JP2016216581A - Photocurable resin composition and method of manufacturing device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition containing a radical polymerization initiator which has an appropriate molar extinction coefficient at 365 nm while retaining transmittance, has high transmittance in the visible light region after curing, and is neutral.SOLUTION: A photocurable resin composition contains: a compound represented by the general formula (A) in the figure that generates radicals upon light exposure; and a radical polymerizable compound.SELECTED DRAWING: None

Description

  Some embodiments according to the present invention include a photocurable resin composition containing a compound that can be used as a radical polymerization initiator that generates radicals upon irradiation with light such as ultraviolet rays, and the photocurable resin composition. The present invention relates to a device manufacturing method using an object.

  Lithography, flexography, UV curable ink for silk screen, solder resist, etch resist for electronic industry materials, color filter resist, UV powder paint, water based UV paint, UV absorber paint, paint for woodworking products In radicals such as plastics and metal coatings, radically polymerizable compounds (radical polymerizable monomers, etc.) that are polymerized by radicals and radicals that generate radicals by irradiating light such as ultraviolet rays and initiate polymerization of radically polymerizable compounds A photocurable resin composition having a polymerization initiator is used. As radical polymerization initiators, for example, acetophenone-based radical polymerization initiators are known (see Patent Documents 1 and 2).

  Then, 2,2-dimethoxy-1,2-diphenylethane-1-one, which is known as an acetophenone-based radical polymerization initiator, generates radicals by self-cleavage by irradiation with light such as ultraviolet rays. It is a compound that initiates polymerization of a polymerizable compound, and is marketed by BASF under the product name IRGACURE651. The above-mentioned 2,2-dimethoxy-1,2-diphenylethane-1-one is used as another acetophenone-based radical polymerization initiator such as 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE184, BASF) and 2-hydroxy- Compared with 1- {4- [4- {2-hydroxy-2-methylpropionyl} -benzyl] -phenyl} -2-methylpropan-1-one (IRGACURE127, manufactured by BASF), molar absorption at a wavelength of 365 nm There is an advantage that i-line (wavelength 365 nm), which is a wavelength component contained in a bright line of light emitted from an industrially useful high-pressure mercury lamp or the like, can be effectively used. The 2,2-dimethoxy-1,2-diphenylethane-1-one is advantageous in that the desired cured product can be obtained with high sensitivity due to the high reactivity of the methyl radical generated by photolysis.

  Unlike the thermal polymerization, the photopolymerization using such a radical polymerization initiator does not require heating, and a cured product can be obtained by irradiation with light such as ultraviolet rays near room temperature. Compared to thermal polymerization, there is an advantage that a cured product can be obtained in a very short time, which is a useful technique widely used industrially.

On the other hand, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE907, manufactured by BASF) has high transparency in the visible light region and is used as an optical material. It has good transmittance at 365 nm and can be used for thick films.
In addition, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (IRGACURE OXE01, manufactured by BASF) and ethanone-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE02, manufactured by BASF) is also used as a compound having a high molar absorption coefficient of 365 nm and good sensitivity.

Japanese Patent Laid-Open No. 02-180909 JP 49-55646 A

  The IRGACURE 651 is suitable for thick film applications because of its good transmittance at 365 nm. However, since it tends to be colored after photocuring, there is a problem in using it for optical materials that require high transparency. In addition, in the case of including a step of diluting and preparing a resin in a solvent in order to apply a resin layer with a uniform film thickness as in photolithography, a radical polymerization initiator is used in the process of volatilizing the solvent before curing. There is a problem of volatilization. The effect of this volatilizing phenomenon appears more prominently when the amount of radical polymerization initiator added is increased in order to shorten the curing time.

  On the other hand, the IRGACURE 907 can be used for thick film applications, but has high volatility and exhibits basicity due to the introduction of nitrogen atoms, so there are problems when used as a component of a composition that is preferably used under acidic conditions. is there.

  In addition, IRGACURE OXE01 and IRGACURE OXE02 have a problem that they are not suitable for thick film applications because of insufficient transmittance at 365 nm. IRGACURE OXE01 has absorption in a visible light region of 400 nm or more. Since IRGACURE OXE02 introduces a nitrogen atom to improve the molar extinction coefficient of 365 nm and exhibits basicity like IRGACURE907, there is a problem when it is used as a component of a composition that is preferably used under acidic conditions.

  In view of such circumstances, some aspects of the present invention have a moderate molar extinction coefficient at 365 nm and maintain the transmittance, and have a high transmittance in the visible light region of 400 nm or more after curing and are neutral. It is an object of the present invention to provide a photocurable resin composition containing a specific compound. In addition, some embodiments of the present invention provide a photocurable resin composition containing a specific compound that has low volatility in a process of volatilizing a solvent before curing, and a method for manufacturing a device using the same. Let it be an issue.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following general formula (II) having a structure in which a specific substituent is introduced at the para position of the 2,2-alkoxy 1,2-diphenylethane-1-one skeleton It has been found that the compound represented by A) becomes a radical polymerization initiator that satisfies the above-mentioned problems, and has completed the present invention.

  One embodiment of the present invention is a photocuring comprising a compound represented by the following general formula (A) that generates a radical by light (hereinafter also referred to as “compound (A)”) and a radical polymerizable compound. It is an adhesive resin composition.

(In the general formula (A), R ¹ and R ² each represents a linear or branched alkyl group or alkenyl group which may have a substituent, and may be the same or different from each other. ³ , R ⁴ , R ⁵ and R ⁶ are each a linear or branched alkyl group, alkyloxy group, alkylthio group, alkenyl group, alkenyloxy group, alkenylthio group, aryl which may have a substituent. Oxy group, arylthio group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylcarbonylamino group, alkenylcarbonylamino group, aryl Carbonylamino group, alkylsulfo A group selected from the group consisting of a ruoxy group, an alkenylsulfonyloxy group, an arylsulfonyloxy group, an alkylsulfonyl group and an alkenylsulfonyl group, and a nitro group, which may be the same or different from each other. m represents an integer of 0 to 4, respectively.

One aspect of the present invention is a resist film forming step of forming a resist film on a substrate using the photocurable resin composition,
A photolithographic step of exposing the resist film in a pattern using an active energy ray;
And a pattern forming step of obtaining a photoresist pattern by developing the exposed resist film.

  According to some embodiments of the present invention, a radical polymerization initiator that has a molar extinction coefficient at 365 nm moderately and maintains transmittance, and has high transmittance in the visible light region of 400 nm or more after curing and is neutral. The photocurable resin composition containing can be provided. In addition, according to some embodiments of the present invention, there are provided a photocurable resin composition containing a specific compound that has low volatility in a process of volatilizing a solvent before curing, and a device manufacturing method using the same. can do.

