KR101972164B1 - Solvent for the production of photoresist - Google Patents

Abstract

(상기 화학식 중, R¹ 내지 R⁴는 동일하거나 상이하고, 각각 C_{1 -2}의 알킬기이고, R¹과 R³ 또는 R²와 R⁴는 서로 결합하여 각각 환을 형성하고 있을 수도 있음)A problem to be solved by the present invention is to provide a solvent or a solvent composition for photoresist which is excellent in solubility of an oxime ester photopolymerization initiator having high sensitivity and does not impair the characteristics of a paste composition for electronic materials.
A solving means of the present invention is a solvent or a solvent composition for dissolving an oxime ester photopolymerization initiator, which comprises a solvent A having at least one compound selected from the group consisting of a compound represented by the following formula (A) Solvent or solvent composition.
≪ Formula (A) >

(Wherein R ¹ to R ⁴ are the same or different and each is an alkyl group of C _{1 -2} , and R ¹ and R ³ or R ² and R ⁴ may be bonded to each other to form a ring)

Description

[0001] SOLVENT FOR THE PRODUCTION OF PHOTORESIST [0002]

The present invention relates to a solvent or a solvent composition for photoresist preparation excellent in solubility of a photopolymerization initiator, and a composition for preparing a photoresist comprising the solvent or the solvent composition for the photoresist.

In general, coloring of a display body such as a liquid crystal display or the like requires a color filter composed of pixel regions of red (R), green (G), blue (B), and yellow (Y) between two substrates . However, if the pixel areas of the color filter are buried without gaps, a contrast degradation occurs at the boundary thereof. In order to prevent this problem, a black matrix is generally formed in which pixel regions of respective colors are divided by black partition walls.

In general, a photoresist is used to form a black matrix or a color filter. The black matrix includes a metal shielding material and a non-metal shielding material. Recently, resin black matrix has been increasing as a non-metallic black matrix in terms of environment. The resin black matrix paste contains a light-shielding material, a binder resin, a polyfunctional monomer, a photopolymerization initiator, a solvent, and the like.

The black matrix is produced through the following steps (1) to (6).

(1) A black matrix paste is combined. (2) After coating on a substrate, the layer is thinned. (3) The solvent is evaporated at about 100 ° C to dry. (4) Light curing is performed by irradiating ultraviolet light having a intensity of about 100 mJ / cm ² . (5) Spray the sodium carbonate aqueous solution to wash unnecessary parts of the resin. (6) Heat curing at about 200 ° C.

In the light curing of the black matrix, the light reaching the deep portion is weakened due to the mixing of the light shielding agent contained in the paste composition. Therefore, it is necessary to contain a large amount of photopolymerization initiator having high sensitivity in the paste composition. And an oxime ester-based photopolymerization initiator having a carbazole skeleton as a photopolymerization initiator having high sensitivity (Patent Document 1). However, they are insoluble and it is difficult to dissolve a large amount of them in a solvent.

Therefore, in Patent Document 2, a mixed solvent containing cyclohexanone and cyclohexanone is used as a solvent for a paste of a black matrix from the solubility in a photopolymerization initiator (Patent Document 2). However, cyclohexanone is a concern for ecotoxicity, and as a VOC-regulated compound, an alternative solvent is required because there are regulations such as the necessity of setting an organic solvent operation leader.

Other commonly used solvents for color filters and black matrix applications include propylene glycol monomethyl ether acetate, 3-methoxybutanol acetate, 1,6-hexanediol diacetate, 1,3- Butylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanol acetate, propylene glycol diacetate, dipropylene glycol diacetate, di Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are used (Patent Document 3, Patent Document 4).

Japanese Patent No. 4448381 Japanese Patent Application Laid-Open No. 2009-173560 Japanese Patent Application Laid-Open No. 2009-271502 Japanese Patent Application Laid-Open No. 2010-249869

Accordingly, an object of the present invention is to provide a solvent or a solvent composition for photoresist which is excellent in solubility of an oxime ester-based photopolymerization initiator having high sensitivity in the production of photoresist and does not impair the properties of the paste composition for electronic materials .

