JP7192796B2 - Curable resin composition, laminate, optical filter and compound - Google Patents

Description

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

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

Such laminates are required to have resin layers that are excellent in various performances such as scratch resistance, adhesion to the substrate or upper layer, and hardness (for example, Patent Documents 1 and 2).

Japanese Patent No. 6041372 JP 2017-47683 A

In recent years, the development of laminates in which base material/resin layer/inorganic film is formed has progressed, and lamination materials for obtaining such laminates have been studied. Laminates used for optical members and the like are required to have high adhesion at the interface of each layer after long-term storage in a high-temperature and high-humidity environment as one of the reliability evaluations. had room for further improvement to satisfy this requirement. In addition, if the surface hardness of the resin layer is low, it leads to the occurrence of scratches that cause defects. , it was 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, particularly adhesion to an inorganic film.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that the above problems can be solved by the following configuration example, and have completed the present invention.
A configuration example of the present invention is as follows.

式（Ａ１）中、Ｒ¹およびＲ²はそれぞれ独立して、水素原子またはメチル基であり、Ｘ³～Ｘ⁵はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～２０炭化水素基であり、Ｙ¹およびＹ²はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～４０の有機基であり、ｍは０～２０の整数であり、ｍが２以上の場合、複数のＸ⁴およびＹ¹はそれぞれ同一でも異なっていてもよく、

式（Ａ２）中、Ｒ³～Ｒ⁶はそれぞれ独立して、水素原子またはメチル基であり、Ｘ⁶～Ｘ¹⁰はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～２０炭化水素基であり、Ｙ³およびＹ⁴はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～４０の有機基であり、ｎは０～２０の整数であり、ｎが２以上の場合、複数のＸ⁷、Ｘ¹⁰、Ｙ⁴およびＲ⁶はそれぞれ同一でも異なっていてもよい。[1] A curable resin composition containing at least one compound (A) selected from compounds represented by the following formulas (A1) and (A2) and a polymerization initiator (D):

In formula (A1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, and X ³ to X ⁵ are each independently a carbon number of 6 to 20 having an alicyclic hydrocarbon group. a hydrogen group, Y ¹ and Y ² are each independently an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and m is 2 or more; , the 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, and X ⁶ to X ¹⁰ are each independently a carbon number of 6 to 20 having an alicyclic hydrocarbon group. a hydrogen group, Y ³ and Y ⁴ are each independently an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and n is 2 or more; In that case, multiple X ⁷ , X ¹⁰ , Y ⁴ and R ⁶ may be the same or different.

[2] 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 having 10 to 20 carbon atoms and having an adamantane ring. ] The curable resin composition according to .

式（ｙ１）～（ｙ４）中、２つの＊はそれぞれ式（Ａ１）または（Ａ２）中のウレタン結合を構成するＮとの結合位置を示し、式（ｙ５）中のＥにおける２つの＊のうち、一方は、イソシアヌル環のＮと結合する結合位置を示し、他方は、式（Ａ１）または（Ａ２）中のウレタン結合を構成するＮとの結合位置を示す。[3] At least one of Y ¹ to Y ² and at least one of Y ³ to Y ⁴ are each independently a group represented by any one of the following (y1) to (y5) , the curable resin composition according to [1] or [2]:

In formulas (y1) to (y4), two * indicate the bonding position with N constituting the urethane bond in formula (A1) or (A2), respectively, and two * in E in formula (y5) Of these, one represents the bonding position to N of the isocyanuric ring, and the other represents the bonding position to N constituting the urethane bond in formula (A1) or (A2).

式（Ｂ）中、Ｒ¹⁰は水素原子またはメチル基であり、Ｌは炭素数６～２０の脂環式炭化水素基を有する有機基である。[4] The curable resin composition according to any one of [1] to [3], containing a compound (B) represented by the following formula (B):

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

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

[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 compound (B) has a molecular weight of 180-600.

