KR20180133312A - Resin, curable composition, cured product, method for producing cured product, and method for producing microlens - Google Patents

Abstract

The present invention provides: a thermosetting resin which is cured well regardless of the type of the substrate when curing is carried out on a substrate, and capable of forming a cured product in which a dimensional change occurs or light transmittance is lowered or is hardly lowered when used under a high temperature environment; a curable composition comprising the resin; a cured product formed by curing the resin; a method for producing the cured product using the resin; and a method for producing microlens using the resin. The resin containing a structural unit of a specific structure having a block isocyanate group, a structural unit of a specific structure having a hydroxyl group, and a structural unit of a specific structure having a hydrocarbon group containing two or more benzene rings by combination of the structural units is used.

Description

Technical Field The present invention relates to a resin, a curable composition, a cured product, a method for producing a cured product, and a method for manufacturing a micro-

The present invention relates to a resin composition comprising a resin including structural units of a specific structure, a curable composition containing the resin, a cured product obtained by curing the resin, a method of producing a cured product using the resin, To a method of manufacturing a microlens.

BACKGROUND ART Heretofore, a curable resin material has been used in various applications. By selecting the partial structure of the curable resin or the kind of the additive to be used together with the curable resin, a cured product exhibiting various properties is formed using the curable resin.

For example, in a cured product used for forming a planarizing film or a microlens in an image display element or an optical element, it is desired that the cured product has good transparency and solvent resistance and a high refractive index.

As the curable resin used for forming the planarizing film or the microlens, for example, a copolymer containing a structural unit containing an epoxy group and a structural unit containing a biphenyl group is known (see Patent Document 1). )

International Publication No. 2015/122109

However, when a cured film is formed using a resin having an epoxy group as described in Patent Document 1, it is difficult to form a cured film sufficiently cured depending on the type of the substrate, or when the cured film is used under a high- The dimension of the thickness may fluctuate or the light transmittance of the transmissive film may decrease.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for curing a substrate, which is cured well regardless of the type of the substrate and which causes dimensional changes when used under a high temperature environment, A curable composition containing the resin, a cured product obtained by curing the resin, a method of producing a cured product using the resin, and a method of producing a cured product using the above- It is an object of the present invention to provide a method of manufacturing a microlens using a resin.

The present inventors have found that by using a resin containing a structural unit of a specific structure having a block isocyanate group, a structural unit of a specific structure having a hydroxyl group, and a structural unit of a specific structure having a hydrocarbon group containing two or more benzene rings in combination, The present invention has been accomplished on the basis of these findings.

The first aspect of the present invention is a resin comprising a structural unit represented by the following formula (a1), a structural unit represented by the following formula (a2), and a structural unit represented by the following formula (a3)

[Chemical Formula 1]

(Formula (a1), (a2), and (a3) of, R ¹ is, and each is independently a hydrogen atom, or a methyl group, R ² is a single bond, or carbon atoms, one alkyl group of more than five or less, R ³ is a block isocyanate group, R ⁴ is a divalent hydrocarbon group, R ⁵ is a single bond or a divalent linking group, and R ⁶ is an organic group containing two or more benzene rings.)

A second aspect of the present invention is a curable composition comprising a resin and a solvent according to the first aspect.

A third aspect of the present invention is a cured product obtained by curing a resin according to the first aspect.

In a fourth aspect of the present invention,

A molding step of molding the resin according to the first aspect into a predetermined shape,

A curing step of curing the molded resin by heating

Based on the total weight of the cured product.

In a fifth aspect of the present invention,

A lens material layer forming step of forming a lens material layer by crosslinking a resin layer obtained by applying a composition containing a resin according to the first aspect on a substrate by heating;

A lens pattern forming step of forming a lens pattern by forming a resist pattern on a lens material layer and then reflowing the resist pattern by heating,

A shape transfer process for dry-etching the lens material layer and the lens pattern using the lens pattern as a mask and transferring the shape of the lens pattern to the lens material layer

The method of manufacturing a microlens according to claim 1,

According to the present invention, there is provided a curable resin composition comprising a curable resin capable of forming a cured product having good curability and having a high refractive index, a curable composition containing the resin, a cured product obtained by curing the resin, A method of producing water, and a method of manufacturing a microlens using the above-mentioned resin can be provided.

«Resin»

The resin includes a structural unit represented by the following formula (a1), a structural unit represented by the following formula (a2), and a structural unit represented by the following formula (a3).

(2)

(Formula (a1), (a2), and (a3) of, R ¹ is, and each is independently a hydrogen atom, or a methyl group, R ² is a single bond, or carbon atoms, one alkyl group of more than five or less, R ³ is a block isocyanate group, R ⁴ is a divalent hydrocarbon group, R ⁵ is a single bond or a divalent linking group, and R ⁶ is a hydrocarbon group containing two or more benzene rings.)

Hereinafter, the structural unit represented by formula (a1) is also referred to as "structural unit A1", the structural unit represented by formula (a2) is also referred to as "structural unit A2", and the structural unit represented by formula (a3) Is also referred to as " structural unit A3 ".

The structural unit A1 represented by the formula (a1) has a block isocyanate group as R ³ . The block isocyanate group means a group in which an isocyanate group is blocked by a heat-labile protecting group.

Therefore, when the above-mentioned resin having the structural unit A1 is heated, the protecting group in the block isocyanate group is eliminated, and an active isocyanate group is produced.

The isocyanate group generated by heating readily reacts with a functional group having an active hydrogen. Here, the structural unit A2 represented by the formula (a2) has a hydroxyl group which is a functional group having an active hydrogen group. Therefore, when the above-mentioned resin is heated, an isocyanate group which is active in the structural unit A1 is produced. The isocyanate group (-NCO) reacts with the hydroxyl group in the structural unit A2, and crosslinking by the urethane bond (-NH-CO-O-) proceeds to form a cured product.

The structural unit represented by the above formula (a3) has, as R ⁶ , a hydrocarbon group containing two or more benzene rings. Here, the hydrocarbon group containing two or more benzene rings contributes to the high refractive index of the cured product.