Another object of the present invention is to provide a photoresist composition which comprises the above-mentioned solvent or solvent composition for photoresist and is excellent in coatability, pigment dispersibility, dye solubility, epoxy resin / acrylic resin solubility, dryness and safety .

As a result of intensive studies to solve the above problems, the present inventors have found that solubility of a high oxime ester-based photopolymerization initiator can be realized by using a specific solvent. Further, it is possible to further improve the coating properties, the pigment dispersibility, the dye solubility, the epoxy resin-acrylic resin solubility, the drying property, the safety and the like by mixing this solvent and a solvent generally used for electronic materials as necessary Respectively. The present invention has been completed based on these findings.

That is, the present invention relates to a solvent or a solvent composition for dissolving an oxime ester-based photopolymerization initiator, which comprises a solvent A containing at least one compound selected from the group consisting of a compound represented by the following formula (A) Or a solvent composition.

≪ Formula (A) >

(Wherein R ¹ to R ⁴ are the same or different and each is a C _{1 -2} alkyl group, and R ¹ and R ³ or R ² and R ⁴ may be bonded to each other to form a ring)

It is preferable that the solvent or the solvent composition for producing a photoresist of the present invention further contains at least one solvent B which is compatible with the solvent A. [

In the solvent or solvent composition for producing a photoresist of the present invention, the solvent A is preferably contained in an amount of 30 wt% or more, more preferably 50 wt% or more.

The oxime ester-based photopolymerization initiator is preferably a compound (P1) represented by the following formula (P1).

≪ Formula (P1) >

(In the formula, R ¹¹ represents a C ₂ acyl group or page noilgi, R ¹² is C _{1 - 6} represents a phenyl group that may have an alkyl group, or a substituent, R ¹³ is the formula (P2) or the formula ( P4)

≪ Formula (P2) >

(Wherein R ¹⁴ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an anthracyl group which may have a substituent, a thienyl which may have a substituent or a thienyl group which may have a substituent R ¹⁵ is a single bond or a divalent group represented by the following formula (P3), and when R ¹⁵ is a single bond, R ¹⁴ may be C ₆ H ₅ SC ₆ H ₄ - )

≪ Formula (P3) >

(In the formula, R ¹⁶ is C _{1 - 2} represents a alkyl group or a phenyl group)

≪ Formula (P4) >

(Wherein R < ¹⁵ > represents a single bond or a group represented by the above formula (P3)

The oxime ester-based photopolymerization initiator is preferably a compound (1) represented by the following formula (1).

≪ Formula (1) >

The oxime ester-based photopolymerization initiator is preferably a compound (2) represented by the following formula (2), and the solvent A is 1,3-dimethyl-3,4,5,6-tetrahydro- It is preferably a pyrimidone.

≪ Formula (2) >

The oxime ester-based photopolymerization initiator is preferably a compound (3) represented by the following formula (3), and the solvent A is 1,3-dimethyl-3,4,5,6-tetrahydro- It is preferably a pyrimidone.

≪ Formula (3) >

Preferably, the solubility of the oxime ester-based photopolymerization initiator at 20 캜 in the solvent or solvent composition for photoresist preparation of the present invention is 4 parts by weight or more based on 100 parts by weight of the solvent composition.

The present invention also provides a photoresist composition comprising an oxime ester photopolymerization initiator and a solvent or solvent composition for the photoresist.

The oxime ester photopolymerization initiator according to the present invention is a photoresist composition comprising a compound (1) represented by the following formula (1), a compound (2) represented by the following formula (2) Is preferably the compound (3) to be displayed.

≪ Formula (1) >

≪ Formula (2) >

≪ Formula (3) >

Preferably, the oxime ester-based photopolymerization initiator is the compound (1). Preferably, the oxime ester-based photopolymerization initiator is the compound (2), and the solvent A is 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone. Preferably, the oxime ester-based photopolymerization initiator is the compound (3), and the solvent A is 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone.

The solvent or solvent composition for photoresist of the present invention has a high solubility in the photopolymerization initiator and does not impair the properties of the paste composition for electronic materials. Further, according to the composition for the production of a photoresist of the present invention, a photoresist composition excellent in coatability, pigment dispersibility, dye solubility, epoxy resin / acrylic resin solubility, dryness and safety can be obtained.