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

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

式（ａ）中、Ｙ"は脂環式炭化水素基を有する炭素数６～４０の有機基であり、Ｘ"は独立して、脂環式炭化水素基を有する炭素数６～２０の炭化水素基であり、Ｒ"は独立して、水素原子またはメチル基であり、ｐは２または３であり、複数のＸ"およびＲ"はそれぞれ同一でも異なっていてもよい。[11] A compound represented by the following formula (a):

In formula (a), Y″ is an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, and X″ is independently a hydrocarbon group having 6 to 20 carbon atoms and having an alicyclic hydrocarbon group. is a hydrogen group, R'' is independently 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）～（ｙ４）中、２つの＊はそれぞれ式（ａ）中のウレタン結合を構成するＮとの結合位置を示し、式（ｙ５）中のＥにおける２つの＊のうち、一方は、イソシアヌル環のＮと結合する結合位置を示し、他方は、式（ａ）中のウレタン結合を構成するＮとの結合位置を示す。[13] The compound according to [11] or [12], wherein Y″ is a group represented by any one of the following (y1) to (y5):

In formulas (y1) to (y4), each of the two * indicates the bonding position with N constituting the urethane bond in formula (a), and one of the two * in E in formula (y5) is , indicates the bonding position to N of the isocyanuric ring, and the other indicates the bonding position to N constituting the urethane bond in formula (a).

According to one embodiment of the present invention, it is possible to provide a curable resin composition that has high surface hardness, excellent adhesion, particularly adhesion to an inorganic film, and is capable of forming a resin layer with a small haze value. Moreover, according to one embodiment of the present invention, it is possible to provide a laminate and an optical filter that are excellent in wet heat resistance and have few defects.

<<Curable resin composition, compound>>
The curable resin composition according to one embodiment of the present invention (hereinafter also referred to as “this composition”) includes at least one compound (A ) and a polymerization initiator (D).
A compound according to one embodiment of the present invention (hereinafter also referred to as "compound (a)") is represented by the above formula (a).

Since the present composition contains the compound (A), and by using the compound (a), the surface hardness is high, the haze value is small, and the adhesion to the substrate and the inorganic film is excellent. Also, since the hygroscopicity can be suppressed, a resin layer having excellent adhesion to the inorganic film can be easily obtained.
In addition, since the resin layer easily recovers elasticity and exhibits toughness, it is expected to improve the scratch resistance of the formed film and improve the yield by suppressing microcracks during chip punching. It is conceivable that there is an effect of improving the adhesiveness to the substrate or the inorganic film due to interaction with the inorganic film of the bond and stress relaxation.
Conventional polyfunctional urethane compounds tend to absorb moisture, and their adhesion to substrates and inorganic films decreases when exposed to moist heat. The adhesion with the material and the inorganic film decreased. On the other hand, by using the compounds (A) and (a) having many alicyclic structures, it is possible to form a resin layer that is hydrophobic, resistant to curing shrinkage, and has high hardness, and can be used as a base during curing or during moist heat. It is possible to achieve both adhesion to materials and inorganic films and high hardness.
In addition, since compounds (A) and (a) having a urethane bond are easier to synthesize than compounds having an ester bond, the present invention regarding the compounds (A) and (a) is practical in material development. It can be said that it is expensive.
The present composition and compound (a) can be suitably used for optical members, particularly optical filters, and near-infrared cut filters.

<Compound (A)>
Compound (A) is at least one compound selected from compounds represented by formulas (A1) and (A2) below. The compound represented by the following formula (A1) is more preferable from the viewpoints that a resin layer having excellent adhesion to a substrate and adhesion to an inorganic film during wet heat and small curing shrinkage can be easily obtained. preferable.

［式（Ａ１）中、Ｒ¹およびＲ²はそれぞれ独立して、水素原子またはメチル基であり、Ｘ³～Ｘ⁵はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～２０炭化水素基であり、Ｙ¹およびＹ²はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～４０の有機基であり、ｍは０～２０の整数であり、ｍが２以上の場合、複数のＸ⁴およびＹ¹はそれぞれ同一でも異なっていてもよい。］

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

［式（Ａ２）中、Ｒ³～Ｒ⁶はそれぞれ独立して、水素原子またはメチル基であり、Ｘ⁶～Ｘ¹⁰はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～２０炭化水素基であり、Ｙ³およびＹ⁴はそれぞれ独立して、脂環式炭化水素基を有する炭素数６～４０の有機基であり、ｎは０～２０の整数であり、ｎが２以上の場合、複数のＸ⁷、Ｘ¹⁰、Ｙ⁴およびＲ⁶はそれぞれ同一でも異なっていてもよい。］

[In the formula (A2), R ³ to R ⁶ are each independently a hydrogen atom or a methyl group, and X ⁶ to X ¹⁰ are each independently a C 6-20 a hydrocarbon group, each of Y ³ and Y ⁴ is independently an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and n is 2 or more; , the plurality of X ⁷ , X ¹⁰ , Y ⁴ and R ⁶ may 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 an alicyclic hydrocarbon group.
The number of carbon atoms in 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.