Therefore, when the resin is heated, the curing of the resin proceeds satisfactorily, and as a result, a cured product having a high refractive index is formed.

Hereinafter, essential or optional structural units contained in the resin, a method for producing the resin, and the like will be described.

<Structural unit A1>

The resin includes the structural unit A1 having a block isocyanate group, as described above. The resin may contain two or more kinds of structural units A1 in combination.

The structural unit A1 is a structural unit represented by the above-mentioned formula (a1). In formula (a1), R ¹ is a hydrogen atom or a methyl group.

In formula (a1), R ² is a single bond or an alkylene group having 1 to 5 carbon atoms. The alkylene group may be linear or branched, and preferably is linear. Specific examples of the alkylene group as R ² include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, A 1,4-diyl group, and a pentane-1,5-diyl group.

Among these groups, a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group and a pentane- , Ethane-1,2-diyl group, and propane-1,3-diyl group are more preferable, and ethane-1,2-diyl group is particularly preferable.

In the formula (a1), R ³ is a block isocyanate group. As described above, the block isocyanate group means a group in which an isocyanate group is blocked by a heat-labile protecting group.

Such a heat-labile protecting group is formed by reacting an isocyanate group with a blocking agent to give a protecting group.

Examples of such blocking agents include, for example, hydroxyl group-containing compounds other than alcohol compounds, phenol compounds, alcohol compounds and phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, Compounds, urea compounds, acid amide compounds (lactam compounds), acid imide compounds, triazole compounds, pyrazole compounds, pyrrole compounds, mercapane compounds, and bisulfate.

Examples of the alcoholic compound include alcohols such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, 2-ethylhexyl alcohol, 1-octanol, 2-octanol, cyclohexyl alcohol, ethylene glycol, , 2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2- (hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-2-ethoxyethanol, n- (2-ethoxyethoxy) ethanol, 2- (4-ethoxybutoxy) ethanol, 2- (2-butoxyethoxy) ethanol, N, Butyl-2-hydroxyacetamide, N-morpholine ethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidinethanol, 2-hydroxymethylpyridine, furfuryl alcohol , 12-hydroxystearic acid, and 2-hydroxyethyl methacrylate.

Examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, Phenol, 4-n-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-n-butylphenol, 3- butylphenol, 2-n-hexylphenol, 3-n-butylphenol, 3-tert-butylphenol, 2- (2-ethylhexyl) phenol, 4-n-hexylphenol, 2- (2-ethylhexyl) phenol, 3- 2-n-nonylphenol, 3-n-nonylphenol, 4-n-nonylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5 -Dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3-di-n-propylphenol, di-n-propylphenol, 3,5-di-n-propylphenol, 2,3-diisopropyl Diisopropylphenol, 2,5-diisopropylphenol, 2,6-diisopropylphenol, 3,4-diisopropylphenol, 3,5-diisopropylphenol, 3-iso 2-methylphenol, 4-isopropyl-2-methylphenol, 5-isopropyl-2-methylphenol, 6- Isopropyl-4-methylphenol, 3-isopropyl-4-methylphenol, 5-isopropyl-3-methylphenol, Butylphenol, 2,5-di-n-butylphenol, 2,6-di-n-butylphenol, Di-n-butylphenol, 3,5-di-n-butylphenol, 2,3-di-sec-butylphenol, 2,4- Di-sec-butylphenol, 2,6-di-sec-butylphenol, 3,4-di-sec-butylphenol, 3,5- Di-tert-butylphenol, 2,5-ditert-butylphenol, 2,6-ditert-butylphenol, 3,4 ditert-butylphenol, 3,5- Phenol, 2,3-di-n-octylphenol, 2,4-di-n-octylphenol, 2,5-di-n-octylphenol, 2,6- Phenol, 3,5-di-n-octylphenol, 2,3-di-2-ethylhexylphenol, 2,4-di-2-ethylhexylphenol, 2,5- 2-ethylhexylphenol, 3,4-di-2-ethylhexylphenol, 3,5-di-2-ethylhexylphenol, 2,3-dinonylphenol, Di-n-nonylphenol, 2,6-dinonylphenol, 3,4-dinonylphenol, 3,5-dinonylphenol, 2-nitrophenol, 3- 2-chlorophenol, 4-chlorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, Phenol, styrenated phenol (mono-, di- or tri-substituent of phenol by the? -Methylbenzyl group), methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl 4-hydroxybenzoate , 4 - [(dimethylamino) methyl] phenol, 4 - [(dimethylamino) methyl] There may be mentioned bis (4-hydroxyphenyl) acetic acid, 2-hydroxy-pyridine, 2-hydroxyquinoline, 8-hydroxyquinoline and 2-chloro-3-pyrimidin dinol.

Examples of the hydroxyl group-containing compound other than the alcohol compound and the phenol compound include, for example, N-hydroxysuccinimide and triphenylsilanol.

Examples of the active methylene-based compound include meldrum acid, dialkyl malonate (e.g., dimethyl malonate, diethyl malonate, di-n-butyl malonate, di tert- butyl malonate, di- Butyl malonate, ethyl sec-butyl malonate, tert-butyl methyl malonate, tert-butyl ethyl malonate, diethyl methyl malonate, dibenzyl malonate, (Such as methyl acetoacetate, ethyl acetoacetate, acetoacetic acid n-butylacrylate, and the like), acetoacetic acid alkyl (e.g., methyl acetoacetate, ethyl acetoacetate, Propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, tert-butyl acetoacetate, benzyl acetoacetate and phenyl acetoacetate), 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate. .

Examples of the amine compound include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6,6-tetramethylpiperidinyl) amine, di- , Diisopropylamine, isopropylethylamine, 2,2,4-trimethylhexamethylenamine, 2,2,5-trimethylhexamethylenamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis (3, Butylpyridine, tert-butylmethylamine, tert-butylethylamine, tert-butyl n-propylamine, tert-butyl n-butylamine , tert-butylbenzylamine, tert-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino) -2,2,6,6 -Tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, and 6-aminocaproic acid.

Examples of the imine compound include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, and guanidine.