[Solvent or solvent composition for photoresist preparation]

The solvent or the solvent composition for photoresist of the present invention is a solvent or a solvent composition for dissolving the oxime ester photopolymerization initiator and includes a solvent A having at least one compound selected from the group consisting of compounds represented by the following formula (A) .

≪ Formula (A) >

(Wherein R ¹ to R ⁴ are the same or different and each is a C _{1 -2} alkyl group, and R ¹ and R ³ or R ² and R ⁴ may be bonded to each other to form a ring)

<Solvent A>

The solvent A contained in the solvent for forming a photoresist of the present invention contains at least one compound selected from the group consisting of compounds represented by the following formula (A). Examples of the ring include a 2-imidazolidinone ring and a 2-pyrimidone ring.

&Lt; Formula (A) >

(Wherein R ¹ to R ⁴ are the same or different and each is an alkyl group of C _{1 -2} , and R ¹ and R ³ or R ² and R ⁴ may be bonded to each other to form a ring)

Specific examples of the solvent A include tetramethyl urea, tetraethyl urea, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro- 1H) pyrimidone, and preferably 1,3-dimethyl-2-imidazolidinone, tetramethyl urea, 1,3-dimethyl-3,4,5,6-tetrahydro- 1H) pyrimidinone. These may be used alone, or two or more of them may be used in combination. By using the solvent A, the oxime ester-based photopolymerization initiator can be dissolved at a high concentration.

The content of the solvent A in the solvent for forming a photoresist or the solvent composition is preferably 30 wt% or more (for example, 30 to 100 wt%), more preferably 50 wt% or more (for example, 50 to 100 wt% . When the content of the solvent A is less than 30% by weight, the solubility of the oxime ester-based photopolymerization initiator may not be sufficient. The content of the solvent A is the total amount of the two or more solvents in combination.

<Solvent B>

The solvent A contained in the solvent for forming a photoresist of the present invention may be used in combination with a solvent B generally used for electronic materials and compatible with the solvent A. When the oxime ester photopolymerization initiator is used in combination with the solvent B to form a photoresist composition, the oxime ester photopolymerization initiator is dissolved at a high concentration, and the coating property, the pigment dispersibility, the dye solubility, the epoxy resin / acrylic resin solubility, Composition, safety and the like can be improved.

The solvent B is not particularly limited as long as it is compatible with the solvent A, and examples thereof include (mono, di, tri) alkylene glycol monoalkyl ether, (mono, di) alkylene glycol dialkyl ether, (Cycloalkyl) acetates, C _{3 - 6} alcohols, C _{3 - 6} alkane diols, C _{3 - 6} alkane diol monoalkyl ethers, C _{3 - 6} alkanes, diol alkyl ether acetate, C _{3 - 6} alkane diol diacetate, glycerol triacetate, hydroxycarboxylic acid esters, hydroxycarboxylic acid diethyl ester, alkoxy, carboxylic acid esters, cyclic ketones, lactones, cyclic ethers, amides, pyridine Aromatic acetic acid, amines, and the like.

(Mono, di, tri) alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, Propylene glycol monomethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol n-butyl ether, Methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, and tripropylene glycol n-butyl ether.

(Mono, di) alkylene glycol dialkyl ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether , Propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, Methyl ethyl ether, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl n-butyl ether and the like.

(Mono, di) alkylene glycol alkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, di Ethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate , Dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate The like can be given.

Examples of the (mono, di) alkylene glycol diacetate include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, and dipropylene glycol diacetate. (Cyclo) alkyl acetates include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, cyclohexanol acetate and the like.

C _{3 - 6} As the alcohol, such as n- propyl alcohol, isopropyl alcohol, n- butyl alcohol, sec- butyl alcohol, tert- butyl alcohol, n- pentyl alcohol, n- hexyl alcohol, 2-hexyl alcohol and the like. C _{3 - 6} As the alkanediol, and the like such as 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol. C _{3 - 6} Examples of alkanediol mono alkyl ethers, and the like such as 3-methoxybutanol.

