TWI575311B - Solvent or solvent composition for photoresist production - Google Patents

Description

Solvent or solvent composition for photoresist production

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

In general, the colorization of a display such as a liquid crystal display display is required to be in the field of pixels such as red (R) or green (G) or blue (B) or yellow (Y) between two substrates. A color filter constructed. However, if there is no gap between the respective pixel areas of the color filter, a contrast reduction or the like is generated at the boundary thereof. In order to prevent the problem, a black matrix in which the pixel areas of the respective colors are distinguished by black partition walls is usually formed.

In general, photoresist is used in the formation of black matrices or color filters. For the black matrix, there are those who use metal shading materials, and those who use non-metal shading materials. In recent years, due to environmental concerns, as a non-metallic black matrix, the resin black matrix is increasing. 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 manufactured by the following steps (1) to (6).

(1) Blending the black matrix paste. (2) After application to the substrate, thinning is performed. (3) The solvent was evaporated at about 100 ° C and dried. (4) UV curing is performed at a intensity of about 100 mJ/cm ^{2 to} carry out photocuring. (5) Spraying an aqueous solution of sodium carbonate to wash unnecessary resin components. (6) Heating at about 200 ° C for thermal hardening.

In the light hardening of the black matrix, the shading contained in the paste composition When the agent is blended, the light in the deep part becomes weak. Therefore, a large amount of a highly sensitive photopolymerization initiator must be contained in the paste composition. An oxime ester photopolymerization initiator having a carbazole skeleton is mentioned as a photopolymerization initiator having high sensitivity (Patent Document 1). However, these systems are poorly soluble and it is difficult to dissolve a large amount in a solvent.

Then, in Patent Document 2, as a solvent for a paste of a black matrix, a cyclohexane ketone and a mixed solvent containing cyclohexanone are used because of solubility in a photopolymerization initiator (Patent Document 2). However, the cyclohexanone is an ecotoxicity factor, and as a VOC-restricted compound, there is a need for a person in charge of the establishment of an organic solvent, and there is a limit to find a substitute solvent.

Other commonly used solvents for color filters and black matrix applications are propylene glycol monomethyl ether acetate, 3-methoxybutanol acetate, 1, due to coating properties or pigment dispersibility. 6-hexanediol diacetate, 1,3-butanediol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol II Ethyl ether, cyclohexanol acetate, propylene glycol diacetate, dipropylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. (Patent Document 3, Patent Literature) 4).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4438381

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-173560

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-271502

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-249869

In view of the above, it is an object of the present invention to provide a solvent or a solvent for producing a photoresist which is excellent in solubility in an oxime-based photopolymerization initiator having high sensitivity and which does not impair the properties of a paste composition for use in an electronic material. Composition.

Further, another object of the present invention is to provide a solvent or a solvent composition containing the above-mentioned photoresist, which is excellent in coatability, pigment dispersibility, dye solubility, epoxy resin, acrylic resin solubility, drying property, safety, and the like. Excellent photoresist manufacturing composition.

As a result of intensive studies to solve the above problems, the present inventors have found that high solubility of an oxime ester photopolymerization initiator can be achieved by using a specific solvent. Further, it has been found that the coating property, the pigment dispersibility, the dye solubility, the solubility of the epoxy resin, the acrylic resin, the drying property, and the safety can be further improved by mixing the solvent with a solvent generally used for electronic materials. Wait. The present invention has been completed based on such knowledge.

In other words, the present invention provides a solvent or a solvent composition for dissolving a photopolymerization initiator containing a solvent A, which is a solvent or a solvent composition for dissolving an oxime ester photopolymerization initiator, and the solvent A contains Having a selected from the formula (A) (In the above formula, R ¹ to R ⁴ are the same or different, 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 each) At least one compound of the group.

The solvent or solvent composition for producing a photoresist of the present invention preferably 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% by weight or more, and more preferably 50% by weight or more.

