisocyanate (manufactured by Evonik, molecular weight : 222) 26.481 g (0.12 mol) was dissolved in 19 g of methyl ethyl ketone (MEK), and 0.405 g of dioctyltin dilaurate was added, and then the temperature was raised to 70°C while stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate was added and the reaction was continued at 70°C. When it was confirmed in the infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group almost disappeared, the reaction was terminated. The reaction mixture was purified by silica gel column chromatography using ethyl acetate/hexane as an eluent, thereby obtaining urethane acrylate compound (A-1) (molecular weight: 667) .

The proton nuclear magnetic resonance ( ¹ H-nuclear magnetic resonance, ¹ H-NMR) spectrum of the compound (A-1) was measured using a nuclear magnetic resonance apparatus (trade name "JNM-ECX400", manufactured by JEOL Ltd.) . The results are as follows, and it was confirmed that the obtained compound (A-1) had a structure represented by the following formula (A-1). ¹ H-NMR (DMSO-d ₆ ); m, 1H), 5.86 (d, 2H), 6.06 (t, 2H), 6.21 (d, 2H), 6.82 (s, 1H), 6.93 (s, 1H)

[chemical 15]

[Synthesis Example 2] Synthesis of compound (A-2) In a reaction vessel with a stirring device, a thermometer and a condenser, 0.0194 g of 2,6-di-tert-butyl-4-methylphenol was prepared at room temperature , 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222), 27.047 g (0.12 mol), and norbornane diisocyanate (manufactured by Mitsui Chemicals Co., Ltd., molecular weight: 206 ) 24.7 g (0.12 mol) was dissolved in 19 g of MEK, 0.405 g of dioctyltin dilaurate was added, and the temperature was raised to 70° C. while stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate was added and the reaction was continued at 70°C. When it was confirmed in the infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group almost disappeared, the reaction was terminated. The reaction mixture was purified by silica gel column chromatography using ethyl acetate/hexane as an eluent, thereby obtaining urethane acrylate compound (A-2) (molecular weight: 651) .

From the result and molecular weight of Synthesis Example 1, the structure of the obtained compound (A-2) is considered to be represented by the following formula (A-2). [chemical 16]

[Synthesis Example 3] Synthesis of Compound (A-3) In a reaction vessel with a stirring device, a thermometer and a condenser, 0.0194 g of 2,6-di-tert-butyl-4-methylphenol was prepared at room temperature , 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222) 27.047 g (0.12 mol), and 1,3-hydroxylylene diisocyanate (active material chemical ( Katsuzai Chemical (Katsuzai Chemical) Co., Ltd., molecular weight: 194) 23.3 g (0.12 mol) was dissolved in 19 g of MEK, 0.405 g of dioctyltin dilaurate was added, and the temperature was raised to 70°C while stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate was added and the reaction was continued at 70°C. When it was confirmed in the infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group almost disappeared, the reaction was terminated. The reaction mixture was purified by silica gel column chromatography using ethyl acetate/hexane as an eluent, thereby obtaining urethane acrylate compound (A-3) (molecular weight: 639) .

From the result and molecular weight of Synthesis Example 1, the structure of the obtained compound (A-3) is considered to be represented by the following formula (A-3). [chemical 17]

[Synthesis Example 4] Synthesis of Compound (A-4) In a reaction vessel with a stirring device, a thermometer and a condenser, 0.0194 g of 2,6-di-tert-butyl-4-methylphenol was prepared at room temperature , 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222) 27.047 g (0.12 mol), and 4,4'-methylene bis(cyclohexyl isocyanate) (win Made by Evonik, molecular weight: 262) 31.4 g (0.12 mol) was dissolved in 19 g of MEK, 0.405 g of dioctyltin dilaurate was added, and the temperature was raised to 70° C. while stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate was added and the reaction was continued at 70°C. When it was confirmed in the infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group almost disappeared, the reaction was terminated. The reaction mixture was purified by silica gel column chromatography using ethyl acetate/hexane as an eluent, thereby obtaining urethane acrylate compound (A-4) (molecular weight: 707) .