C _{3 - 6} As the alkanediol alkyl ether acetate, and the like such as 3-methoxybutanol acetate. C _{3 - 6} and the like are exemplified as the alkane diol diacetate, 1,3-butylene glycol acetate, 1,4-butanediol diacetate, 1,6-diacetate.

Examples of the hydroxycarboxylic acid ester include methyl lactate and ethyl lactate. Examples of the hydroxycarboxylic acid diester include lactic acid methyl acetate, lactic acid ethyl acetate and the like. Examples of the alkoxycarboxylic acid ester include methyl methoxypropionate and ethyl ethoxypropionate.

Examples of cyclic ketones include cyclopentanone, cyclohexanone, and 4-ketoisoperolone. Examples of the lactones include? -Butyrolactone,? -Butyrolactone,? -Caprolactone,? -Valerolactone,? -Valerolactone and? -Acetyl-? -Butyrolactone. As the cyclic ether, tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydrofurfuryl acetate and the like are exemplified.

As amides, dimethylformamide and the like are exemplified. Examples of the pyridine include pyridine, methylpyridine and the like. Examples of the aromatic acetate include phenyl acetate and the like. As the amines, diethylamine, triethylamine and the like are exemplified. The solvent B exemplified above may be used alone, or two or more of them may be used in combination.

The content of the solvent B in the solvent for forming a photoresist or the solvent composition is preferably, for example, 0 to 70% by weight, more preferably 0 to 50% by weight. If the content of the solvent B exceeds 70% by weight, the solubility of the oxime ester-based photopolymerization initiator may not be sufficient. The content of the solvent B is the total amount of two or more of them in combination.

The mixing ratio (weight) of the solvent A and the solvent B in the solvent for forming a photoresist or the solvent B is, for example, 100/0 to 30/70, preferably 100/0 to 50/50. When the amount of the solvent B is larger than that of the solvent A / the solvent B is 30/70, the solubility of the oxime ester-based photopolymerization initiator may not be sufficient. The amounts of the solvent A and the solvent B are the sum of the amounts of the two solvents when they are used in combination.

&Lt; Oxime ester-based photopolymerization initiator >

The oxime ester-based photopolymerization initiator is not particularly limited, and examples thereof include compounds represented by the following formula (P1).

&Lt; Formula (P1) >

(In the formula, R ¹¹ represents a C ₂ acyl group or page noilgi, R ¹² is C _{1 - 6} represents a phenyl group that may have an alkyl group, or a substituent, R ¹³ is the formula (P2) or the formula ( P4)

&Lt; Formula (P2) >

(Wherein R ¹⁴ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an anthracyl group which may have a substituent, a thienyl which may have a substituent or a thienyl group which may have a substituent R ¹⁵ is a single bond or a divalent group represented by the following formula (P3), and when R ¹⁵ is a single bond, R ¹⁴ may be C ₆ H ₅ SC ₆ H ₄ - )

&Lt; Formula (P3) >

(In the formula, R ¹⁶ is C _{1 - 2} represents a alkyl group or a phenyl group)

&Lt; Formula (P4) >

(Wherein R &lt; ¹⁵ &gt; represents a single bond or a group represented by the above formula (P3)

In the above formula (P1), examples of the C ₂ acyl group exemplified as R ¹¹ include an acetyl group and the like. In the above formula (P1), examples of the phenoyl group exemplified as R ¹¹ include a benzoyl group and the like. Examples of the C _1-6 alkyl group represented by R ¹² in the above formula (P1) include a methyl group and a hexyl group. In the above formula (P1), examples of the substituent which the phenyl group in R ¹² may have include a methyl group, a methoxypropyloxy group and the like.

Examples of the substituent that R ¹⁴ may have include a phenyl group, a naphthyl group, an anthracyl group or a thienyl group in the above formula (P2) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- tert- butyl and the like of C _{1 - 4} alkyl group; Such as C ₁ -C ₆ alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and 2,2- _{- 4} alkoxy group, and the like.

C ₁ is exemplified as R ¹⁶ In the formula (P3) _- as the _second group, for example, a methyl group, an ethyl group or the like.