Examples of the oxime compounds include formaldehyde compounds such as formaldehyde oxime, acetaldoxime, acetoxime, methylethylketooxime, cyclohexanone oxime, diacetylmonooxime, benzophenone oxime, 2,2,6,6-tetramethylcyclo But are not limited to, hexanone oxime, diisopropyl ketone oxime, methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4- Ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzophenone oxime, and 2 -Heptanone oxime, and the like.

Examples of the carbamate-based compound include phenyl N-phenylcarbamate and the like.

Examples of the urea compound include urea, thiourea, and ethylene urea.

Examples of the acid amide-based (lactam-based) compound include acetanilide, N-methylacetamide, acetic acid amide,? -Caprolactam,? -Valerolactam,? -Butyrolactam, - piperazin dione, and laurolactam.

Examples of the acid imide compound include succinic acid imide, maleic acid imide, and phthalimide.

Examples of triazole-based compounds include 1,2,4-triazole, benzotriazole and the like.

Examples of the pyrazole compound include pyrazole, 3,5-dimethylpyrazole, 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-ditert- 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, Phenylpyrazole, and the like.

Examples of pyrrole-based compounds include pyrrole, 2-methylpyrrole, 3-methylpyrrole, and 2,4-dimethylpyrrole.

Examples of the mercapane-based compound include n-butyl mercaptan, n-dodecyl mercaptan, n-hexyl mercaptan, thiophenol, and pyridine-2-thiol.

Examples of the bisulfite include sodium bisulfite and the like.

Among the structural units A1 represented by the above-mentioned formula (a1), the following structural formula (a1-1), formula (a1-2), or formula (a1-3 ) Is preferable.

(3)

(Wherein R ¹ and R ² are the same as those in the formula (a1), and R ⁷ is independently an alkyl group having 1 to 4 carbon atoms And R &lt; ⁸ &gt; each independently represents a halogen atom or an organic group having 1 to 6 carbon atoms and R &lt; ⁹ &gt; each independently represents an organic group having 1 to 6 carbon atoms, a is an integer of 0 or more and 3 or less.)

Examples of the organic group represented by R ⁷ in the formula (a1-1) include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, a phenyl group, a carbon A phenylalkyl group having 7 or more and 12 or less atoms, or an acyl group having 2 to 12 carbon atoms. Among these groups, an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

The alkyl group may be linear or branched.

In formula (a1-1), two R ^a7 may be the same or different.

In the formula (a1-2), R ^a8 is a substituent on the pyrazolyl group, and each independently is a halogen atom or an organic group having 1 to 6 carbon atoms.

Preferable examples of R ^a8 include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aliphatic And an acyl group.

The R ^{a8 is preferably a} halogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, More preferably 3 or less, and particularly preferably a methyl group.

In the formula (a1-2), a is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less.

Examples of the organic group represented by R ^a9 in formula (a1-3) include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, a phenyl group, And phenylalkyl groups having 7 or more and 12 or less atoms.

In formula (a1-3), two R ^a9 may be the same or different.

The structural unit A1 is added to the resin by copolymerizing a (meth) acrylic acid ester represented by the following formula (a-I) with a monomer giving another structural unit.

Among the (meth) acrylic acid esters represented by the formula (aI), the (meth) acrylic acid esters represented by the following formulas (aI-1), (aI-2) (meth) acrylic acid ester represented by the formula (aI-1a), (aI-2a) or (aI-3a)

The structural unit A1 may exist in a block form in the resin, or may exist in a random form. From the viewpoint that the isocyanate group generated in the structural unit A1 by heating and the hydroxyl group easily react well, the structural unit A1 is preferably present at random in the resin.

[Chemical Formula 4]

As specific preferred examples of the (meth) acrylic acid ester which gives the structural unit A1, the following compounds may be mentioned.

[Chemical Formula 5]

Of these, the following (meth) acrylic acid esters are preferable because of the ease of production of the resin and the ease of obtaining a resin having good curability.

[Chemical Formula 6]

The amount of the structural unit A1 in the resin is not particularly limited within the range not hindering the object of the present invention. The content of the structural unit A1 in the resin is preferably at least 15 mol%, more preferably at least 15 mol% and at most 45 mol%, based on the total structural units of the resin, from the viewpoint of curability. The content of the structural unit A1 in the resin is preferably 20% by mole or more and 40% by mole or less, more preferably 25% by mole or more and 35% by mole or less, Or less.

<Structural unit A2>

The structural unit A2 is a structural unit represented by the above-mentioned formula (a2). In formula (a2), R ¹ is a hydrogen atom or a methyl group.

In formula (a2), R ⁴ is a divalent hydrocarbon group. The hydrocarbon group as R ^{4 may be} an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group having an aliphatic portion and an aromatic portion. In view of the curability of the resin, it is preferable that R ⁴ is a divalent aliphatic hydrocarbon group. When R ⁴ is a divalent aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof, preferably a linear chain.

The number of carbon atoms of the hydrocarbon group as R ⁴ is not particularly limited. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 2 or more and 10 or less, and particularly preferably 2 or more and 6 or less. When the hydrocarbon group is an aromatic group or a hydrocarbon group having an aliphatic portion and an aromatic portion, the number of carbon atoms is preferably 6 or more and 20 or less, more preferably 6 or more and 12 or less.

Specific examples of the divalent aliphatic hydrocarbon group include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, Diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane- Diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane- , Pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, , And eicosan-1, 20-diyl group.

Of these, preferred are methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, Diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, Diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane -1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, and icosaic-1,20-diyl group are preferable, and methylene group, ethane- -1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, More preferably an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,9-diyl group, A 1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

Specific examples of the bivalent aromatic hydrocarbon group include a p-phenylene group, an m-phenylene group, an o-phenylene group, a naphthalene-1,4-diyl group, a naphthalene- Dienes and the like, and p-phenylene group and m-phenylene group are preferable, and p-phenylene group is more preferable.

The structural unit A2 is added to the resin by copolymerizing a (meth) acrylic acid ester represented by the following formula (a-II) with a monomer giving another structural unit.