<1> Photocurable resin composition One aspect of the present invention contains a compound (compound (A)) represented by the following general formula (A) that generates a radical by light and a radical polymerizable compound. It is a photocurable resin composition.

(In the general formula (A), R ¹ and R ² each represents a linear or branched alkyl group or alkenyl group which may have a substituent, and may be the same or different from each other. ³ , R ⁴ , R ⁵ and R ⁶ are each a linear or branched alkyl group, alkyloxy group, alkylthio group, alkenyl group, alkenyloxy group, alkenylthio group, aryl which may have a substituent. Oxy group, arylthio group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylcarbonylamino group, alkenylcarbonylamino group, aryl Carbonylamino group, alkylsulfo A group selected from the group consisting of a ruoxy group, an alkenylsulfonyloxy group, an arylsulfonyloxy group, an alkylsulfonyl group and an alkenylsulfonyl group, and a nitro group, which may be the same or different from each other. m represents an integer of 0 to 4, respectively.

(Compound represented by formula (A): Compound (A))
First, the compound (A) will be described.
In the above formula, as the linear or branched alkyl group or alkenyl group of R ¹ and R ² , the total number of carbon atoms is 1 to 4 respectively when giving high mobility or high activity to the generated radical. It is preferable that the alkyl group has 1 to 4 carbon atoms in total.

Specifically, R ¹ and R ² are each an alkyl group such as methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl; and at least one carbon-carbon single bond of the alkyl group is carbon. -An alkenyl group substituted by a carbon double bond;
Each of R ¹ and R ² may be the same as or different from each other, but is preferably the same from the viewpoint of ease of synthesis.

In the above formula, each of R ³ and R ⁴ linear or branched alkyl group, alkyloxy group, alkylthio group, alkenyl group, alkenyloxy group, alkenylthio group, aryloxy group, arylthio group, alkylcarbonyloxy group, Alkenylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylcarbonylamino group, alkenylcarbonylamino group, arylcarbonylamino group, alkylsulfonyloxy group, alkenylsulfonyl As the oxy group, arylsulfonyloxy group, alkylsulfonyl group, and alkenylsulfonyl group, those having a total number of carbon atoms of 20 or less that are readily available from the market are preferable. More preferably, the total number of carbon atoms that can be obtained at low cost is preferably 12 or less, and the total number of carbon atoms is preferably 8 or less in consideration of compatibility with the photocurable resin.

As R ³ and R ⁴ , an alkyl group, an alkyloxy group, an alkylthio group, an alkenyl group, an alkenyl group can be used because raw materials are easily available on the market, the synthesis process is small, and the compound (A) is neutral. Electron donating groups such as an oxy group, an alkenylthio group, an aryloxy group and an arylthio group are preferred.
Each of R ³ and R ⁴ may be the same as or different from each other, but is preferably the same from the viewpoint of ease of synthesis.

In the above formula, each of R ⁵ and R ⁶ linear or branched alkyl group, alkyloxy group, alkylthio group, alkenyl group, alkenyloxy group, alkenylthio group, aryloxy group, arylthio group, alkylcarbonyloxy group, Alkenylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylcarbonylamino group, alkenylcarbonylamino group, arylcarbonylamino group, alkylsulfonyloxy group, alkenylsulfonyl As the oxy group, arylsulfonyloxy group, alkylsulfonyl group, and alkenylsulfonyl group, those having a total number of carbon atoms of 20 or less that are readily available from the market are preferable. More preferably, the total number of carbon atoms that can be obtained at low cost is preferably 12 or less, and the total number of carbon atoms is preferably 8 or less in consideration of compatibility with the photocurable resin. n and m are each 0 to 4, preferably 0 to 2, and preferably 0 in view of easy availability of raw materials from the market.

When n and m are not 0, that is, when the compound (A) has R ⁵ and R ⁶ , R ⁵ and R ⁶ are alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, alkyloxy Electron attractive groups such as carbonyloxy group, alkenyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylsulfonyloxy group, alkenylsulfonyloxy group and arylsulfonyloxy group are preferred. This is because synthetic raw materials can be easily obtained from the market. Alkylcarbonyloxy groups and arylcarbonyloxy groups are more preferred because they further have the advantage of being rich in commercially available derivatives.

By adding a hetero atom such as an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom and a nitrogen atom to the substituent, the interaction between molecules is increased, or the molecular weight is increased and the volatility can be lowered. Furthermore, the compatibility with a radically polymerizable compound and the solubility in the composition can be adjusted by appropriately containing these heteroatoms in the above substituent.
Among the above-mentioned substituents containing heteroatoms, substituents containing atoms having unshared electron pairs such as oxygen atoms, sulfur atoms, phosphorus atoms, and nitrogen atoms are intermolecular interactions such as hydrogen bonds and intermolecular due to polarization. This is particularly suitable because the volatility can be reduced by the electrostatic interaction.
Each of R ⁵ and R ⁶ may be the same as or different from each other, but is preferably the same from the viewpoint of ease of synthesis.

  A typical example of the compound (A) is a 2,2-alkoxy 1,2-di-phenylethane-1-one derivative in which a carbonyl group conjugated with a phenyl group and a phenyl group are adjacent to each other through the carbonyl group. Therefore, even when irradiated with light having a relatively long wavelength of 313 nm to 365 nm among light such as ultraviolet rays (for example, wavelength of 200 nm to 400 nm), radicals are efficiently generated within a short time even at room temperature, for example. Occur. Therefore, the compound (A) having the derivative structure is useful as a radical polymerization initiator.

In addition, since it is possible to utilize i line | wire (wavelength 365nm) contained in the bright line of the light which an industrially useful high pressure mercury lamp emits for the radical generation | occurrence | production from the said compound (A) which has the said derivative structure, Compound (A) has the advantage that it is easy to use industrially.
Moreover, since the molecular weight and the electronic state of the aromatic ring can be adjusted by appropriately selecting the substituents of R ^{3 to} R ⁶ on the two phenyl groups of the compound (A), volatility, radical generation efficiency, etc. It is possible to adjust the absorption characteristics. For example, even when the photocurable resin composition containing the compound is cured in the chamber, contamination in the chamber can be suppressed.