The alicyclic hydrocarbon groups contained in X ³ to X ¹⁰ include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, a cyclopropenediyl group, cyclobutenediyl, cyclopentenediyl, cyclohexenediyl, cycloheptenediyl, cyclooctenediyl, bicyclo[2.2.1]heptanediyl, trimethylbicyclo[2.2.1]heptanediyl, bicyclo[2 .2.2]octanediyl group, adamantanediyl group, bicyclo[2.2.1]heptenediyl group, bicyclo[2.2.2]octenediyl group, cyclohexanedimethyl group, tricyclodecanedimethyl group, pentacyclodecanedimethyl group etc.
Among these, a cyclohexanedimethyl group and an adamantanediyl group are preferable, and even if the concentration of cross-linking groups is low, a resin layer with high hardness can be easily obtained, and a resin layer with excellent balance between high hardness and low curing shrinkage can be easily obtained. An adamantanediyl group is particularly preferred because it can be obtained. That is, at least one of X ³ to X ⁵ and at least one of X ⁶ to X ¹⁰ , preferably X ³ to X ¹⁰ are each independently a hydrocarbon having 10 to 20 carbon atoms and having an adamantane ring. is preferred, and an adamantanediyl group is particularly preferred.

The number of carbon atoms in the organic groups 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 groups contained in Y ¹ to Y ⁴ include the same groups as the alicyclic hydrocarbon groups contained in X ³ to X ¹⁰ .

At least one of Y ¹ to Y ² from the standpoint of being able to easily obtain a resin layer having excellent adhesion to the base material and the inorganic film, and particularly having excellent adhesion to the inorganic film even under wet heat. and at least one of Y ³ to Y ⁴ , preferably Y ¹ to Y ⁴ is each independently a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, or an alicyclic carbonized It is preferably an organic group having 15 to 40 carbon atoms containing a hydrogen group and an isocyanurate ring, more preferably a group containing a cyclohexane ring or a norbornane ring, and any one of the following (y1) to (y5) more preferably a group represented by

In formulas (y1) to (y4), two * indicate the bonding position with N constituting the urethane bond in formula (A1) or (A2), respectively, and two * in E in formula (y5) Of these, one represents the bonding position to N of the isocyanuric ring, and the other represents the bonding position to N constituting the urethane bond in formula (A1) or (A2).
The position of —CH ₂ —* in formula (y3) is preferably the meta or para position of *—CH ₂ —Cy (Cy is a cyclohexane ring).

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

The compound (A) has a high surface hardness, a small haze value, and can easily obtain a resin layer having excellent adhesion to the substrate and the inorganic film. It is preferably a compound represented by

In formula (a), Y″ is an organic group having 6 to 40 carbon atoms having an alicyclic hydrocarbon group, and includes 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, and includes 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; 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 to 5000, because it has a high surface hardness, a small haze value, and can easily obtain a resin layer having excellent adhesion to the substrate and the inorganic film. More preferably 500-2000.

The method for synthesizing the compound (A) is not particularly limited, and it can be synthesized by a conventionally known method. is preferably reacted. In addition, a compound represented by the following formula (a3) may be used in this reaction.

（式（ａ１）中、ＲおよびＸ¹はそれぞれ、前記Ｒ¹およびＸ³と同義である。）

(In formula (a1), R and X ¹ are synonymous with R ¹ and X ³ above, respectively.)

（式（ａ２）中、Ｙは前記Ｙ¹と同義であり、ｑは２または３である。）

(In formula (a2), Y has the same definition as Y ¹ above, and q is 2 or 3.)

（式（ａ３）中、Ｘ²は前記Ｘ³と同義である。）

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

The reaction is preferably carried out in the presence of a catalyst, solvent, etc. conventionally used for the reaction between hydroxy groups and isocyanate groups.
Moreover, the reaction is preferably carried out under heating, and the reaction temperature is preferably 50 to 90°C.

The content of the compound (A) in the present composition is preferable from the viewpoint that a resin layer having a high surface hardness, a small haze value, and excellent adhesion to the substrate and the inorganic film can be easily obtained. is 1% by mass or more, more preferably 10% by mass or more, particularly preferably 30% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

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

As the polymerization initiator (D), a known photopolymerization initiator can be used, and if necessary, a thermal polymerization initiator may be used in combination.

Examples of the polymerization initiator (D) include photopolymerization initiators described in JP-A-2008-276194 and JP-A-2003-241372.