The structural unit A2 may exist in a block form in the resin, or may exist randomly. The structural unit A2 is preferably present at random in the resin, since the isocyanate group generated in the structural unit A1 by heating is likely to react well with the hydroxyl group.

(7)

(In the formula (a-II), R ¹ and R ⁴ are the same as in the formula (a2).)

Specific preferred examples of the (meth) acrylic acid ester to which the structural unit A2 is given include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, Hydroxyphenylmethacrylate, 3-hydroxyphenylmethacrylate, 3-hydroxyphenylmethacrylate, 4-hydroxybutylmethacrylate, 4-hydroxyphenylmethacrylate, 4-hydroxyphenylmethacrylate, And the like.

Of these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable.

The amount of the structural unit A2 in the resin is not particularly limited within the range not hindering the object of the present invention.

The amount of the structural unit A2 in the resin is preferably at least 15 mol%, more preferably at least 15 mol% and at most 45 mol%, based on the total structural units of the resin. The content of the structural unit A1 in the resin is preferably 20% by mole or more and 40% by mole or less, more preferably 25% by mole or more and 35% by mole or less, Or less.

In the resin, the number of moles of the structural unit A1 and the number of moles of the structural unit A2 are preferably 80/100 or more and 100/80 or less, more preferably 90/100 or more and 100/80 or more, More preferably 90 or less, and particularly preferably 95/100 or more and 100/95 or less. It is most preferable that the number of moles of the structural unit A1 and the number of moles of the structural unit A2 in the resin are equimolar.

<Structural unit A3>

The structural unit A3 is a structural unit represented by the above-mentioned formula (a3). In formula (a3), R ¹ is a hydrogen atom or a methyl group.

In the formula (a3), R ⁶ is an organic group containing two or more benzene rings. By including the structural unit A3 having as an R ⁶ an organic group containing two or more benzene rings, a cured product having a high refractive index can be formed.

The two or more benzene rings included in R ⁶ may be condensed with each other, or may be bonded by a single bond or a linking group.

The number of carbon atoms of R &lt; ⁶ &gt; is not particularly limited within the range not hindering the object of the present invention. The number of carbon atoms of R ⁶ is preferably 10 or more and 50 or less, more preferably 10 or more and 30 or less.

Examples of the organic group containing two or more benzene rings as R ⁶ include groups in which one hydrogen atom has been removed from the following polycyclic compound or a compound having a substituent group introduced into the following polycyclic compound. X is -O-, -S-, -CO-, -SO ₂ -, -CO-NH-, -CO-NH-CO-, -NH-CO-NH-, -CO- , -CO-O-CO-, -O -CO-O-, -SO 2, -NH-, -SS-, -CH 2 -, -CH (CH 3) -, or -C (CH _{3) 2} - to be.

[Chemical Formula 8]

Examples of the substituent that can be introduced into the above polycyclic compound include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, An aliphatic acyl group having a number of 2 or more and 6 or less, a nitro group, and a cyano group.

When a substituent is introduced into the above polycyclic compound, the number of substituents is not particularly limited, but is preferably 4 or less, and is preferably 1 or 2.

As the R ⁶ described above, a group represented by the following formula is preferable.

R ¹⁰ , R ¹¹ and R ¹³ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 1 to 6 carbon atoms An alkoxy group of 2 to 6 carbon atoms, an aliphatic acyl group of 2 to 6 carbon atoms, a nitro group, and a cyano group, R ¹² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and b And c each independently represent an integer of 0 or more and 4 or less, and d is an integer of 0 or more and 7 or less.

[Chemical Formula 9]

Among these groups, a group represented by the following formula is preferable from the viewpoint of a good effect of making a high refractive index and an easy introduction into a resin, and a biphenyl group in which two bs are all 0 in the following formula is more preferable Do.

[Chemical formula 10]

The group R ⁶ described above is bonded to the main chain of the resin via R ⁵ . R ⁵ is a single bond or a divalent linking group.

The divalent linking group is not particularly limited within the scope of not hindering the object of the present invention. Preferred examples of the divalent connecting group, carbon atoms, alkylene group of 1 or more and 6 or less, -O-, -S-, -CO-, -SO 2 -, -CO-NH-, -CO-NH-CO-, - NH-CO-NH-, -CO- O-, -CO-O-CO-, -O-CO-O-, -SO 2, the top 2 is selected from the group consisting of -NH-, and -SS- and , And groups obtained by combining two or more divalent groups selected from the above-mentioned groups.

R ⁶ is preferably a single bond, an alkylene group having 1 to 6 carbon atoms, and -CO-O-, more preferably a single bond, -CO-O-, -CO- Represents a terminal of a bonding hand bonded to R &lt; ⁶ &gt; in the formula (a3)). When R ⁶ is an alkylene group, the alkylene group may be linear or branched.

From the above, as the structural unit A3, a structural unit represented by the following formula (a3-1) is preferable. In formula (a3-1), R ¹ , R ¹⁰ , and b are each as described above.

(11)

The structural unit A3 is added to the resin by copolymerizing an unsaturated compound represented by the following formula (a-III) with a monomer giving another structural unit.

The structural unit A3 may exist in a block form in the resin, or may exist in a random form. It is preferable that the structural unit A3 and the structural unit A2 are randomly present in the resin since the structural unit A1 and the structural unit A2 are uniformly distributed in the resin.

As the unsaturated compound represented by the formula (a-III), a (meth) acrylic acid ester represented by the following formula (a-III-1) is preferable and a (meth) acrylic acid ester represented by the following formula desirable. In the formulas (a-III), (a-III-1) and (a-III-1a), R ¹ , R ⁵ , R ⁶ , R ¹⁰ and b are as described above.

[Chemical Formula 12]

Specific examples of the unsaturated compound giving the structural unit A3 include acrylic acid (1,1'-biphenyl-4-yl) ester, methacrylic acid (1,1'-biphenyl- , 1'-biphenyl-3-yl) ester, methacrylic acid (1,1'-biphenyl- 1'-biphenyl.

Among these, acrylic acid (1,1'-biphenyl-4-yl) ester and methacrylic acid (1,1'-biphenyl-4-yl) ester are preferable.