The solvent or the solvent composition for a photoresist of the present invention is a compound represented by the following formula (1), a compound (2) represented by the following formula (2), or an oxime ester photopolymerization initiator The compound (3) represented by the following formula (3) is particularly preferably used, and two or more of them may be used in combination.

&Lt; Formula (1) >

&Lt; Formula (2) >

&Lt; Formula (3) >

When the solvent or the solvent composition for producing a photoresist of the present invention is used for the compound (2) represented by the formula (2) or for the compound (3) represented by the formula (3) , 3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone are preferable.

In the solvent or solvent composition for photoresist preparation of the present invention, an oxime ester-based photopolymerization initiator (for example, compounds (1), (2) or (3) (About 4 to 90 parts by weight), preferably 5 parts by weight or more (about 5 to 90 parts by weight), based on 100 parts by weight of the solvent or the solvent composition, , More preferably at least 6 parts by weight (about 6 to 90 parts by weight), even more preferably at least 8 parts by weight (about 8 to 90 parts by weight), particularly preferably at least 10 parts by weight )to be. The dissolution amount of the oxime ester-based photopolymerization initiator is a total amount thereof when two or more kinds are used in combination.

[Composition for Photoresist Preparation]

The composition for preparing a photoresist of the present invention is characterized by containing the oxime ester-based photopolymerization initiator and the solvent or solvent composition for the photoresist preparation.

The content of the oxime ester-based photopolymerization initiator in the composition for preparing a photoresist of the present invention is, for example, 4 wt% or more (about 4 to 90 wt%), preferably 5 wt% (About 6 to 90 wt%), more preferably 8 wt% or more (about 8 to 90 wt%), particularly preferably 10 wt% or more (about 10 to 90 wt%) can do. The content of the oxime ester-based photopolymerization initiator is a total amount of two or more of them in combination.

The content of the solvent or solvent composition for photoresist in the composition for preparing a photoresist of the present invention is, for example, not more than 96% by weight (about 10 to 96% by weight), preferably not more than 95% , More preferably not more than 94 wt% (about 10 to 94 wt%), more preferably not more than 92 wt% (about 10 to 92 wt%), particularly preferably not more than 90 wt% ).

The content of the solvent A in the composition for preparing a photoresist of the present invention is, for example, not more than 96% by weight (about 3 to 96% by weight), preferably not more than 95% (About 3 to 94% by weight), more preferably about 92% by weight (about 3 to 92% by weight), particularly preferably about 90% by weight . The content of the solvent A is the total amount of the two or more solvents in combination.

The oxime ester-based photopolymerization initiator is preferably a compound (1) represented by the following formula (1).

&Lt; Formula (1) >

The oxime ester-based photopolymerization initiator contained in the photoresist composition of the present invention is preferably a compound (2) represented by the following formula (2). In this case, the solvent A is preferably 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidone.

&Lt; Formula (2) >

The oxime ester-based photopolymerization initiator contained in the photoresist composition of the present invention is preferably a compound (3) represented by the following formula (3). In this case, the solvent A is preferably 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidone.

&Lt; Formula (3) >

The solvent A contained in the composition for preparing a photoresist of the present invention is preferably 4 times (weight) or more based on the oxime ester-based photopolymerization initiator solubility to the oxime ester-based photopolymerization initiator. The amount of the solvent A to be used may be, for example, 0.1 to 100 times (weight), preferably 1 to 50 times (weight), more preferably 1.5 to 25 times (weight) relative to the oxime ester photopolymerization initiator. The amount of the oxime ester-based photopolymerization initiator and the amount of the solvent A to be used is the total amount for each of the two or more kinds.

The photoresist composition of the present invention may contain the solvent B as described above in the solvent for forming a photoresist or the solvent composition. It is possible to improve the applicability of the composition for preparing a photoresist, the pigment dispersibility, the dye solubility, the epoxy resin / acrylic resin solubility, the drying property, the safety and the like by incorporating the oxime ester photopolymerization initiator at a high concentration .