Regarding the volatility, there is a tendency that a reduction in volatility is observed by selecting a substituent having a high molecular weight as a substituent for R ³ , R ⁴ , R ⁵ and R ⁶ . More specifically, as the substituents for R ³ , R ⁴ , R ⁵ and R ⁶ , the molecular weight of the substituent itself is more preferably 30 or more.
Regarding radical generation efficiency, radical generation efficiency tends to be increased by using a substituent as an electron-withdrawing group. Therefore, the substituents for R ⁵ and R ⁶ are preferably electron withdrawing groups. The substituents for R ³ and R ⁴ are preferably electron donating groups as described above, but may be electron withdrawing groups.

  Since the above compound (A) has a structure of 2,2-alkoxy 1,2-diphenylethane-1-one or 2,2-alkenyloxy 1,2-diphenylethane-1-one, it serves as a radical polymerization initiator. Works. Moreover, since the said compound (A) has absorption in i line | wire (wavelength 365nm), i line | wire which is a wavelength component contained abundantly in an industrially useful high pressure mercury lamp etc. can be utilized effectively. By adding a substituent to the para-position of the aromatic ring, it is possible to suppress a longer wavelength after exposure and to improve the transmittance in the visible light region of 400 nm or more. Moreover, volatility can be reduced by having a specific substituent.

The molar extinction coefficient at 365 nm of the compound (A) is preferably 1.0 × 10 ⁵ cm ² / mol or more. The molar absorption at 365 nm is more preferably 1.0 × 10 ⁵ cm ² / mol or more and 1.0 × 10 ⁶ cm ² / mol or less.
In order to make the molar extinction coefficient at 365 nm within the above range, the structure of the compound (A) may be used.

The molar extinction coefficient of the compound (A) at 400 nm or more is preferably 1.0 × 10 ³ cm ² / mol or less. In order to set the molar extinction coefficient at 400 nm within the above range, the structure of the compound (A) may be used.
The pKa of the compound (A) is preferably 6.5 to 7.5, and more preferably 6.2 to 7.2. In order to set the pKa of the compound (A) within the above range, the structure of the compound (A) may be used.
In the present invention, pKa is measured as follows.
Dissolve 1.0 mmol of measurement sample in 100 ml of 75% by weight ethanol aqueous solution, and use 0.01N sodium hydroxide and 0.01N hydrochloric acid with an automatic titrator (GT-200, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Obtained using a titration method.

(Method for producing compound (A))
As a method for producing a 2,2-alkoxy1,2-di-phenylethane-1-one derivative that is a typical example of the compound (A), when n and m in the general formula (A) are 0, For example, it includes a step of reacting 4,4′-dihydroxybenzyl and an orthocarboxylic acid trialkyl ester in the presence of an acid catalyst.
First, 4,4′-dihydroxybenzyl and orthocarboxylic acid trialkyl ester are diluted with a reaction solvent containing, for example, alkyl alcohol, and reacted in the presence of an acid catalyst. Thereby, 4,4′-dihydroxybenzyl is acetalized.

4,4′-Dihydroxybenzyl can be prepared from 4,4′-dimethoxybenzyl which is readily available on the market. Specifically, for example, it can be obtained by reacting hydrogen bromide with 4,4′-dimethoxybenzyl.
The orthocarboxylic acid trialkyl ester can be appropriately selected in consideration of the desired performance, production cost, and the like. Typical examples include orthoformate trialkyl ester, orthoacetic acid trialkyl ester, orthochloroacetic acid. Examples thereof include trialkyl esters, orthopropionic acid trialkyl esters, orthobutyric acid trialkyl esters, orthoisobutyric acid trialkyl esters, orthovaleric acid trialkyl esters and orthobenzoic acid trialkyl esters. In the case where emphasis is placed on the production at a low cost, among the above-mentioned orthocarboxylic acid trialkyl esters, the most versatile and inexpensive ortho formic acid trimethyl ester is preferable.

  As said alkyl alcohol, the alcohol which has a linear or branched alkyl group which is liquid at 25 degreeC, for example is preferable. Further, the alkyl alcohol preferably has the same alkyl group as the alkyl group of the orthocarboxylic acid trialkyl ester. By doing so, even if an acetal exchange reaction occurs, no by-product is produced.

  Examples of the acid catalyst include Bronsted acid and Lewis acid. Examples of the Bronsted acid include sulfuric acid, hydrogen chloride, trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic acid, and trifluoromethanesulfonic acid. Lewis acids include cerium (III) trifluoromethanesulfonate, hafnium trifluoromethanesulfonate (IV), lanthanum trifluoromethanesulfonate (III), yttrium trifluoromethanesulfonate (III), neodymium trifluoromethanesulfonate (III) and Examples include Lewis acids that are stable in an aqueous solution such as indium (III) trifluoromethanesulfonate, but are not limited thereto.

Conditions for reacting 4,4′-dihydroxybenzyl and orthocarboxylic acid trialkyl ester in the presence of an acid catalyst can be appropriately set according to the target product. Typical reaction conditions are, for example, a reaction at 0 to 70 ° C. for 10 to 100 hours.
After reacting 4,4′-dihydroxybenzyl and orthocarboxylic acid trialkyl ester in the presence of an acid catalyst, further esterification is carried out to bond the ester group directly to the phenyl group, thereby obtaining the above compound (A) can be obtained.

Examples of the compound used for the esterification reaction include carboxylic acid chlorides, carboxylic acid anhydrides, sulfonic acid chlorides, and dialkyl dicarbonates.
The reaction conditions for esterifying a product obtained by reacting 4,4′-dihydroxybenzyl and orthocarboxylic acid trialkyl ester in the presence of an acid catalyst can be appropriately set according to the target product. Typical reaction conditions are, for example, reacting at 10 to 100 ° C. for 1 to 10 hours under basic conditions.
Examples of a method for introducing a target substituent not only in the para position but also in the ortho position and the meta position include the following. Friedelcraft acylation reaction of alkylbenzene derivatives, alkoxybenzene derivatives and thioalkoxybenzene derivatives with oxalyl chloride, or coupling reaction with oxalyl chloride using halides such as alkoxybenzene derivatives, thioalkoxybenzene derivatives and aniline derivatives as Grignard reagents Alkyl group, alkyloxy group, alkylthio group, alkenyl group, alkenyloxy group, alkenylthio group, aryloxy group, arylthio group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyl Oxy group, alkenyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylcarbonylamino group, alkenylcarbonyl Amino group, arylcarbonylamino group, an alkylsulfonyloxy group, alkenyloxy sulfonyloxy group, an arylsulfonyloxy group, an alkylsulfonyl group and alkenyl-sulfonyl group or the like can be obtained benzyl derivative having.