The amount of the structural unit A3 in the resin is not particularly limited within the range not hindering the object of the present invention. The amount of the structural unit A3 in the resin is preferably 30 mol% or more and 50 mol% or less, more preferably 35 mol% or more and 50 mol% or less in the total structural units of the resin, from the viewpoint of both good curability and high refractive index of the cured product , And particularly preferably from 40 mol% to 50 mol%.

<Other structural units>

The resin may contain other structural units in addition to the above-mentioned structural units A1, A2, and A3 insofar as the object of the present invention is not impaired.

Examples of other structural units include structural units derived from (meth) acrylic acid esters. A constituent unit may be used. (Meth) acrylic acid is acrylic acid, or methacrylic acid. (Meth) acrylic acid ester is represented by the following formula (a-4-1), and is not particularly limited so long as it does not hinder the purpose of the present invention.

[Chemical Formula 13]

In the formula (a-IV), R ^a1 is a hydrogen atom or a methyl group. R ^a11 is an organic group which does not have an active hydrogen-containing group capable of reacting with an isocyanate group generated from a block isocyanate group in the structural unit A1.

Examples of the group containing active hydrogen include a hydroxyl group, a mercapto group, an amino group, and a carboxyl group. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched, and cyclic.

The substituent other than the hydrocarbon group in the organic group of R ^a11 is not particularly limited as long as the effect of the present invention is not impaired and may be a halogen atom, an alkylthio group, an arylthio group, a cyano group, a silyl group, an alkoxy group, an alkoxycarbonyl group, An aryloxyalkyl group, an arylthioalkyl group, an N, N-disubstituted amino group (-NRR ': R and R' each independently represents a hydrocarbon group), a nitro group, a nitro group, an acyl group, an acyloxy group, an alkoxyalkyl group, an alkylthioalkyl group, And the like). The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.

As R ^a11 , an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group is preferable, and these groups may be substituted with a halogen atom, an alkyl group, or a heterocyclic group. When these groups include an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is of a linear or branched chain type, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- , n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, Decyl groups, and the like.

When R ^a11 is a group containing an alicyclic group or an alicyclic group, preferred alicyclic groups include monocyclic alicyclic groups such as cyclopentyl group and cyclohexyl group, adamantyl group, norbornyl group, isobornyl group, tricyclo A cyclohexyl group, a nonyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Examples of the monomers other than the (meth) acrylic acid ester to which other structural units are imparted include allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers may be used alone or in combination of two or more.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caprylate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; .

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- Alkyl vinyl ethers such as ether, 2-ethylbutyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether and tetrahydrofurfuryl vinyl ether; And vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-beta-phenylbutylate, vinyl benzoate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrene include styrene, such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, Alkylstyrenes such as styrene, ethoxymethylstyrene and acetoxymethylstyrene, alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene and tetrachloro But are not limited to, styrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, And halostyrene such as methylstyrene.

When the resin contains other structural units in addition to the above-mentioned structural units A1, A2, and A3, the total amount of the structural units A1, A2, and A3 in the resin is such that the total amount of the structural units Is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more.

It is preferable that the resin does not contain any other structural unit but consists only of the structural unit A1, the structural unit A2, and the structural unit A3 in that the cured product has high refractive index and good curability.

<Production method of resin>

The method for producing the resin described above is not particularly limited. In general, after a predetermined amount of the monomer giving the above-mentioned structural unit A1, the structural unit A2, and the structural unit A3 and, if necessary, the monomer giving another structural unit are mixed in a predetermined amount, The polymerization is carried out in the temperature range of, for example, 50 DEG C to 120 DEG C to obtain a resin. The resin is often obtained as a solution in an organic solvent, but the resin obtained as a solution can be blended with the curable composition as it is, or can be used as it is as a curable composition.

The weight average molecular weight of the resin obtained by the above method is preferably 30,000 or more, more preferably 35,000 or more and 100,000 or less, and particularly preferably 40000 or more and 80000 or less. The weight average molecular weight is the molecular weight in terms of polystyrene measured by GPC. When the weight average molecular weight of the resin is large to some extent, it is easy to form a cured product having excellent solvent resistance and thermal decomposition resistance.

The solution of the resin thus obtained may be mixed with a poor solvent such as hexane, diethyl ether, methanol or water to precipitate the resin, and the precipitated resin may be recovered and used. The precipitated resin is preferably washed after filtration and then dried under normal pressure or reduced pressure at such a temperature that the block isocyanate group in the structural unit A1 is not decomposed. In this way, the resin of the powdered object can be recovered. The powdery resin may be used as it is or may be used in combination with the curable composition described later.

&Quot; Curing Composition &quot;

The curable composition includes the above-mentioned resin and a solvent. The kind of the solvent is not particularly limited within the range not hindering the object of the present invention. The curable composition may contain two or more kinds of solvents in combination.

In view of the fact that the solvent does not react with the isocyanate group generated from the block isocyanate group in the structural unit A1 even when the solvent remains at the time of curing the resin, the solvent is preferably a compound having no group containing an active hydrogen capable of reacting with an isocyanate group .

Examples of the group containing active hydrogen include a hydroxyl group, a mercapto group, an amino group, and a carboxyl group.

In addition, since the solvent can be removed under a reduced pressure, for example, at a temperature at which curing of the resin does not proceed, a solvent having a group containing an active hydrogen can not necessarily be used.

Preferable examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monopropyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monoethyl ether acetate; and monoalkyl ethers of glycols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monobutyl ether acetate and the like; aromatic solvents such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, 2-heptanone, cyclopentanone, and cyclohexanone Ketones such as ethyl acetate, butyl acetate, ethoxyacetate, hydroxyacetate, 3-methoxybutylacetate, 3-methyl-3-methoxybutyl acetate, ethyl 2-hydroxypropionate, Methyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, Butyl lactate, and? -Butyrolactone.

Of these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl lactate, and lactic acid are preferable in view of the leveling property of the coating film when the curable composition is applied. Butyl is preferable, and propylene glycol monomethyl ether acetate, 2-heptanone, cyclopentanone, and cyclohexanone are more preferable.