In order to further improve the coating property, it is possible to use, for example, a composition for preparing a photoresist such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, Propylene glycol monomethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, (Mono-, di-, tri-, and tri-substituted) glycols such as propylene glycol methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether or tripropylene glycol n- Alkylene glycol monoalkyl ethers; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, di Propylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl ethyl ether, (Mono, di) alkylene glycol dialkyl ethers such as dipropylene glycol methyl n-butyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether Acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether (Mono, di) alkylene glycol alkyl ether acetates such as acetone, dipropylene glycol propyl ether acetate or dipropylene glycol butyl ether acetate Agent; (Mono, di) alkylene glycol diacetates such as ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate or dipropylene glycol diacetate; Or an alkoxycarboxylic acid ester such as methyl methoxypropionate or ethyl ethoxypropionate as the solvent B is effective.

Further, in order to improve the pigment dispersion and propylene glycol monomethyl ether monomethyl acetate such as C _{3 - 6} alkylene glycol alkyl ether acetate; It is effective to a combination of such ₆ alkanediol alkyl ether acetate as a solvent B _- or C _3, such as 3-methoxybutanol acetate.

Further, in order to improve the dye solubility, propylene glycol monomethyl ether, mono-C ₃ of the ₆ alkylene glycol monoalkyl ether; Propylene glycol monomethyl ether monomethyl acetate such as C _{3 - 6} alkylene glycol alkyl ether acetate; 3-methoxy butanol, etc. of C _{3 - 6} alkane diol mono alkyl ether; C _3, such as 3-methoxybutanol _acetate-6 alkanediol alkyl ether acetate; Hydroxycarboxylic acid esters such as methyl lactate or ethyl lactate; Hydroxycarboxylic acid diesters such as lactic acid methyl acetate or lactic acid ethyl acetate; n- propyl alcohol, isopropyl alcohol, n- butyl alcohol, sec- butyl alcohol, tert- butyl alcohol, n- pentyl C _3, such as alcohol, n- hexyl alcohol, or 2-ethylhexyl _alcohol-6 alcohol; It is effective to a combination of such ₆ alkane diols as solvent B _- or 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, etc. of C _3.

In order to further improve the solubility of the epoxy resin / acrylic resin, it is preferable to use ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Diethyleneglycol n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl (Mono-, di-, tri-) alkylene glycols such as ethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether and tripropylene glycol n- Monoalkyl ethers; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, di Propylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl ethyl ether, (Mono, di) alkylene glycol dialkyl ethers such as dipropylene glycol methyl n-butyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether Acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether (Mono, di) alkylene glycol alkyl ether acetates such as dipropylene glycol propyl ether acetate, dipropylene glycol propyl ether acetate and dipropylene glycol butyl ether acetate; (Mono, di) alkylene glycol diacetates such as ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate and dipropylene glycol diacetate; Cyclic ketones such as cyclopentanone, cyclohexanone, and 4-ketoisophosphorone; lactones such as? -butyrolactone,? -butyrolactone,? -caprolactone,? -valerolactone,? -valerolactone and? -acetyl-? -butyrolactone; Cyclic ethers such as tetrahydrofuran, tetrahydrofurfuryl alcohol and tetrahydrofurfuryl acetate; Amides such as dimethylformamide; Pyridine such as pyridine or methylpyridine; Aromatic acetates such as phenyl acetate; Or an amine such as diethylamine or triethylamine as solvent B is effective.

(Mono, di) C (meth) acrylates such as propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl n-propyl ether and dipropylene glycol methyl n-butyl ether _3-6 alkylene glycol C _{1 - 2} alkyl, C _{3 - 4} alkyl ethers; Or a (cyclo) alkyl acetate such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, cyclohexanol acetate or the like as solvent B is effective. The solvent B exemplified above may be used alone, or two or more of them may be used in combination.

[Example]

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

<Single>

Example 1

(1) (manufactured by Daicel's laboratory, which was synthesized by a method in accordance with the method described in Japanese Patent Application Laid-open No. 2006-516246) as an oxime ester photopolymerization initiator was used, and 1,3-dimethyl- A solution was prepared using 3,4,5,6-tetrahydro-2 (1H) pyrimidinone (DMTHP) to give the initiator concentration described in Table 1 (4 wt% to 15 wt%), The container was shaken by hand with light shaking, and the dissolution was visually confirmed.