(Radically polymerizable compound)
The radical polymerizable compound is a compound having one or more radical polymerizable groups in one molecule. The kind and number of radical polymerizable groups in one molecule of the radical polymerizable compound can be appropriately set according to properties such as the desired viscosity of the coating film, hardness of the cured product, and transmittance. For example, in order to further improve the hardness, a plurality of radical polymerizable groups can be provided in one molecule.

  Examples of the radical polymerizable compound having only one radical polymerizable group in one molecule (hereinafter also referred to as “monofunctional radical polymerizable compound”) include (meth) acrylic acid, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl ( (Meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) Acrylate Methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl ( (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, biphenyl (meth) acrylate, biphenoxyethyl (meth) Acrylate, biphenoxyethoxyethyl (meth) acrylate, naphthalene (meth) acrylate, naphthaleneoxyethyl (meth) acrylate, naphthaleneoxyethoxyethyl (meth) acrylate, phenanthrene (meth) acrylate, phenanthreneoxyethyl (meth) acrylate, phenanthreneoxy Ethoxyethyl (meth) acrylate, anthracene (meth) acrylate, anthraceneoxyethyl (meth) acrylate, anthraceneoxyethoxyethyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, phenyl epoxy (meth) acrylate, (meth) acryloylmorpholine, diacetone (meth) acrylamide, N- [2- (meth) acryloylethyl] -1,2-cyclohexanedicarboximide, N- [2- (meta Monofunctional (meth) such as) acryloylethyl] -1,2-cyclohexanedicarbomido-1-ene and N- [2- (meth) acryloylethyl] -1,2-cyclohexanedicarbomido-4-ene Acrylate monomers; vinyl monomers such as N-vinylpyrrolidone, styrene, α-methylstyrene, vinyltoluene, 4-hydroxystyrene, allyl acetate, vinyl acetate, vinyl propionate and vinyl benzoate;

  Examples of the radical polymerizable compound having two radical polymerizable groups in one molecule (hereinafter also referred to as “bifunctional radical polymerizable compound”) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol pivalic acid ester di (meth) acrylate, bis (oxymethyl) Tricyclo [5.2.1.0 (2,6)] decanedi (meth) acrylate, 2,2-bis (4- (acryloxydiethoxy) phenyl) propane, 2,2-bis (4- (methacryloxy) Diethoxy) phenyl) propane, tricyclo [5.2.1.0 (2,6)] decane-3,8-diyldimethyldimethacrylate, bisphenol-A-diglycidyl ether di (meth) acrylate, 1,4- Ethylene oxide modified diacrylate of cyclohexanedimethanol, ethylene oxide modified tetrabromobisphenol-A-di (meth) acrylate, phenyl di (meth) acrylate, phenyldioxyethyl (meth) acrylate, phenyldioxyethoxyethyl (meth) acrylate, Biphenyl di (meth) acrylate Biphenyldioxyethyl (meth) acrylate, biphenyldioxyethoxyethyl (meth) acrylate, naphthalene di (meth) acrylate, naphthalene dioxyethyl (meth) acrylate, naphthalene dioxyethoxyethyl (meth) acrylate, phenanthrene (meth) Bifunctional such as acrylate, phenanthrene dioxyethyl (meth) acrylate, phenanthrene dioxyethoxyethyl (meth) acrylate, anthracene di (meth) acrylate, anthracene dioxyethyl (meth) acrylate and anthracene dioxyethoxyethyl (meth) acrylate (Meth) acrylate monomers and the like.

  Examples of the radical polymerizable compound having three or more radical polymerizable groups in one molecule (hereinafter, also referred to as “polyfunctional radical polymerizable compound”) include phenyl tri (meth) acrylate, phenyl trioxyethyl (meth) acrylate, Phenyltrioxyethoxyethyl (meth) acrylate, biphenyltri (meth) acrylate, biphenyltrioxyethyl (meth) acrylate, biphenyltrioxyethoxyethyl (meth) acrylate, naphthalenetri (meth) acrylate, naphthalenetrioxyethyl (meth) Acrylate, naphthalene trioxyethoxyethyl (meth) acrylate, phenanthrene tri (meth) acrylate, phenanthrene trioxyethyl (meth) acrylate, phenanthrene trioxyethoxyethyl ( Acrylate), anthracentri (meth) acrylate, anthracentrioxyethyl (meth) acrylate, anthracenoxyoxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, tetra Methylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate And tris-6-functional (meth) acrylates such as tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate Tomonoma, and the like.

Furthermore, examples of the radical polymerizable compound that is an oligomer having two or more radical polymerizable groups in one molecule include oligomer (meth) acrylates such as urethane (meth) acrylate and ester (meth) acrylate.
In the present specification, the name (meth) acryloyl is used as a general term for acryloyl and methacryloyl.
The blending ratio of the monofunctional radical polymerizable compound, the bifunctional radical polymerizable compound, and the polyfunctional radical polymerizable compound is as follows. It is preferable that they are 0-100 mass parts of polymeric compounds, and 0-50 mass parts of polyfunctional radically polymerizable compounds.

(Photocurable resin composition)
The photocurable resin composition concerning one aspect of this invention contains the said compound (A) and a radically polymerizable compound, It is characterized by the above-mentioned.
As described above, the compound (A) functions as a radical photopolymerization initiator. Therefore, it can be set as the photocurable resin composition which concerns on some aspects of this invention used suitably in various fields by setting it as the structure containing the said compound (A) and the said radically polymerizable compound. . Suitable fields include lithography, flexography, silk screen UV curable ink, solder resist, etch resist for electronic industry materials, color filter resist, bump forming resist, UV powder coating, water-based UV Examples include paints, UV absorber combined paints, woodwork finish paints, plastics and metal coatings.

  For example, the photocurable resin composition according to some embodiments of the present invention can be prepared by diluting the compound (A) and the radical polymerizable compound with a non-polymerizable organic solvent. In addition, if the said compound (A) and the said radically polymerizable compound are selected suitably, the photocurable resin composition which does not contain an organic solvent can also be prepared.

  The amount of the compound (A) contained in the photocurable resin composition is appropriately selected depending on the intended use and properties. As an example, content of the said compound (A) is 0.1-60 mass parts with respect to 100 mass parts of photocurable resin composition components except the said compound (A) and an organic solvent, and is typical. Specifically, it is 0.5 to 30 parts by mass, and more typically 1 to 10 parts by mass.