The amount of the solvent to be used in the curable composition is not particularly limited and is appropriately determined depending on the use of the curable composition, considering the viscosity and the like.

The amount of the solvent to be used is preferably set so that the solid content concentration in the curable composition is at least 5 mass%, more preferably at least 8 mass%, and even more preferably at least 10 mass% . The amount of the solvent to be used is preferably set so that the solid content concentration in the curable composition is 50 mass% or less, more preferably 45 mass% or less, and 40 mass% or less desirable.

The resin composition may further contain various additives insofar as the object of the present invention is not impaired. Examples of the additives include crosslinking agents, ultraviolet absorbers, sensitizers, plasticizers, antioxidants, light stabilizers, adhesion aids, and fillers (for example, high refractive index fillers such as zirconium oxide fine particles).

«Hard Goods»

The above-mentioned resin is molded into a desired shape and then heated to form a cured product. Such a cured product contains the structural unit A3 derived from the above-mentioned resin and has a high refractive index.

The refractive index of the cured product is preferably 1.55 or more, more preferably 1.56 or more, and more preferably 1.58 or more. The upper limit of the refractive index is not particularly limited, but is, for example, 1.70 or less.

&Lt; Process for producing cured product &

Hereinafter, a method for producing a cured product of the resin will be described.

The production method of the cured product,

A molding step of molding the resin into a predetermined shape,

A curing step of curing the molded resin by heating

.

In the molding step, the shape of the molded resin and the molding method of the resin are not particularly limited.

Examples of the method of molding the resin include a method of applying a composition containing a solvent and a resin on a substrate and thereafter removing the solvent from the coating film, a method of applying a solution of a composition containing a solvent and a resin on a substrate Thereafter, a method of removing the solvent and a method of removing the solvent from the composition in the mold after filling the mold with the concave portion of a predetermined shape with the solution of the composition containing the solvent and the resin.

The method of applying the composition on the substrate is not particularly limited. For example, using a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater and a slit coater, or a spinner (rotary coating device) or a curtain flow coater, Can be coated on the substrate so as to have a desired film thickness to form a coating film.

After the composition including the solvent and the resin is formed by the above method, the resin is appropriately subjected to a heat treatment (pre-bake (post-apply bake (PAB)) treatment to remove the solvent, .

The temperature of the prebake is suitably selected in consideration of the boiling point of the solvent. The prebake may be performed at a low temperature under reduced pressure to prevent the resin from hardening before the solvent is sufficiently removed.

The pre-baking method is not particularly limited and may be carried out by, for example, (i) hot plate baking at a temperature of 80 ° C or more and 120 ° C or less (preferably 85 ° C or more and 100 ° C or less, more preferably 85 ° C or more and 95 ° C or less) (Ii) a method of allowing to stand for several hours or more at room temperature for several days or less, (iii) a method of heating the hot air heater or infrared heater for several tens of minutes to several hours or less A time in the range, a method of removing the solvent by putting the substrate.

The resin thus formed is heated (post-baked) to form a cured resin. The curing temperature is not particularly limited as long as the curing of the resin proceeds satisfactorily and thermal denaturation or thermal decomposition of the cured product does not occur.

The upper limit of the curing temperature is preferably 250 DEG C or lower, for example, and preferably 230 DEG C or lower. The lower limit of the curing temperature is preferably 120 DEG C or higher, more preferably 130 DEG C or higher.

The resin of the present embodiment can be cured at a low temperature. For example, the resin can be cured at 180 ° C or lower and can be cured at 150 ° C or lower.

By the above method, a cured product of the above-mentioned resin is produced.

&Lt; Microlens Manufacturing Method &gt;

Hereinafter, a method of manufacturing a microlens using the resin will be described.

A method of manufacturing a microlens,

A lens material layer forming step of forming a lens material layer by crosslinking a resin layer obtained by applying a composition containing the resin on a substrate by heating;

A lens pattern forming step of forming a lens pattern by forming a resist pattern on the lens material layer and then reflowing the resist pattern by heating;

A shape transferring step of dry-etching the lens material layer and the lens pattern using the lens pattern as a mask and transferring the shape of the lens pattern to the lens material layer

.

Examples of the substrate include a substrate such as a silicon wafer on which an image element including a photodiode (organic photodiode, inorganic photodiode or the like), a color filter layer or the like is formed, and a silicon wafer on which an antireflection film is additionally formed in some cases.

The composition comprising the above resin is typically a curable composition comprising the above resin and a solvent. The method of applying the composition on the substrate is not particularly limited. As a specific example of the method of applying the composition on a substrate, the above-mentioned method can be mentioned for the method for producing the cured product.

The formed coating film is suitably subjected to heat treatment (pre-baking (post-apply baking (PAB)) treatment to remove the solvent in the coating film to form a resin layer.

The specific method of prebaking is as described above for the production method of the cured product.

The upper limit of the curing temperature in the lens material layer forming step is, for example, preferably 250 DEG C or lower, and more preferably 230 DEG C or lower. The lower limit of the curing temperature is preferably 120 deg. C or higher, more preferably 130 deg. C or higher.

The heating temperature in the lens material layer forming step can be set to, for example, 180 deg. C or lower and can be set to 150 deg. C or lower from the viewpoint of the process construction in the case of using an organic photodiode have.

The film thickness of the formed lens material layer is preferably in the range of 100 nm to 4.0 m, more preferably in the range of 400 nm to 2.0 m.

The heating conditions for the reflow in the lens pattern forming step differ depending on the kind of each component in the composition used for forming the resist pattern, the compounding ratio, the film thickness of the resist pattern, and the like, but the heating temperature is, Or more and 150 占 폚 or less (preferably 70 占 폚 or more and 140 占 폚 or less), and the heating time is, for example, about 0.5 minute to 60 minutes (preferably 1 minute to 50 minutes).

The film thickness of the resist pattern is preferably in the range of 100 nm to 4.0 m, more preferably in the range of 400 nm to 2.0 m.

Dry etching in the shape transfer process is not particularly limited, and for example, dry etching by plasma (oxygen, argon, CF _4, etc.) or corona discharge can be used.