From the result and molecular weight of Synthesis Example 1, the structure of the obtained compound (A-4) is considered to be represented by the following formula (A-4). [chemical 18]

[Synthesis Example 5] Synthesis of Compound (A-5) In a reaction vessel with a stirring device, a thermometer and a condenser, 0.0194 g of 2,6-di-tert-butyl-4-methylphenol was prepared at room temperature , 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222), 27.047 g (0.12 mol), and isophorone diisocyanate (manufactured by Evonik, molecular weight : 222) 26.481 g (0.12 mol) was dissolved in 19 g of MEK, 0.405 g of dioctyltin dilaurate was added, and the temperature was raised to 70° C. while stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 23.8 g of 1,4-cyclohexanedimethanol monoacrylate (manufactured by Nippon Chemical Co., Ltd., molecular weight: 198) was added ( 0.12 mol), continue the reaction at 70°C. When it was confirmed in the infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group almost disappeared, the reaction was terminated. The reaction mixture was purified by silica gel column chromatography using ethyl acetate/hexane as an eluent, thereby obtaining urethane acrylate compound (A-5) (molecular weight: 643) .

From the result and molecular weight of Synthesis Example 1, the structure of the obtained compound (A-5) is considered to be represented by the following formula (A-5). [chemical 19]

[Synthesis Example 6] Synthesis of Compound (A-6) In a reaction vessel with a stirring device, a thermometer and a condenser, 0.0194 g of 2,6-di-tert-butyl-4-methylphenol was prepared at room temperature , 3-hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222) 27.047 g (0.12 mol), and isophorone diisocyanate isocyanurate (trade name : VESTANAT T1890/100, manufactured by Evonik, NCO value: 17.3 wt%) 29.0 g was dissolved in 19 g of MEK, 0.405 g of dioctyltin dilaurate was added, and the temperature was raised to 70°C while stirring . After confirming that the solution became uniform and transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate and 29.0 g of isocyanurate bodies of isophorone diisocyanate were added, and the reaction was continued at 70°C. When it was confirmed in the infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group almost disappeared, the reaction was terminated. The reaction mixture was purified by silica gel column chromatography using ethyl acetate/hexane as an eluent, thereby obtaining urethane acrylate compound (A-6) (molecular weight: 1334) .

The results of ¹ H-NMR measurement of compound (A-6) measured using the same apparatus as described above are as follows, and it was confirmed that the structure of the obtained compound (A-6) is represented by the following formula (A-6) Structure. ¹ H-NMR (DMSO-d ₆ ); ), 6.06 (m, 3H), 6.21 (m, 3H), 6.99 (m, 3H)

[chemical 20]

[Example 1] Preparation of Curable Resin Composition Solution 3.0 g of compound (A-1) and 0.09 g of compound (D-1) were added to a 20 mL sample tube, and diluted with 10 g of MEK to prepare a curable resin composition.

[Example 2-Example 11 and Comparative Example 1-Comparative Example 4] Preparation of Curable Resin Composition A composition was prepared in the same manner as in Example 1 except that the compounds described in Table 1 were used so as to have the ratios described in Table 1. In addition, the numerical value described in the column of the composition of Table 1 is the ratio (mass part) of the compound used when the total of compounds (A)-(C) is 100 mass parts. The details of Compound (B-1) to Compound (B-4), Compound (C-1) to Compound (C-3), and Compound (D-1) to Compound (D-3) listed in Table 1 Shown in Table 2.

[Haze measurement] On a substrate (norbornane-based resin film [manufactured by JSR Co., Ltd., Arton FEKE100, film thickness 100 μm]), the obtained resin layer was coated so that the thickness of the obtained resin layer became 3 μm. The curable resin compositions obtained in the above-mentioned Examples and Comparative Examples were irradiated with ultraviolet rays in a nitrogen atmosphere to be cured to obtain a substrate with a resin layer. Using the obtained base material with a resin layer, a method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7136 was used, and a haze meter (manufactured by Toyo Seiki Works, trade name: Haze -gard) II), the haze value of the substrate with the resin layer was measured. The case where the haze value was 0.1 or less was judged as favorable. The results are shown in Table 1.

[Pencil Hardness Test] The hardness of the resin layer in the obtained base material with a resin layer was measured by the pencil hardness test similarly to haze measurement in accordance with the method described in JISK5600-5-4. Specifically, after humidity-conditioning the substrate with the resin layer at a temperature of 25°C and a humidity of 60%RH for 2 hours, the surface of the resin layer was scratched with a load of 4.9 N using a test pencil, and five Among the inspection materials, the highest pencil hardness among which three or more were not damaged was set as an evaluation value. The case where the pencil hardness was B or more was judged as favorable. The results are shown in Table 1.