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-phenylpropan-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-propionyl)-benzyl]phenyl}-2-methyl-propane -1-one and other α-hydroxyalkylphenones; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl ) butan-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4- morpholinophenyl)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)butanone and 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)butanone dialkoxyacetophenones such as 2,2-dimethoxy-1,2-diphenylethan-1-one and 2,2-diethoxyacetophenone.

Acylphosphine oxide compounds include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Examples of biimidazole compounds include 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'-tetraphenyl-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)-6-(4-methoxy naphthyl)-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)ethenyl]-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2 -methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine. be done.

Examples of oxime ester compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropan-1-one-2-imine , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]ethan-1-imine and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl} -9H-carbazol-3-yl]ethan-1-imine.

Benzoin compounds include, for example, 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′-methyldiphenylsulfide, 3,3′,4,4′-bis(diethylamino)benzophenone, 4, 4'-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

Among these, acylphosphine oxide compounds and alkylphenone compounds are preferable, and alkylphenone compounds are more preferable, from the viewpoint that a resin layer having excellent curability and transparency can be easily obtained.

The content of the polymerization initiator (D) in the composition is such that a resin layer having high surface hardness, a small haze value, and excellent adhesion to the substrate and the inorganic film can be easily obtained. , preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, preferably 15 parts by mass or less, relative to a total of 100 parts by mass of the compound (A) and the following compounds (B) and (C); More preferably, it is 8 parts by mass or less.

<Compound (B)>
The present composition is a compound (B ) may contain.
The compound (B) contained in the present composition may be one kind, or two or more kinds.

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 the hydrogen atom of the alicyclic structure is a group or atom other than a (meth)acryloyl group, such as a hydroxy group, a hydrocarbon group or a halogen atom It may be a group substituted with.
Examples of the alicyclic hydrocarbon group for L include the same groups as those exemplified for X ³ .
The number of carbon atoms in the organic group in L is preferably 8 or more, more preferably 10 or more, and preferably 15 or less, more preferably 12 or less.

Alicyclic hydrocarbon groups contained in L include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl cyclooctenyl group, bicyclo[2.2.1]heptanyl group, bicyclo[2.2.2]octanyl group, tricyclo[3.3.1.1 ^3,7 ]decanyl group, bicyclo[2.2.1 ]heptenyl group, bicyclo[2.2.2]octenyl group, and the like. Among these, a tricyclo[3.3.1.1 ^3,7 ]decanyl group is particularly preferable in that a resin layer having an excellent balance between high hardness and low cure shrinkage can be easily obtained.

The compound (B) is not particularly limited, but cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, di Cyclopentanyl (meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, isobornyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl -2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate, 3-phenyl carbamoyl-1-adamantyl (meth)acrylate and the like.

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

When the present composition contains the compound (B), the content of the compound (B) in the present composition is such that the resin layer has a high surface hardness, a small haze value, and excellent adhesion to the substrate and the inorganic film. is preferably from 1 to 50% by mass, more preferably from 1 to 30% by mass.
Further, the content ratio of the compound (A) and the compound (B) in the present composition (mass of compound (A):mass of compound (B)) is preferably 1 for the same reason as described above. :99-99:1, more preferably 80:20-50:50.

<Other ingredients>
The present composition may contain conventionally known components other than the compounds (A) and (B) and the polymerization initiator (D).
The other components include, for example, polyfunctional (meth)acrylic monomers other than compounds (A) and (B) (hereinafter also referred to as "compound (C)"), monofunctional (meth)acrylates other than compound (B) Acrylic monomers, solvents, antioxidants, ultraviolet absorbers, dyes, antireflection agents, hard coating agents, antistatic agents, metal complex compounds, leveling agents, antifoaming agents, and coupling agents.
Each of these other components may be one kind, or two or more kinds.

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. Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (Meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like. In addition, tricyclodecanedimethanol di(meth)acrylate, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, isocyanurate skeleton-containing di- or tri(meth)acrylate, bisphenol A skeleton-containing di(meth) acrylates and the like.

The content of the compound (C) in the present composition is preferable from the viewpoint that a resin layer having high surface hardness, a small haze value, and excellent adhesion to the substrate and the inorganic film can be easily obtained. is 5% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less.
Further, the ratio of compound (C) to 100% by mass of the compounds (A) to (C) in the present composition is preferably 10% by mass or more, more preferably 20% by mass, for the same reason as described above. % or more, preferably 55% by mass or less, more preferably 45% by mass or less.