  Examples of the organic solvent contained in the photocurable resin composition include ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methoxyethyl acetate, propylene glycol monomethyl ether acetate Ester compounds such as diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, dioxane and the like; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane and hexane; methylene chloride and chlorobenzene And halogen-based hydrocarbons such as chloroform; alcohols such as methanol, ethanol, normal propanol and isopropanol;

  The photocurable resin composition according to some embodiments of the present invention may contain a photoradical polymerization initiator other than the compound (A). Examples of the other photo radical polymerization initiators include acetophenone, benzophenone, benzyldialkyl ketal, α-hydroxyalkylphenones, α-aminoacetophenones, acylphosphine oxides, titanocenes and oxime esters, trihalomethyltriazines, Other examples include compounds having a trihalomethyl group. When a photo radical polymerization initiator other than the above compound (A) is used, the total amount of the photo radical polymerization initiator in the photo curable resin composition is a photo curable resin composition excluding the photo radical polymerization initiator and the organic solvent. It is preferable that it is 0.1-60 mass parts with respect to 100 mass parts of components, for example.

In addition to the photo radical polymerization initiator as described above, for example, a thermal radical polymerization initiator that generates radicals mainly by heating, such as 2,2′-azobis (isobutyronitrile), benzoyl peroxide, etc., may be used. it can.
In addition to the thermal radical polymerization initiator as described above, it is also possible to add an initiator that generates an acid or a base by light or heat represented by, for example, a sulfonium salt, an iododium salt, and an ammonium salt. . When a thermal radical polymerization initiator and / or an initiator that generates an acid or a base is used, the amount of each compound in the photocurable resin composition depends on the thermal radical polymerization initiator, the initiator that generates an acid or a base, and organic. It is preferable that it is 0.1-60 mass parts with respect to 100 mass parts of photocurable resin composition components except a solvent.

As described above, by including a plurality of polymerization initiators in the composition, for example, multi-stage curing and curing after patterning are facilitated.
The photocurable resin composition according to some embodiments of the present invention includes an adhesiveness imparting agent such as an alkoxysilane compound described below, a photoacid generator described below, and a photosensitization, depending on the intended use and properties. Agents, polymers containing units having specific groups described below, polymerization inhibitors described below, leveling agents, plasticizers, fillers, antifoaming agents, flame retardants, stabilizers, antioxidants, perfumes, thermal crosslinking agents, etc. These additives may be contained, and these may be contained alone or in combination of two or more.

When the photocurable resin composition is applied to a substrate and cured, the photocurable resin composition preferably contains an alkoxysilane compound such as a silane coupling agent in order to improve the adhesion between the two. In order for the alkoxysilane compound to exhibit adhesion imparting properties to the substrate, it is preferable to use acidic conditions when curing. For this reason, it is preferable that the photocurable resin composition contains an alkoxysilane compound because it can exhibit an effect particularly when used in combination with the compound (A) which is almost neutral.
For example, the alkoxysilane compound includes an alkoxysilane compound having a trialkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane. The alkoxysilane compound may be in the form of a low molecular weight compound, but if the alkoxysilane compound further has a polymerizable group, it may be in the form of a homopolymer, for example, co-polymerized with the above radical polymerizable compound. It may be a combined mode.
The content of the alkoxysilane compound in the photocurable resin composition is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the photocurable resin composition component excluding the alkoxysilane compound and the organic solvent. More preferably, it is 20 parts by mass.

  As described above, an alkoxysilane compound is included in the photocurable resin composition in order to impart adhesion to the substrate, but it is preferable to use acidic conditions when the photocurable resin composition is cured. Therefore, it is preferable to include a photoacid generator in the photocurable resin composition. Since the alkoxysilane and the compound (A) are almost neutral, the adhesion imparting effect of the alkoxysilane compound can be efficiently exhibited without inhibiting the acid generated from the photoacid generator. The photoacid generator is not particularly limited as long as it is a commonly used photoacid generator. Examples thereof include onium salt photoacid generators such as sulfonium salts and iodonium salts; nonionic photoacid generators such as imide sulfonates and oxime sulfonates; and the like.

The content of the photoacid generator in the photocurable resin composition of one embodiment of the present invention is 0.01 with respect to 100 parts by mass of the photocurable resin composition component excluding the photoacid generator and the organic solvent. It is preferably ˜20 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass.
When the photoacid generator is contained in the photocurable resin composition within the above range, the patterning performance can be improved when used in combination with a polymer that undergoes a deprotection reaction with an acid. In addition, since the compound (A) which is one embodiment of the present invention is neutral, alkoxysilane is used as a component of a photocurable resin composition for a permanent film such as an insulating film such as a display body using a glass substrate. When the compound is used in combination with a photoacid generator, the adhesion between the insulating film and the substrate can be improved. Furthermore, when using together the crosslinking agent which has a crosslinking action with an acid with a photo-acid generator, the crosslinking density of a photocurable resin composition can be raised.

The polymerization inhibitor is contained in the photocurable resin composition for the purpose of improving storage stability. The content of the polymerization inhibitor in the photocurable resin composition is preferably 0.0001 to 10 parts by mass with respect to 100 parts by mass of the photocurable resin composition component excluding the polymerization inhibitor and the organic solvent, It is more preferable that it is 0.001-1 mass part.
The polymerization inhibitor may contain (4-hydroxy) -phenyl methacrylate, 4-hydroxystyrene, α-methyl 4-hydroxystyrene, or the like as a monomer component constituting the polymer described later.

The photocurable resin composition according to one embodiment of the present invention preferably further contains a polymer containing at least one unit selected from the group consisting of the following (a) to (d).
(A) a unit having a carboxyl group (b) a unit having a group in which the carboxyl group is protected with an acid dissociable group (c) a unit having an oxiranyl group (d) a unit having an oxetanyl group In the case of containing a coalescence, it is preferably 0 to less than 100 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of all components of the photocurable resin composition excluding the organic solvent. More preferred.

When the polymer includes a unit having a carboxyl group (hereinafter, also referred to as “unit (a)”), development characteristics are improved. Examples of the unit (a) include units derived from monomers such as unsaturated carboxylic acids having at least one carboxy group in the molecule such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. It is done.
When the polymer includes a unit having a residue in which carboxyl is protected with an acid dissociable group (hereinafter, also referred to as “unit (b)”), a highly sensitive photocurable resin composition can be obtained. it can. As the acid dissociable group of the unit (b), known acid dissociable groups for the resist can be used, and are not particularly limited. Examples thereof include an ester group, an acetal group, a ketal group, a tetrahydropyranyl group, a t-butyl ester group, a siloxy group, and a benzyloxy group. Examples of the polymer containing a unit having a group in which a carbonyl group is protected with an acid dissociable group include a polymer having a styrene skeleton, a methacrylate or an acrylate skeleton pendant with these acid dissociable groups.