[Moist heat resistance (adhesion) test] In the same manner as the haze measurement, a substrate with a resin layer was obtained. On the resin layer of the obtained substrate with a resin layer, the following inorganic films (dielectric multilayer film, ITO sputtered film, or gold vapor-deposited film) were formed. The obtained substrate with an inorganic film was placed in a constant temperature and humidity chamber at 85° C. and 85% RH for 1000 hours. Thereafter, the adhesiveness between the inorganic film and the resin layer was evaluated as follows. The results are shown in Table 1. Dielectric multilayer film: A film in which SiO ₂ (film thickness: 10 nm to 100 nm) layers and TiO ₂ (film thickness: 10 nm to 120 nm) layers are alternately laminated by a conventionally known vapor deposition method (laminated layer Number 28, total thickness 3 μm) ITO sputtering film: a film formed by vapor-depositing ITO by a known method (thickness: 500 nm) Gold vapor-deposited film: gold vapor-deposited by a known method Formed film (thickness: 500 nm)

Using a cutter, 11 vertical and 11 horizontal notches reaching the resin layer were drawn in a checkerboard pattern on the surface of the inorganic film at intervals of 1 mm, and a total of 100 square grids were drawn. Adhesive tape (cellophane (cellophane) tape (registered trademark), manufactured by Nichiban Co., Ltd., trade name: CT24) was attached to the surface of the notch, and then the adhesive tape was peeled off. The number of objects of the inorganic film remaining on the substrate was evaluated. In 100 squares, when the number of objects of the inorganic film remaining on the base material side was 90 or more even after the tape was peeled off, it was determined that the adhesiveness was good.

[Table 1]

[Table 2]

none

Claims (11)

A curable resin composition comprising at least one compound (A) and a polymerization initiator (D) selected from compounds represented by the following formula (A1) and the following formula (A2):

In formula (A1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, X ³ to X ⁵ are each independently a hydrocarbon group with 6 to 20 carbon atoms having an alicyclic hydrocarbon group, and Y ¹ and Y ² are respectively Independently an organic group with 6 to 40 carbon atoms having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and when m is 2 or more, a plurality of X ⁴ and Y ¹ may be the same or different ;

In formula (A2), R ³ to R ⁶ are each independently a hydrogen atom or a methyl group, X ⁶ to X ¹⁰ are each independently a hydrocarbon group with 6 to 20 carbon atoms having an alicyclic hydrocarbon group, and Y ³ and Y ⁴ are respectively Independently an organic group with 6 to 40 carbon atoms having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and when n is 2 or more, a plurality of X ⁷ , X ¹⁰ , Y ⁴ and R ⁶ may be used are the same or different, at least one of X ³ to X ⁵ and at least one of X ⁶ to X ¹⁰ are each independently a hydrocarbon group with 10 to 20 carbons having an adamantane ring. The curable resin composition according to claim 1, wherein at least one of Y ¹ to Y ² and at least one of Y ³ to Y ⁴ are independently the following (y1) ~ The basis represented by any of the following (y5):

In formula (y1)~formula (y4), the two * respectively represent the bonding position with the N forming the urethane bond in formula (A1) or formula (A2), and the E in formula (y5) Among the two *, one of them represents the bonding position with the N of the isocyanurate ring, and the other represents the bond with the N forming the urethane bond in formula (A1) or formula (A2) Location. The curable resin composition as described in item 1 or item 2 of the scope of patent application, which has a compound (B) represented by the following formula (B):

In the formula (B), R ¹⁰ is a hydrogen atom or a methyl group, and L is an organic group having an alicyclic hydrocarbon group having 6 to 20 carbon atoms. The curable resin composition according to claim 3, wherein the content ratio of the compound (A) to the compound (B) in the curable resin composition (mass of the compound (A) : the mass of compound (B)) is 1:99~99:1. The curable resin composition as described in claim 1 or claim 2, wherein the molecular weight of the compound (A) is 500-5000. The curable resin composition described in claim 3, wherein the molecular weight of the compound (B) is 180-600. A laminate comprising a substrate and a resin layer formed of the curable resin composition described in any one of claims 1 to 6. The laminate according to claim 7, wherein at least one of the base material and the resin layer contains a pigment. An optical filter comprising a laminate and a dielectric multilayer film as described in item 7 or 8 of the scope of application. A compound represented by the following formula (a):

In formula (a), Y" is an organic group with 6 to 40 carbons having an alicyclic hydrocarbon group, X" is independently a hydrocarbon group with 6 to 20 carbons having an alicyclic hydrocarbon group, and R" is independently a hydrogen atom or a methyl group, p is 2 or 3, a plurality of X" and R" can be the same or different, and at least one of the X" is an adamantanediyl group. The compound as described in item 10 of the scope of the patent application, wherein the Y" is a group represented by any one of the following (y1) to the following (y5):

In formula (y1)~formula (y4), the two * respectively represent the bonding position with the N constituting the urethane bond in formula (a), and in the two * of E in formula (y5), One of them represents a bonding position to N of the isocyanurate ring, and the other represents a bonding position to N constituting a urethane bond in formula (a).