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

Examples of such near-infrared absorbing dyes include squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, dithiol-based compounds, diimmonium-based compounds, porphyrin-based compounds, and croconium-based compounds.

The absorption maximum wavelength of the near-infrared absorbing dye is preferably 600 nm or longer, more preferably 620 nm or longer, particularly preferably 650 nm or longer, and preferably 800 nm or shorter, more preferably 760 nm or shorter, and particularly preferably 740 nm or shorter. When the absorption maximum wavelength is in such a wavelength range, both sufficient near-infrared absorption characteristics and visible light transmittance can be achieved. Squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, and croconium-based compounds are particularly preferred as near-infrared absorbing dyes that satisfy such absorption characteristics.

The content of the dye in the present composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more from the viewpoint of excellent visible light transmission and ability to absorb light of a desired wavelength. Yes, preferably 20% by mass or less, more preferably 10% by mass or less.

≪Laminate≫
The resin layer formed from the present composition may be used alone as a resin film, but is preferably used as a laminate with a substrate.
Each of the base material and the resin layer contained in the laminate may be one layer (sheet), or may be two layers (sheet) or more. Further, the resin layer may be present only on one side of the substrate, or may be present on both sides.

The thickness of the resin layer (one layer) may be appropriately selected according to the desired application, preferably 0.1 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.7 μm or more. is 20 μm or less, more preferably 10 μm or less, particularly preferably 5 μm or less.

The substrate is preferably a transparent plate having an average transmittance of 85% or more for light in the wavelength region of 400 to 700 nm, and is preferably made of a material that transmits visible light. , resin substrates, and glass substrates. Among these, the resin base material is preferable because it is excellent in workability and in adhesion to the resin layer.

Examples of resin substrates include polycarbonate resins, acrylic resins, polyester resins, polyether resins, polyolefin resins, epoxy resins, alkyd resins, melamine resins, polyurethane resins, polyimide resins, and polyamides. base resins, norbornene-based resins, and the like.

Examples of glass substrates include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, chemically strengthened glass, physically strengthened glass, copper-containing phosphate glass, copper-containing fluorophosphate glass, and the like. A base material is mentioned.

At least one of the substrate and the resin layer preferably contains a dye. 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 is also within the same range as the content of the dye in the present composition.

The thickness of these substrates may be appropriately selected according to the desired application, preferably 10 μm or more, more preferably 20 μm or more, particularly preferably 25 μm or more, preferably 100 mm or less, more preferably 50 mm or less, Particularly preferably, it is 10 mm or less.

The method for producing the laminate is not particularly limited, and after forming a resin layer (film) from the present composition on a support, the support is peeled off, and the obtained resin layer (film) is used as a substrate. Although it may be laminated, it is preferable to form a laminate by coating the composition on a substrate and curing it.

As the coating method, a known method 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, blade coating method, roller coating method, curtain coating method, slit die coater method, gravure coater method, slit reverse A coater method, a microgravure method, a comma coater method, a screen printing method, and a flexographic printing method can be mentioned.

After applying the composition onto a substrate, for example, the applied composition may be dried before curing as described below.

The curing method is not particularly limited, but includes a method of curing by heating, a method of irradiating with light, and the like, and a method of irradiating with light is particularly preferable.
Light with a wavelength of 200 to 500 nm is preferable for the light to be irradiated. Curing may be accelerated by heating during or after light irradiation.
The temperature condition for light irradiation is preferably 0° C. or higher, more preferably 10° C. or higher, and preferably 100° C. or lower, more preferably 60° C. or lower.
The atmosphere in which the light is irradiated may be the atmosphere, but an inert gas atmosphere is preferable from the viewpoint of reducing the influence of oxygen inhibition. Nitrogen, argon, etc. are mentioned as an inert gas.
The irradiation amount of light (integrated light amount) can be selected, for example, from a range of about 50 to 20000 mJ/cm ² , and is preferably 100 mJ/cm ² or more, more preferably 200 mJ/cm ² or more in a nitrogen atmosphere. Yes, preferably 10000 mJ/cm ² or less, more preferably 8000 mJ/cm ² or less.

The laminate may further have an inorganic film. The inorganic film may be formed on the base material, but is preferably formed on the resin layer from the viewpoint of exhibiting the effect of providing the resin layer more.
Examples of the inorganic film include dielectric multilayer films, conductive films such as ITO films, films of metals such as gold, platinum and copper, their oxides, and alloys containing these metals.