When the polymer has a unit having an oxiranyl group (hereinafter, also referred to as “unit (c)”), it can be crosslinked at a high temperature and in the presence of an acid or base catalyst. Examples of the unit (c) include units having a glycidyl group, a 3,4-epoxycyclohexylmethyl group, and the like. Unit (c) is derived from a monomer having an oxiranyl group.
When the polymer has a unit having an oxetanyl group (hereinafter, also referred to as “unit (d)”), it can be crosslinked in the same manner as the oxiranyl group. Examples of the unit (d) include units having a 3-methyloxetanyl group, a 3-ethyloxetanyl group, and the like. The unit (d) is derived from a monomer having an oxetanyl group.
The units (a) to (d) are each preferably 0 to 100% by mass, and preferably 10 to 50% by mass, based on all units constituting the polymer.

  The photocurable resin composition according to one embodiment of the present invention may further contain a crosslinking agent. Examples of the cross-linking agent include cross-linkable polymers containing units having a phenolic hydroxyl group and a carboxyl group; hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, and the like. Crosslinkable compounds; and the like. When a photocurable resin composition contains a crosslinking agent, it is preferable to make it contain 0-20 mass parts with respect to 100 mass parts of photocurable resin composition components except a crosslinking agent and an organic solvent.

For example, by irradiating the photocurable resin composition with light having a wavelength of 200 to 400 nm, the compound (A) self-cleaves to generate a radical, and using this radical as a trigger, The said compound (A) itself or the radically polymerizable compound added as needed polymerizes, and photocured material is formed. And since the said compound (A) has the substituent of R < ³ > and R < ⁴ > couple | bonded with the para position to each of two phenyl groups, since it can suppress the wavelength increase by a deactivation reaction, the molar absorption coefficient in 400 nm is shown. It can be set as the said range. Further, since the compound (A) and the chemical species generated by cleavage of the compound (A) have R ³ and R ⁴ substituents, and optionally R ⁵ and R ⁶ substituents, the molecular weight is increased. And, since the intermolecular interaction becomes strong, it is not easily volatilized and is held in the photocured product. Therefore, the bleeding out of the radical polymerization initiator component and its cleavage product over time, which has been a problem after photocuring, can be greatly suppressed.

<2> Device Manufacturing Method One embodiment of the present invention includes a resist film forming step of forming a resist film on a substrate using the photocurable resin composition, and an active energy ray to form the resist film. It is a device manufacturing method including a photolithography step of exposing in a pattern and a pattern forming step of developing the exposed resist film to obtain a photoresist pattern.

The active energy ray used for exposure in the photolithography process may be light that can activate radical photopolymerization initiators in some embodiments of the present invention to generate radicals. KrF excimer laser light, ArF excimer laser light , F ₂ excimer laser light, electron beam, UV, visible light, X-ray, electron beam, ion beam, i-ray, EUV, and the like. Preferably, it is i line.

What is necessary is just to follow the manufacturing method of a normal device except using the photocurable resin composition containing the said compound (A).
The substrate is preferably a glass substrate. When the photocurable resin composition contains an alkoxysilane compound, the adhesion between the resist film of the photocurable resin composition and the substrate is improved. The substrate is preferably a plastic substrate.

  EXAMPLES Hereinafter, although it demonstrates still in detail with the Example which concerns on some aspects of this invention, this invention is not restrict | limited at all by these Examples.

<Synthesis of Compound 1>
(Synthesis of 4,4′-dihydroxybenzyl)

  Dissolve 5.0 g of 4,4′-dimethoxybenzyl in 95 ml of acetic acid. To this, 31.2 g of 48 mass% HBr aqueous solution is dropped at 70 ° C. over 10 minutes. After dropping, the mixture is stirred at 110 ° C. for 70 hours. Thereafter, 150 g of water is added for crystallization. This is filtered, and the crystals are washed with 250 g of water and dried to obtain 4.0 g of 4,4′-dihydroxybenzyl which is the target product.

(Synthesis of 2,2-dimethoxy-1,2-di- (4-acetoxy) phenylethane-1-one)

1.6 g of 4,4′-dihydroxybenzyl and 0.16 g of sulfuric acid are dissolved in 12.8 g of methanol to 25 ° C. To this, 4.2 g of trimethyl orthoformate is added dropwise and stirred for 15 hours. After adding 3.0 g of triethylamine at 30 ° C. and stirring for 5 minutes, methanol as a solvent is distilled off. And it crystallizes by adding 14g of acetonitrile to the obtained residue. The crystals obtained by filtering this are dispersed again in 14 g of acetonitrile. After 1.7 g of triethylamine and 0.081 g of dimethylaminopyridine are added thereto, 1.7 g of acetic anhydride diluted with 5.0 g of acetonitrile is added dropwise at 30 ° C. After completion of the dropwise addition, the mixture is stirred at 25 ° C. for 2 hours, and then 64 g of 3 mass% NaHCO ₃ aqueous solution is added and stirred for 5 minutes. Thereafter, the mixture was extracted with 32 g of ethyl acetate, washed 3 times with 10 g of water and once with 10 g of saturated saline, and then the solvent was distilled off to obtain 2,2-dimethoxy-1,2-di- (4 -Acetoxy) phenylethane-1-one (compound 1) 1.35g. The purity of the obtained compound 1 is 99.2%, and the molar extinction coefficient at 365 nm is 1.5 × 10 ⁵ cm ² / mol. The pKa is about 7.
The purity of the compound was determined by high performance liquid chromatography (HPLC). The conditions for HPLC analysis are as follows.
Column: SUISEIODO ODS made by SHISEIDO
Eluent: acetonitrile: water = 80: 20 (volume ratio) mixed solvent detection wavelength: 254 nm

<Synthesis of Compound 2>
(Synthesis of 2,2-dimethoxy-1,2-di- (4-methoxy) phenylethane-1-one)

1.8 g of 4,4′-dimethoxybenzyl and 0.16 g of sulfuric acid are dissolved in 12.8 g of methanol to 25 ° C. To this, 4.2 g of trimethyl orthoformate is added dropwise and stirred for 15 hours. After adding 3.0 g of triethylamine at 30 ° C. and stirring for 5 minutes, methanol as a solvent is distilled off. Thereafter, redissolved with 32 g of ethyl acetate, washed 3 times with 10 g of water and once with 10 g of saturated saline, and then the solvent was distilled off to remove 2,2-dimethoxy-1,2-di- ( 1.6 g of 4-methoxy) phenylethane-1-one (compound 2) are obtained. The purity of the obtained compound 2 is 98.9%, and the molar extinction coefficient at 365 nm is 2.1 × 10 ⁵ cm ² / mol. The pKa is about 7.