In the dissolution state, the case where the insoluble matter can not be confirmed visually is indicated as &quot;?: Dissolution &quot;, and the case where the insoluble matter can be confirmed is defined as &quot; x: insoluble &quot;. The same goes for the following.

Examples 2 and 3, Comparative Example 1

The solubility of the oxime ester-based photopolymerization initiator was evaluated in the same manner as in Example 1 except that the solvent was changed to the solvent shown in Table 1.

The results of solubility evaluation of the oxime ester photopolymerization initiators of Examples 1 to 3 and Comparative Example 1 are shown in Table 1.

DMTHP: 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone (Wako Pure Chemical Industries, Ltd.)

DMI: 1,3-dimethyl-2-imidazolidinone (manufactured by Wako Pure Chemical Industries, Ltd.)

TMU: 1,1,3,3-tetramethyl urea (manufactured by Wako Pure Chemical Industries, Ltd.)

ANON: Cyclohexanone (manufactured by Kanto Kagaku)

Example 4

(1H) pyrimidinone (DMTHP) as a solvent under a condition of 20 占 폚 using a compound (2) (manufactured by BASF) as an oxime ester-based photopolymerization initiator. ), A solution was prepared so as to have the initiator concentration (20 wt% to 40 wt%) shown in Table 2, and the container was shaken by hand for about one minute and then dissolved or visually confirmed.

Examples 5 and 6, Comparative Examples 2 and 3

The solubility of the oxime ester-based photopolymerization initiator was evaluated in the same manner as in Example 4 except that the solvent was changed to the solvent shown in Table 2. [

The results of solubility evaluation of the oxime ester photopolymerization initiators of Examples 4 to 6 and Comparative Examples 2 and 3 are shown in Table 2.

DMTHP: 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone (Wako Pure Chemical Industries, Ltd.)

DMI: 1,3-dimethyl-2-imidazolidinone (manufactured by Wako Pure Chemical Industries, Ltd.)

TMU: 1,1,3,3-tetramethyl urea (manufactured by Wako Pure Chemical Industries, Ltd.)

ANON: Cyclohexanone (manufactured by Kanto Kagaku)

MMPGAC: Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd.)

<Mixed solvent system>

Example 7

(1) was used as the oxime ester-based photopolymerization initiator and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) was used as the solvent A (Sol.A) ) Pyrimidinone and 3-methoxybutanol acetate as a solvent B (Sol.B), which is generally used for electronic materials and is known to have good applicability and pigment dispersibility, is mixed at a ratio of 80:20 (weight ratio) . Thereafter, the oxime ester photopolymerization initiator (compound (1)) was adjusted to a solution of the initiator concentration (4 wt% to 7 wt%) described in Table 3 with the mixed solvent under the environment of 20 ° C, And the mixture was visually observed for dissolution.

Examples 8 to 14 and Comparative Examples 4 to 7

The oxime ester-based photopolymerization initiator (compound (1)) was added to the initiator concentration described in Table 3 (4% by weight to 4% by weight) in the same manner as in Example 7, 7% by weight) as a solution, and visually confirmed whether or not the solution was dissolved.

DMTHP: 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone (Wako Pure Chemical Industries, Ltd.)

DMI: 1,3-dimethyl-2-imidazolidinone (manufactured by Wako Pure Chemical Industries, Ltd.)

MBA: 3-methoxybutanol acetate (manufactured by Daicel Chemical Industries, Ltd.)

MMPGAC: Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd.)

1,3 BGDA: 1,3-butylene glycol diacetate (manufactured by Daicel Chemical Industries, Ltd.)