The laminate is a display device such as a touch panel, a membrane switch, a surface material such as a keypad, an electrode substrate of a liquid crystal cell constituting a liquid crystal display element, a retardation film, a film with a transparent electrode for a touch panel, a film for a near-infrared cut filter. It can be suitably used as an optical film such as a near-infrared cut filter (film for).

≪Optical filter≫
An optical filter according to an embodiment of the present invention preferably has the laminate and a dielectric multilayer film. The dielectric multilayer film may be formed directly on the base material, but is preferably formed on the resin layer in order to exhibit the effect of providing the resin layer more effectively.
Although the optical filter is not particularly limited, a near-infrared cut filter is preferred.

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

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

A material having a refractive index of 1.7 or more can be used as a material constituting the high refractive index material layer, and a material having a refractive index ranging from 1.7 to 2.5 is usually 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. and/or those containing a small amount (for example, 0 to 10% relative to the main component) of cerium oxide or the like.

A material having a refractive index of 1.6 or less can be used as a material constituting the low refractive index material layer, and a material having a refractive index ranging from 1.2 to 1.6 is usually selected. Such materials include, for example, silica, alumina, lanthanum fluoride, magnesium fluoride and sodium aluminum hexafluoride.

The method of stacking the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film is formed by stacking these material layers. For example, a dielectric layer in which high refractive index material layers and low refractive index material layers are alternately laminated directly on the laminate by a CVD method, a sputtering method, a vacuum deposition method, an ion-assisted deposition method, an ion plating method, or the like. A body multilayer film can be formed.
At this time, the surface of the resin layer may be surface-treated by corona treatment, plasma treatment, or the like.

The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ, where λ (nm) is the wavelength to be blocked. When the thickness of each layer of the high refractive index material layer and the low refractive index material layer is in this range, the optical film thickness calculated by the product (n×d) of the refractive index (n) and the film thickness (d) However, the value is almost the same as λ/4, and there is a tendency to easily control the blocking and transmission of specific wavelengths from 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 layers or more, more preferably 10 layers or more, and preferably 60 layers or less, as a whole optical filter. More preferably, it is 50 layers or less.

In the case where the optical filter warps when the dielectric multilayer film is formed, in order to solve this problem, the dielectric multilayer film is formed on both sides of the laminate, or the dielectric multilayer film is formed on both sides of the laminate. A method of irradiating the surface on which the film is formed with electromagnetic waves such as ultraviolet rays may be performed. When the electromagnetic wave is applied, the irradiation may be performed during the formation of the dielectric multilayer film, or may be performed separately after the formation.

In the optical filter, the surface opposite to the surface provided with the dielectric multilayer film of the laminate, or the surface of the dielectric multilayer film provided with the laminate, within the range that does not impair the effects of the present invention. A functional film such as an antireflection film, hard coat film, or antistatic film is applied to the opposite side for the purpose of improving the surface hardness of the base material or dielectric multilayer film, improving chemical resistance, antistatic, and scratch removal. can be provided as appropriate.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples.

[Measurement of molecular weight]
The molecular weights of the compounds synthesized in the following synthesis examples were measured by gel permeation chromatography (GPC) using Tosoh Corporation GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) under the following measurement conditions. .
GPC measurement conditions:
・Elution solvent: tetrahydrofuran ・Flow rate: 1.0 mL/min ・Sample concentration: 1.0% by mass
・Sample injection volume: 100 μL
・Column temperature: 40°C
・Detector: Differential refractometer ・Standard substance: Monodisperse polystyrene

[Synthesis Example 1] Synthesis of Compound (A-1) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol, 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), 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 additionally added and the reaction was continued at 70°C. After confirming that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, the reaction was terminated.
Urethane acrylate compound (A-1) was obtained by purifying the reaction mixture by silica gel column chromatography using ethyl acetate/hexane as an eluent (molecular weight: 667).

A ¹ H-NMR spectrum of 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 structure of the obtained compound (A-1) was represented by the following formula (A-1).
¹ H-NMR (DMSO-d ₆ ); δ 1.04 (m, 22H), 1.51 (m, 1H), 2.02 (m, 20H), 2.26 (d, 1H), 2.46 (d, 1H), 3.79 (m, 1H), 5.86 (d, 2H), 6.06 (t, 2H), 6.21 (d, 2H), 6.82 (s, 1H) , 6.93(s, 1H)

[Synthesis Example 2] Synthesis of Compound (A-2) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol, 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, 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 additionally added and the reaction was continued at 70°C. After confirming that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, the reaction was terminated.
By purifying the reaction mixture by silica gel column chromatography using ethyl acetate/hexane as an eluent, a urethane acrylate compound (A-2) was obtained (molecular weight: 651).