The above oxime ester-based photopolymerization initiator is preferably represented by the following formula (P1) The compound (P1) is represented. [In the above formula, R ¹¹ represents a C ₂ fluorenyl group or a phenyl fluorenyl group; R ¹² represents a C _1-6 alkyl group or a phenyl group which may have a substituent; and R ¹³ represents a formula (P2) (In the above formula, R ¹⁴ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a mercapto group which may have a substituent, a thienyl group which may have a substituent, or a diphenyl group which may have a substituent a thioether group; R ¹⁵ represents a single bond or is represented by the following formula (P3) (In the above formula, R ¹⁶ represents a C _1-2 alkyl group or a phenyl group.) represents a divalent group. Further, when R ¹⁵ is a single bond, the R ¹⁴ system may also be C ₆ H ₅ SC ₆ H ₄ -. Or the base represented by the following formula (P4) ₂ ON-R ¹⁵ - (P4) (in the above formula, the R ¹⁵ single bond or the base represented by the above formula (P3)). ]

The above oxime ester photopolymerization initiator is preferably represented by the following formula (1) Represented as compound (1).

Further, the above oxime ester-based photopolymerization initiator is preferably represented by the following formula (2) The compound (2) represented by the solvent A is preferably 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone.

Further, the above oxime ester-based photopolymerization initiator is preferably represented by the following formula (3) The compound (3) represented by the solvent A is preferably 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone.

The solvent or solvent composition for producing a photoresist of the present invention preferably has a solubility in an oxime ester photopolymerization initiator at 20 ° C of 4 parts by weight or more based on 100 parts by weight of the solvent composition.

Furthermore, the present invention provides a composition for producing a photoresist, which comprises an oxime ester-based photopolymerization initiator, a solvent or a solvent composition for producing the above-mentioned photoresist.

In the composition for producing a resist of the present invention, the oxime ester-based photopolymerization initiator is preferably a compound (1) represented by the following formula (1) or a compound (2) represented by the following formula (2). Or the compound (3) represented by the following formula (3).

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

The solvent or solvent composition for producing a photoresist of the present invention is a property of a photopolymerization initiator which has high solubility and does not impair the use of a paste composition for electronic materials. Further, according to the composition for producing a photoresist of the present invention, a composition for producing a photoresist which is excellent in coatability, pigment dispersibility, dye solubility, epoxy resin, acrylic resin solubility, drying property, safety, and the like can be obtained. .

[Formation of the Invention] [Solvent or solvent composition for photoresist production]

The solvent or solvent composition for producing a photoresist of the present invention contains a solvent or a solvent composition for dissolving an oxime ester-based photopolymerization initiator of the solvent A, and the solvent A has a selected from the group consisting of the following formula (A) (In the above formula, R ¹ to R ⁴ are the same or different, 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 each) At least one compound of the group.

<solvent A>

The solvent A or the solvent composition for producing a photoresist of the present invention contains at least one selected from the group consisting of the following formula (A). (In the above formula, R ¹ to R ⁴ are the same or different, 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 each) A compound of the group of compounds. Examples of the ring include a 2-imidazolidinone ring and a 2-pyrimidinone ring.

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

The content of the solvent A in the solvent or solvent composition for resist production is preferably 30% by weight or more (for example, 30 to 100% by weight), more preferably 50% by weight or more (for example, 50 to 100% by weight). %). When the content of the solvent A is less than 30% by weight, the solubility of the oxime ester photopolymerization initiator may be insufficient. In addition, in the case where the content of two or more kinds of the solvent A is used in combination, the total amount of these is the same.

<Solvent B>

The solvent A contained in the solvent for producing a photoresist or the solvent composition of the present invention may be further mixed with a solvent B which is generally used in the use of an electronic material and which is compatible with the solvent A. By using in combination with solvent B, the oxime ester When the photopolymerization initiator is dissolved to form a composition for producing a photoresist, the oxime ester photopolymerization initiator is dissolved at a high concentration, and the coating property, pigment dispersibility, dye solubility, and epoxy resin can be further improved. ‧Acrylic resin solubility, drying, safety, etc.

The solvent B is not particularly limited as long as it is compatible with the solvent A, and examples thereof include (mono, di, and tri) alkanediol monoalkyl ethers and (mono and di) alkanediol dialkyl groups. Ether, (mono, di) alkanediol alkyl ether acetate, (mono, di) alkanediol diacetate, (cyclo) alkyl acetate, C _3-6 alcohol, C _3-6 alkane Glycol, C _3-6 alkanediol monoalkyl ether, C _3-6 alkanediol alkyl ether acetate, C _3-6 alkanediol diacetate, triacetin, hydroxycarboxylate A hydroxycarboxylic acid diester, an alkoxycarboxylate, a cyclic ketone, a lactone, a cyclic ether, a decylamine, a pyridine, an aromatic acetate, an amine, or the like.