<Synthesis of Compound 3>
(Synthesis of 4,4′-dimethylthiobenzyl)

  Add 18.7 g of thioanisole to 56 g of methylene chloride and bring to 0 ° C. To this is added 11.6 g of aluminum chloride. To this, 10.0 g of oxalyl chloride is added dropwise over 10 minutes. After dropping, the mixture is stirred at 0 ° C. for 1 hour. After further stirring at 25 ° C. for 1 hour, 100 g of water is added and the mixture is separated. The obtained organic layer is further washed with 50 g of water three times, and then the solvent is distilled off. By recrystallizing the obtained residue using ethanol, 10.7 g of 4,4′-dimethylthiobenzyl which is the target product is obtained.

(Synthesis of 2,2-dimethoxy-1,2-di- (4-methylthio) phenylethane-1-one)

Except for using 4,4′-dimethylthiobenzyl instead of 4,4′-dimethoxybenzyl, the same operation as in the above <Synthesis of Compound 2> was carried out to give 2,2-dimethoxy-1,2-di -(4-Methylthio) phenylethane-1-one (compound 3) is obtained in a yield of 82 mol% and a purity of 98.3%. The molar extinction coefficient at 365 nm is in the range of 2.0 × 10 ^{5 to} 1.5 × 10 ⁶ cm ² / mol, and the pKa is about 7.

<Synthesis of Compound 4>
Synthesis of 2,2-dimethoxy-1,2-di- (4-methanesulfonyl) phenylethane-1-one)

Add 3.0 g of 2,2-dimethoxy-1,2-di- (4-methylthio) phenylethane-1-one and 0.07 g of potassium hydroxide to 27 g of methanol and bring to 25 ° C. To this, 4.7 g of 35% hydrogen peroxide solution is dropped over 10 minutes. After dropping, the mixture is stirred at 25 ° C. for 3 hours. Thereafter, methanol is distilled off, and 28 g of methylene chloride is added for extraction. This is separated, and the obtained organic layer is further washed with 20 g of water three times, and then the solvent is distilled off. The obtained residue is purified by column chromatography (methylene chloride), whereby 2,2-dimethoxy-1,2-di- (4-methanesulfonyl) phenylethane-1-one (Compound 4), which is the target product. 2.7 g, 97.6% purity. The molar extinction coefficient at 365 nm is in the range of 1.0 × 10 ^{5 to} 1.0 × 10 ⁶ cm ² / mol, and the pKa is about 7.

<Volatility test>
Compound 1 (2,2-dimethoxy-1,2-di- (4-acetoxy) phenylethane-1-one) obtained above and compound 3 (2,2-dimethoxy-1,2-di-) The volatility of (4-methylthio) phenylethane-1-one) is evaluated. IRGACURE651 is used for comparison. Compound 1, Compound 3 and IRGACURE 651 were weighed in a 5.00 mg aluminum container, and each was measured at 130 ° C. and 15 ° C. using a differential thermal-thermal mass simultaneous measurement apparatus (TG-DTA: TG-DTA 2000S manufactured by Material Analysis and Characterization). Volatility is evaluated by measuring the mass loss rate per minute.

  As a result, in both cases of Compound 1 and Compound 3 to which an acetyl group and a methylthio group are added, the volatility is sufficiently reduced as compared with the conventional IRGACURE 651 at the temperature used in the solvent volatilization step. Recognize.

Example 1
<Synthesis of Copolymer A>
3.0 g of methacrylic acid, 8.7 g of glycidyl methacrylate, 3.4 g of 2-hydroxyethyl methacrylate, (4-hydroxy) -phenyl methacrylate, 1.8 g of styrene, dimethyl-2,2′-azobis (2 -Methyl propionate) is dissolved in propylene glycol-1-monomethyl ether acetate (PGMEA) and deoxygenated. This is dripped in 7.5 g of PGMEA previously heated at 85 degreeC over 4 hours. After dropping, the mixture is stirred for 2 hours and then cooled. It reprecipitates by dripping at 220 g of hexane after cooling. This is filtered and vacuum dried to obtain 10.4 g of the desired copolymer A.

<Preparation of photocurable resin composition>
Copolymer A obtained above, propylene glycol diglycidyl ether acrylic acid adduct (trade name: epoxy ester 70PA, manufactured by Kyoeisha Chemical Co., Ltd.) (monomer A), pentaerythritol tetraacrylate (trade name: LIGHT Acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.) (Monomer B) and Compound 1 as a radical polymerization initiator were weighed and diluted with propylene glycol monomethyl ether acetate (PGMEA) at room temperature (25 ° C.). The mixture is stirred and mixed to prepare a photocurable resin composition. Details of the formulation are shown in Table 2.

<Sensitivity evaluation>
The obtained photocurable resin composition is spin-coated on a silicon wafer that has been subjected to a hexamethylene disilazane (HMDS) treatment in advance, and then pre-baked (PB) at 130 ° C. for 3 minutes to produce a film of about 10 μm. . Using a high pressure mercury lamp with an exposure wavelength of 365 nm ± 5 nm as a light source using a band pass filter, an exposure apparatus (HMW-661C-3, manufactured by Oak Manufacturing Co., Ltd.) is used via a photomask. The photocurable resin composition is cured by exposing to light. After curing, a pattern of 100 μm is created by developing with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute and washing with pure water for 1 minute, and the minimum exposure amount at that time is defined as sensitivity (E _max ). The integrated exposure amount of the sample is calculated from the illuminance obtained by using a 365 nm light receiver of an illuminometer (UIT-150-A, manufactured by USHIO INC.). The results are shown in Table 3.

<Transmittance evaluation>
The obtained photocurable resin composition is spin-coated on non-alkali glass, and then pre-baked (PB) at 130 ° C. for 1 minute to produce a film of about 10 μm. An exposure apparatus (HMW-661C-3, manufactured by Oak Manufacturing Co., Ltd.) is used without a photomask as a high pressure mercury lamp with an exposure wavelength of 365 nm ± 5 nm using a bandpass filter. The photocurable resin composition is cured by exposing to 1000 mJ / cm ² . After curing, the visible light transmittance is determined by measuring the transmittance at 400 nm with an ultraviolet-visible light measuring device (UV-VIS). Transparency is good when the 400 nm transmittance in a 10 μm thick film is 95% or more. The results are shown in Table 3.