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

[Synthesis Example 3] Synthesis of compound (A-3) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol, 3- Hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222) 27.047 g (0.12 mol), and 1,3-hydrogenated xylylene diisocyanate (manufactured by Active Material Chemical Co., Ltd., molecular weight : 194) was dissolved in 19 g of MEK, and after adding 0.405 g of dioctyltin dilaurate, 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 additionally added and the reaction was continued at 70°C. After confirming that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, the reaction was terminated.
By purifying the reaction mixture by silica gel column chromatography using ethyl acetate/hexane as an eluent, a urethane acrylate compound (A-3) was obtained (molecular weight: 639).

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

[Synthesis Example 4] Synthesis of compound (A-4) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol, 3- Hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222) 27.047 g (0.12 mol), and 4,4′-methylenebis(cyclohexyl isocyanate) (manufactured 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 additionally added and the reaction was continued at 70°C. After confirming that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, the reaction was terminated.
By purifying the reaction mixture by silica gel column chromatography using ethyl acetate/hexane as an eluent, a urethane acrylate compound (A-4) was obtained (molecular weight: 707).

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

[Synthesis Example 5] Synthesis of Compound (A-5) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol, 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 the 3-hydroxy-1-adamantyl acrylate was dissolved and the solution became transparent, 1,4-cyclohexanedimethanol monoacrylate (manufactured by Nippon Kasei Co., Ltd., molecular weight: 198) 23.8 g (0. 12 mol) was added and the reaction was continued at 70°C. After confirming that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, the reaction was terminated.
By purifying the reaction mixture by silica gel column chromatography using ethyl acetate/hexane as an eluent, a urethane acrylate compound (A-5) was obtained (molecular weight: 643).

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

[Synthesis Example 6] Synthesis of Compound (A-6) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 0.0194 g of 2,6-di-t-butyl-4-cresol, 3- Hydroxy-1-adamantyl acrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight: 222) 27.047 g (0.12 mol), and an isocyanurate of isophorone diisocyanate (trade name: VESTANAT T1890/100, manufactured by Evonik, NCO value: 17.3 wt%) was dissolved in 19 g of MEK, and after adding 0.405 g of dioctyltin dilaurate, the temperature was raised to 70°C while stirring. After confirming that the solution became homogeneous and transparent, 27.047 g of 3-hydroxy-1-adamantyl acrylate and 29.0 g of the isocyanurate of isophorone diisocyanate were added, and the reaction was continued at 70°C. After confirming that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, the reaction was terminated.
By purifying the reaction mixture by silica gel column chromatography using ethyl acetate/hexane as an eluent, a urethane acrylate compound (A-6) was obtained (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. It was confirmed that it was a structure represented by
¹ H-NMR (DMSO-d ₆ ); δ1.04-2.02 (m, 87H), 2.26 (m, 3H), 2.46 (m, 3H), 3.79 (m, 3H) , δ5.86 (m, 3H), 6.06 (m, 3H), 6.21 (m, 3H), 6.99 (m, 3H)

[Example 1] Preparation of curable resin composition solution To a 20 mL sample tube, add 3.0 g of compound (A-1) and 0.09 g of compound (D-1), dilute with 10 g of MEK, and obtain a curable resin. A composition was prepared.

[Examples 2 to 11 and Comparative Examples 1 to 4] Preparation of curable resin composition Compositions were prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were used in the proportions shown in Table 1. was prepared. The numerical values shown in the column of composition in Table 1 are the proportions (parts by mass) of the compounds used when the total of the compounds (A) to (C) is 100 parts by mass.
Details of compounds (B-1) to (B-4), compounds (C-1) to (C-3) and compounds (D-1) to (D-3) described in Table 1 are shown in Table 2. .

[Haze measurement]
The curable resin composition obtained in the above examples and comparative examples was applied to a substrate (norbornene resin film [manufactured by JSR Corporation, Arton FEKE100, film thickness 100 μm]), and the thickness of the resulting resin layer was 3 μm. It was applied so as to be as thick as possible, and cured by irradiating with ultraviolet rays in a nitrogen atmosphere to obtain a base material with a resin layer. Using the obtained resin layer-attached substrate, the haze of the resin layer-attached substrate is measured using a haze meter (trade name: Haze Guard II, manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS K 7136. values were measured. A haze value of 0.1 or less was judged to be good. Table 1 shows the results.