Through the above steps, by using the above-mentioned resin, it is possible to form a microlens having a high refractive index and a small decrease in dimensional change and transparency in use under a high temperature environment. Therefore, the microlenses formed by the above method are preferably used in various applications.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Example 1]

100 parts by mass of a monomer mixture composed of 35% by mole of a methacrylic acid ester (M1) represented by the following formula, 35% by mole of a methacrylic acid ester (M2) represented by the following formula and 30% by mole of a methacrylic acid ester , And 100 parts by mass of propylene glycol monomethyl ether in a flask were mixed and dissolved. The flask was heated to 75 deg. C by an oil bath, and then a solution of 5 parts by mass of 2,2'-azobisisobutyronitrile in propylene glycol monomethyl ether was slowly added dropwise to the flask. After completion of dropwise addition, reaction was carried out for 20 hours while maintaining the temperature.

[Chemical Formula 14]

As a result of the polymerization, Resin 1 comprising the structural unit of the following formula was obtained. In the following formula, the numerical value at the lower right of the parentheses means the content of each structural unit in the resin. The weight average molecular weight of the obtained Resin 1 as measured by GPC in terms of polystyrene was 50,000.

[Chemical Formula 15]

[Examples 2 to 5]

A resin was obtained in the same manner as in Example 1 except that the monomer composition was changed to the composition shown in Table 1 below. Resin 2 to resin 5 were used for the resins obtained in Examples 2 to 5, respectively.

The weight average molecular weights of Resins 2 to 5 were all 50000, as in Resin 1 obtained in Example 1.

[Examples 6 to 10 and Comparative Example 1]

In Examples 6 to 10, 99.94 parts by mass of the resin shown in Table 2 and 0.06 parts by mass of a surfactant (PolyFox PF-656 (Omunoba)) were dissolved in propylene glycol monomethyl ether acetate at a solid concentration of 15 mass% To obtain a curable composition.

In Comparative Example 1, Comparative Resin 1 (weight average molecular weight: 50,000) having the following structure was used. In the following formula, the numerical value at the lower right of the parentheses means the content of each structural unit in the resin.

[Chemical Formula 16]

The obtained curable composition was coated on a silicon substrate with a thickness to form a cured film having a thickness of 1 占 퐉 to form a coating film. The formed film was subjected to prebaking at 90 DEG C for 90 seconds and postbaking at 150 DEG C for 5 minutes to obtain a cured film. The film thickness of the obtained cured film is taken as T1.

Subsequently, the obtained cured film was immersed in acetone at room temperature for 10 minutes, and then the film thickness of the cured film after immersion was measured. The film thickness of the cured film after immersion is defined as T2.

Based on the measurement results of T1 and T2,

Remaining film ratio (%) = T2 / T1 × 100

To calculate the residual film ratio. The curability was evaluated based on the calculated residual film ratio according to the following criteria. The results are shown in Table 2.

(Evaluation Criteria for Curability)

?: Remaining film ratio of 95% or more

?: Residual film ratio of 90% or more and less than 95%

X: Residual film ratio is less than 90%

According to Table 2, in Examples 6 to 10 using Resins 1 to 5 including the aforementioned structural units A1, A2, and A3, the coating film was cured well enough to exhibit a residual film ratio of 90% or more Can be done.

On the other hand, in Comparative Example 1 using the comparative resin 1 containing a structural unit derived from glycidyl methacrylate instead of the structural unit A1, the residual film ratio of the formed cured film was less than 90% It was not.

[Example 11, Comparative Example 2, and Comparative Example 3]

In Example 11, a curable composition containing the resin 1 used in Example 9 was used. In Comparative Example 2, the curable composition used in Comparative Example 1 was used. In Comparative Example 3, 100 parts by mass of Comparative Resin 2 (weight average molecular weight: 50,000) having the following structure and a curing composition obtained by dissolving 1 mass part of the thermal acid generator in propylene glycol monomethyl ether acetate to have a solid content concentration of 15 mass% did. In addition, K-PURE (registered trademark) CXC-1821 manufactured by King Industries was used as the thermal acid generator herein.

[Chemical Formula 17]

The curable composition was applied on a silicon substrate or on a color filter (CF) containing a basic amine component at a film thickness at which a cured film with a film thickness of 1 占 퐉 was formed to form a coating film. The formed film was subjected to prebaking at 90 DEG C for 90 seconds and postbaking at 150 DEG C for 5 minutes to obtain a cured film. The film thickness of the obtained cured film is taken as T1.

Subsequently, the obtained cured film was immersed in acetone at room temperature for 10 minutes, and then the film thickness of the cured film after immersion was measured. The film thickness of the cured film after immersion is defined as T2.

Based on the measurement results of T1 and T2,

Remaining film ratio (%) = T2 / T1 × 100

To calculate the residual film ratio. The values of the calculated residual film ratios are shown in Table 3.

According to Table 3, in Example 11 using Resin 1 containing the structural units A1, A2, and A3 described above, even on a Si substrate or in a CF atmosphere in a basic atmosphere, It can be understood that the coating film can be sufficiently cured.

On the other hand, in Comparative Example 2 using the comparative resin 1 including the structural unit derived from glycidyl methacrylate instead of the structural unit A1, the residual film ratio of the cured film formed on the Si substrate and also on the CF substrate was less than 90% Curing did not proceed as in the examples.

In Comparative Example 3 using the comparative resin 2 containing a structural unit derived from glycidyl methacrylate, the curing proceeded well on the Si substrate by the use of the thermal acid generator. However, in the curing on the Si substrate and the curing in the CF in the basic atmosphere, there was a large difference in the residual film ratio of the cured film.

[Example 12 and Comparative Examples 4 to 6]

In Example 12 and Comparative Examples 4 to 6, the film thickness of the cured film and the thermal stability against the light transmittance were evaluated.

In Example 12, a cured film formed on a Si substrate was used as in Example 11. In Comparative Example 4, a cured film formed on a Si substrate was used in the same manner as in Comparative Example 2. In Comparative Example 5, a cured film formed on a Si substrate was used as in Comparative Example 3.