<Glass adhesion evaluation>
A composition shown in Table 2 was mixed with 0.5 g of N-triisopropylbenzenesulfonyloxy-1,8-naphthalimide as a photoacid generator and 10 g of 3-methacryloxypropyltrimethoxysilane as an alkoxysilane compound. A photocurable resin composition for glass adhesion test is prepared.

The obtained photocurable resin composition is spin-coated on an alkali-free glass, and then prebaked (PB) at 100 ° C. for 2 minutes to produce a film of about 10 μm. An exposure apparatus (HMW-661C-3, manufactured by Oak Manufacturing Co., Ltd.) is used without a photomask as a high pressure mercury lamp with an exposure wavelength of 365 nm ± 5 nm using a bandpass filter. The photocurable resin composition is cured by exposure to 200 mJ / cm ² . After curing, prebaking is performed at 120 ° C. for 3 minutes.
After that, according to JIS K5400, 100 grids of 1 mm are prepared in a 1 cm square with a cutter and peeled off by adhesion, and the remaining number of grids on the glass substrate is confirmed with an optical microscope. The glass substrate adhesion is evaluated by performing a cross-cut test under the condition that no lattice is peeled off from the glass substrate and all the cases where peeling is confirmed are x. The results are shown in Table 4.

(Example 2)
As a radical polymerization initiator, in place of the compound 1 (2,2-dimethoxy-1,2-di- (4-acetoxy) phenylethane-1-one, the compound 2 (2,2-dimethoxy-1,2- A photocurable resin composition is prepared in the same manner as in Example 1 except that -di- (4-methoxy) phenylethane-1-one is used, and various evaluations are performed in the same manner as in Example 1.

(Comparative Example 1)
A photocurable resin composition is prepared in the same manner as in Example 1 except that IRGACURE 651 is used in place of Compound 1 as a radical polymerization initiator, and various evaluations are performed in the same manner as in Example 1.

(Comparative Example 2)
A photocurable resin composition is prepared in the same manner as in Example 1 except that IRGACURE907 is used in place of the compound 1 as a radical polymerization initiator, and various evaluations are performed in the same manner as in Example 1.

As shown in Table 3, when using compounds 1 and 2 having a substituent at the para-position as a radical polymerization initiator, the sensitivity comparable to that of the comparative example can be maintained and high visible light transmittance can be maintained. I can do it.
On the other hand, IRGACURE 651 having no substituent at the para position is colored after exposure and the visible light transmittance is reduced to 93%. This is thought to be because the conjugation length is extended by causing a rearrangement reaction in which the radical after photolysis recombines to the para-position, resulting in a longer wavelength. In the case of having a substituent at the para position, it is considered that no coloration was observed even by light irradiation because the conjugation length does not increase and the wavelength does not increase because reattachment cannot be performed at the para position. .
Since Irgacure 907 has a methylthio group at the para-position of the benzoyl radical, it can suppress the increase in wavelength, and the 2-morpholino-isopropyl radical generated after cleavage has a short conjugation length, so the effect of increasing the wavelength is small even when transferred. , Visible light transmittance can be maintained. However, the sensitivity is slightly inferior to the others.

As shown in Table 4, in Examples 1 and 2 and Comparative Example 1, peeling from the glass substrate was not observed, and high glass substrate adhesion was exhibited. This is considered to be due to the effect that the glass adhesion is increased by heating after exposure because the silane coupling agent is hydrolyzed by the acid generated in the exposed portion due to the effect of the photoacid generator.
On the other hand, most of Comparative Example 2 is peeled off from the substrate. This is because, in Comparative Example 2, IRGACURE907 used as the radical polymerizable initiator has an amino group, so that the acid generated by exposure is neutralized, and hydrolysis of the silane coupling agent does not proceed and the glass adhesion is low. This is thought to be due to inadequate.
From the above results, it can be said that the photocurable resin composition according to some embodiments of the present invention is suitable for optical material applications that can achieve both high glass adhesion and visible light transmittance.

  According to some embodiments of the present invention, light comprising a radical polymerization initiator that has a moderate molar extinction coefficient at 365 nm and retains transmittance, and has high transmittance in the visible light region after curing and is neutral. A curable resin composition can be provided.

Claims (10)

The photocurable resin composition containing the compound represented by the following general formula (A) which generate | occur | produces a radical by light, and a radically polymerizable compound.

(In the general formula (A), R ¹ and R ² each represents a linear or branched alkyl group or alkenyl group which may have a substituent, and may be the same or different from each other. ³ , R ⁴ , R ⁵ and R ⁶ are each a linear or branched alkyl group, alkyloxy group, alkylthio group, alkenyl group, alkenyloxy group, alkenylthio group, aryl which may have a substituent. Oxy group, arylthio group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyloxy group, alkenyloxycarbonyloxy group, aryloxycarbonyloxy group, alkylcarbonylamino group, alkenylcarbonylamino group, aryl Carbonylamino group, alkylsulfo A group selected from the group consisting of a ruoxy group, an alkenylsulfonyloxy group, an arylsulfonyloxy group, an alkylsulfonyl group and an alkenylsulfonyl group, and a nitro group, which may be the same or different from each other. m represents an integer of 0 to 4, respectively.   The photocurable resin composition according to claim 1, wherein the n and m are 0.   The photocurable resin composition according to claim 1 or 2, further comprising an alkoxysilane compound.   The photocurable resin composition according to any one of claims 1 to 3, further comprising a photoacid generator.   The photocurable resin composition according to any one of claims 1 to 4, further comprising a polymerization inhibitor. The photocurable resin composition as described in any one of Claims 1-5 which further contains the polymer containing the at least 1 unit selected from the group which consists of following (a)-(d).
(A) Unit having carboxyl group (b) Unit having carboxyl group protected by acid dissociable group (c) Unit having oxiranyl group (d) Unit having oxetanyl group   The photocurable resin composition as described in any one of Claims 1-6 which further contains a crosslinking agent. A resist film forming step of forming a resist film on a substrate using the photocurable resin composition according to claim 1;
A photolithographic step of exposing the resist film in a pattern using an active energy ray;
A pattern forming step of developing the exposed resist film to obtain a photoresist pattern.   The device manufacturing method according to claim 8, wherein the substrate is a glass substrate.   The device manufacturing method according to claim 8, wherein the substrate is a plastic substrate.