[Pencil hardness test]
The hardness of the resin layer in the base material with the resin layer obtained in the same manner as the haze measurement was measured by a pencil hardness test according to the method described in JIS K 5600-5-4.
Specifically, after conditioning the substrate with the resin layer for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, the resin layer surface was scratched with a load of 4.9 N using a test pencil, and 5 samples were obtained. Among them, the highest pencil hardness at which 3 or more specimens were not scratched was used as an evaluation value. When the pencil hardness was B or higher, it was judged to be good. Table 1 shows the results.

[Moisture and heat resistance (adhesion) test]
A substrate with a resin layer was obtained in the same manner as in the haze measurement. The following inorganic film (dielectric multilayer film, ITO sputter film, or gold deposition film) was formed on the resin layer of the obtained base material with a resin layer. The obtained substrate with an inorganic film was placed in a constant temperature and humidity bath under conditions of 85° C. and 85% RH for 1000 hours. After that, the adhesion between the inorganic film and the resin layer was evaluated as follows. Table 1 shows the results.
Dielectric multilayer film: A film in which SiO ₂ (thickness: 10 to 100 nm) layers and TiO ₂ (thickness: 10 to 120 nm) layers are alternately laminated by a conventionally known vapor deposition method (number of layers: 28, total thickness 3 μm)
・ITO sputtered film: A film obtained by sputtering ITO by a conventionally known method (thickness: 500 nm)
- Gold deposition film: A film deposited with gold by a conventionally known method (thickness: 500 nm)

Using a cutter knife, the surface of the inorganic film was cut in a grid pattern at intervals of 1 mm so that 11 vertical and 11 horizontal cuts reached the resin layer, and a total of 100 squares were cut. After attaching an adhesive tape (cellophane tape (registered trademark), manufactured by Nichiban Co., Ltd., trade name: CT24) to the surface of the incision, the adhesive tape was peeled off, and the number of inorganic films remaining on the substrate was evaluated. did. Good adhesion was determined when 90 or more of the inorganic films remained on the substrate side after the tape was peeled off, out of 100 squares.

Claims (8)

a base material;
A resin layer formed from a curable resin composition containing at least one compound (A) selected from compounds represented by the following formulas (A1) and (A2) and a polymerization initiator (D) Laminate with:

In formula (A1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, and X ³ to X ⁵ are each independently a carbon number of 6 to 20 having an alicyclic hydrocarbon group. a hydrogen group, Y ¹ and Y ² are each independently an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and m is 2 or more; , the 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, and X ⁶ to X ¹⁰ are each independently a carbon number of 6 to 20 having an alicyclic hydrocarbon group. a hydrogen group, Y ³ and Y ⁴ are each independently an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and n is 2 or more; , the plurality of X ⁷ , X ¹⁰ , Y ⁴ and R ⁶ may be 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 having an adamantane ring and having 10 to 20 carbon atoms. At least one of Y ¹ to Y ² is each independently a group represented by any one of the following (y1) to (y4) , and at least one of Y ³ to Y ⁴ is the following The laminate according to claim 1, which is a group represented by ( y5 ) :

In formulas (y1) to (y4), two * indicate the bonding position with N constituting the urethane bond in formula (A1) or (A2), respectively, and two * in E in formula (y5) Of these, one represents the bonding position to N of the isocyanuric ring, and the other represents the bonding position to N constituting the urethane bond in formula (A1) or (A2). The laminate according to any one of claims 1 and 2, wherein the curable resin composition contains a compound (B) represented by the following formula (B):

In formula (B), R ¹⁰ is a hydrogen atom or a methyl group, and L is an organic group having an alicyclic hydrocarbon group with 6 to 20 carbon atoms. The content ratio of the compound (A) to the compound (B) in the curable resin composition (mass of compound (A):mass of compound (B)) is 1:99 to 99:1. 4. The laminate according to claim 3. The laminate according to any one of claims 1 to 4, wherein the compound (A) has a molecular weight of 500 to 5,000. 5. The laminate according to claim 3, wherein the compound (B) has a molecular weight of 180-600. The laminate according to any one of claims 1 to 6, wherein at least one of the base material and the resin layer contains a dye. An optical filter comprising the laminate according to any one of claims 1 to 7 and a dielectric multilayer film.