In Comparative Example 6, using the curable composition obtained by dissolving 100 parts by mass of Comparative Resin 3 (weight average molecular weight 10000) having the following structure in propylene glycol monomethyl ether acetate so as to have a solid content concentration of 18% by mass, To form a cured film on the Si substrate. The film thickness T1 of the cured film immediately after formation was measured.

The transmittance LT1 of a light beam having a wavelength of 400 nm was measured for the cured film immediately after formation.

[Chemical Formula 18]

The cured film thus formed was placed in a thermostatic chamber at 150 ° C and taken out at a time point of 200 hours, 500 hours, 1000 hours, and 2000 hours, and the film thickness T3 and the transmittance LT2 of the light beam with a wavelength of 400 nm Respectively. Based on the measurement results of each time,

Film Thickness Reduction Rate (%) = T3 / T1 × 100

Light transmittance reduction rate (%) = LT2 / LT1 × 100

, The film thickness reduction rate and the light transmittance reduction rate at each time were obtained. Table 4 shows the film thickness reduction rate and the light transmittance reduction rate at each time.

According to Table 4, in Example 12 using the resin 1 including the structural unit A1, the structural unit A2, and the structural unit A3 described above, even when the cured film was maintained at 150 DEG C for 2000 hours, the film thickness and the light transmittance did not decrease .

On the other hand, in Comparative Examples 4 to 6 using Comparative Resin 1, Comparative Resin 2, and Comparative Resin 3 containing a structural unit derived from glycidyl methacrylate instead of the structural unit A1, in the cured film formed, 150 C, it was found that the film thickness and the light transmittance were remarkably lowered with the lapse of time.

[Examples 13 to 15 and Comparative Example 7]

Resin 6 and comparative resin 4 were obtained in the same manner as in Example 1 except that the monomer composition was changed to the composition shown in Table 5 below. M4 shown in Table 5 is styrene.

In Examples 13 to 15 and Comparative Example 7, 99.94 parts by mass of the resin shown in Table 5 and 0.06 parts by mass of a surfactant (PolyFox PF-656 (Omunoba)) were added to propylene glycol monomethyl ether acetate, And a solids concentration of 15% by mass to obtain a curable composition.

Using each of the curable compositions, a cured film having a thickness of 1 占 퐉 was formed in the same manner as in Example 6, and the refractive index of the cured film formed was measured. The measurement results of the refractive index are shown in Table 5.

According to Table 5, it can be seen that in Examples 13 to 15 using the resin 1 including the structural unit A1, the structural unit A2, and the structural unit A3 described above, a cured film exhibiting a refractive index of 1.56 or more can be formed.

On the other hand, in Comparative Example 7 using the comparative resin 4 including a structural unit derived from styrene which contains only one benzene ring instead of the structural unit A3, only a cured film having a refractive index of about 1.54 could not be formed.

Claims (15)

A resin comprising a structural unit represented by the following formula (a1), a structural unit represented by the following formula (a2), and a structural unit represented by the following formula (a3).
[Chemical Formula 1]

(Formula (a1), (a2), and (a3) of, R ¹ is each independently a hydrogen atom, or a methyl group, and, R ² is a single bond, or a carbon atom number 1-5 alkylene group, R ³ is A block isocyanate group, R ⁴ is a divalent hydrocarbon group, R ⁵ is a single bond or a divalent linking group, and R ⁶ is an organic group containing two or more benzene rings.) The method according to claim 1,
A structural unit represented by the following formula (a1), a structural unit represented by the following formula (a1-1), a structural unit represented by the following formula (a1-2), and a structural unit represented by the following formula &Lt; / RTI &gt; wherein at least one of the structural units selected from &lt; RTI ID = 0.0 &gt;
(2)

(Wherein R ¹ and R ² are the same as in the above formula (a1), and R ⁷ is each independently selected from the group consisting of carbon atoms of 1 to 10, And R ⁸ each independently represents a halogen atom or an organic group having 1 to 6 carbon atoms, R ⁹ is independently an organic group having 1 to 6 carbon atoms, and a is an organic group having 0 to 3 It is an integer.) The method according to claim 1,
Wherein R &lt; ⁴ &gt; is a divalent chain aliphatic hydrocarbon group. The method according to claim 1,
Wherein the structural unit represented by the formula (a3) is a structural unit represented by the following formula (a3-1).
(3)

(Wherein R ¹ is the same as in the above formula (a3), R ¹⁰ is each independently a halogen atom or an organic group having 1 to 6 carbon atoms, b is 0 to 4 It is an integer.) The method according to claim 1,
Wherein the proportion of the structural unit represented by the formula (a1) in the total structural units of the resin is 15 mol% or more. The method according to claim 1,
Wherein the proportion of the structural unit represented by the formula (a3) in the total structural units of the resin is 30 mol% or more and 50 mol% or less. The method according to claim 1,
Wherein the ratio of the number of moles of the structural unit represented by the formula (a1) to the number of moles of the structural unit represented by the formula (a2) is 80/100 or more and 100/80 or less. The method according to claim 1,
A resin having a weight average molecular weight of 30,000 or more. A curable composition comprising the resin according to any one of claims 1 to 8 and a solvent. A cured product obtained by curing the resin according to any one of claims 1 to 8. 11. The method of claim 10,
A cured product having a refractive index of 1.55 or more. A method for producing a resin composition, comprising: a molding step of molding the resin according to any one of claims 1 to 8 into a predetermined shape;
And a curing step of curing the molded resin by heating. 13. The method of claim 12,
Wherein the heating temperature in the curing step is 180 占 폚 or less. A lens material layer forming process for forming a lens material layer by crosslinking a resin layer obtained by applying a composition comprising a resin according to any one of claims 1 to 8 on a substrate by heating,
A lens pattern forming step of forming a lens pattern by forming a resist pattern on the lens material layer and then reflowing the resist pattern by heating;
And a shape transfer step of dry-etching the lens material layer and the lens pattern using the lens pattern as a mask, and transferring the shape of the lens pattern to the lens material layer. 15. The method of claim 14,
Wherein the heating temperature in the lens material layer forming step is 180 占 폚 or less.