ANON: Cyclohexanone (manufactured by Kanto Kagaku)

Example 15

(2) as the oxime ester-based photopolymerization initiator and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) benzene as the solvent A (Sol.A) ) Pyrimidinone and 3-methoxybutanol acetate as a solvent B (Sol.B), which is generally used for electronic materials and is known to have good applicability and pigment dispersibility, is mixed at a ratio of 80:20 (weight ratio) . Thereafter, the oxime ester-based photopolymerization initiator (compound (2)) was adjusted to a solution of the initiator concentration (5 wt% to 30 wt%) described in Table 4 as the mixed solvent under the environment of 20 ° C, And the mixture was visually observed for dissolution.

Examples 16 to 20, Comparative Examples 8 and 9

The oxime ester photopolymerization initiator (compound (2)) was added to the initiator concentration (5 wt% to 5 wt%) shown in Table 4 under the environment of 20 DEG C, 30% by weight) as a solution, and the dissolution was visually confirmed.

DMTHP: 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidinone (Wako Pure Chemical Industries, Ltd.)

MBA: 3-methoxybutanol acetate (manufactured by Daicel Chemical Industries, Ltd.)

MMPGAC: Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd.)

ANON: Cyclohexanone (manufactured by Kanto Kagaku)

As can be seen from Tables 1 and 3, a mixed solvent of Solvent A (Sol. A) alone (Examples 1 to 3) and Solvent A (Sol.A) and Solvent B (Sol.B) Examples 7 to 14) exhibited excellent solubility of the compound (1) in the conventionally used mixed solvents containing cyclohexanone and cyclohexanone (Comparative Examples 1 and 4 to 7). As can be seen from Tables 2 and 4, the solvent A (Sol. A) alone (Examples 4 to 6) and the mixed solvent of Solvent A (Sol.A) and Solvent B (Sol.B) (Examples 15 to 20) were superior in solubility of Compound (2) to conventionally used mixed solvents containing cyclohexanone and cyclohexanone (Comparative Examples 2, 3, 8 and 9).

The solvent or solvent composition for photoresist of the present invention dissolves the oxime ester photopolymerization initiator at a high concentration, so that the photoresist can be efficiently produced.

Claims (14)

A solvent or a solvent composition for dissolving at least one oxime ester photopolymerization initiator selected from a compound (1) represented by the following formula (1) and a compound (2) represented by the following formula (2) And a compound represented by the following general formula (1): &quot; (1) &quot;
&Lt; Formula (1) >

&Lt; Formula (2) >

&Lt; Formula (A) &gt;

(Wherein R ¹ to R ⁴ are the same or different and each is a C _1-2 alkyl group, and R ¹ and R ³ , or R ² and R ⁴ may be bonded to each other to form a ring ) The solvent or solvent composition according to claim 1, further comprising at least one solvent B compatible with the solvent A. The solvent or solvent composition according to claim 2, wherein the solvent A comprises 30 wt% or more. The solvent or solvent composition according to claim 2, wherein the solvent A comprises 50 wt% or more. A solvent or a solvent composition for dissolving an oxime ester photopolymerization initiator represented by the following formula (2), wherein the solvent or solvent composition comprises at least 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) Solvent or solvent composition.
&Lt; Formula (2) >

The organic electroluminescent device according to any one of claims 1 to 4, wherein at least one member selected from the group consisting of a compound (1) represented by the following formula (1) and a compound (2) represented by the following formula (2) Wherein the solubility of the oxime ester photopolymerization initiator in the solvent or the solvent composition is 4 parts by weight or more based on 100 parts by weight of the solvent or the solvent composition.
&Lt; Formula (1) >

&Lt; Formula (2) >

At least one oxime ester photopolymerization initiator selected from a compound (1) represented by the following formula (1) and a compound (2) represented by the following formula (2) A composition for the production of a photoresist, which comprises a solvent or a solvent composition according to claim 1.
&Lt; Formula (1) >

&Lt; Formula (2) >

A photoresist composition comprising a solvent or a solvent composition comprising at least an oxime ester photopolymerization initiator represented by the following formula (2) and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) &Lt; / RTI >
&Lt; Formula (2) &gt;

The solvent or solvent composition according to claim 5, wherein the solubility of the oxime ester-based photopolymerization initiator represented by the following formula (2) at 20 占 폚 is 4 parts by weight or more based on 100 parts by weight of the solvent or the solvent composition.
&Lt; Formula (2) >

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