Examples of the (mono, di, and tri) alkanediol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, and diethylene glycol monomethyl ether. Diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol monoethyl ether , dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether and the like.

Examples of the (mono and di)alkylene glycol dialkyl ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropylene. 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, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl n-propyl ether , dipropylene glycol methyl n-butyl ether and the like.

Examples of the (mono- or di-)alkylene glycol alkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and 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 diethyl ether acetate, dipropylene glycol propyl ether Acetate, dipropylene glycol butyl ether acetate, and the like.

Examples of the (mono- or di-)alkylene glycol diacetate include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, and dipropylene glycol diacetate. The (cyclo)alkyl acetate may, for example, be methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate or cyclohexyl acetate.

Examples of the C _3-6 alcohol include n-propanol, isopropanol, n-butanol, secondary butyl alcohol, tertiary butyl alcohol, n-pentanol, n-hexanol, and 2-hexanol. The C _3-6 alkanediol may, for example, be 1,3-butanediol, 1,4-butanediol or 1,6-hexanediol. As the C _3-6 alkanediol monoalkyl ether, 3-methoxybutanol or the like can be exemplified.

The C _3-6 alkanediol alkyl ether acetate may, for example, be 3-methoxybutanol acetate or the like. As the C _3-6 alkanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, and 1,6-hexanediol diacetate can be exemplified. Wait.

Examples of the hydroxycarboxylic acid esters include methyl lactate and ethyl lactate. As the hydroxycarboxylic acid diester, methyl lactate or ethyl acetate lactate can be exemplified Ester and the like. The alkoxycarboxylate may, for example, be methyl methoxypropionate or ethyl ethoxypropionate.

Examples of the cyclic ketone include cyclopentanone, cyclohexanone, and 4-oxoisophorone. Examples of the lactones include β-butyrolactone, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, α-ethinyl-γ-butyrolactone, and the like. Examples of the cyclic ether include tetrahydrofuran, tetrahydrofurfuryl alcohol, and tetrahydrofurfuryl acetate.

Examples of the guanamines include dimethylformamide and the like. Examples of the pyridines include pyridine and picoline. As the aromatic acetate, phenyl acetate or the like can be exemplified. Examples of the amines include diethylamine and triethylamine. The solvent B exemplified above may be used singly or in combination of two or more.

The content of the solvent B in the solvent or solvent composition for photoresist production is, for example, preferably from 0 to 70% by weight, and more preferably from 0 to 50% by weight. When the content of the solvent B is more than 70% by weight, the solubility of the oxime ester photopolymerization initiator may be insufficient. In addition, when the content of the solvent B is used in combination of two or more kinds, it is the total amount of these.

The mixing ratio (by weight) of the solvent A and the solvent B in the solvent or solvent composition for photoresist production is, for example, 100/0 to 30/70, preferably 100/0 to 50/50. . When the solvent B is more than the solvent A/solvent B 30/70, the solubility of the oxime ester photopolymerization initiator is insufficient. In addition, when the amount of the solvent A or the solvent B is used in combination of two or more kinds, the total amount is determined.

<肟 ester photopolymerization initiator>

The oxime ester photopolymerization initiator is not particularly limited, and examples thereof include the following formula (P1). Expressed as a compound.

In the above formula, R ¹¹ represents a C ₂ fluorenyl group or a phenyl fluorenyl group; R ¹² represents a C _1-6 alkyl group or a phenyl group which may have a substituent; and R ¹³ represents a formula (P2) [In the above formula, R ¹⁴ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a fluorenyl group which may have a substituent, a thienyl group which may have a substituent, or a diphenyl group which may have a substituent a thioether group; R ¹⁵ represents a single bond or is represented by the following formula (P3) (In the above formula, R ¹⁶ represents a C _1-2 alkyl group or a phenyl group.) represents a divalent group. Further, when R ¹⁵ is a single bond, the R ¹⁴ system may also be C ₆ H ₅ SC ₆ H ₄ -. Or a group represented by the following formula (P4) ₂ ON-R ¹⁵ - (P4) (wherein R ¹⁵ represents a single bond or a group represented by the above formula (P3)).

In the above formula (P1), the C ₂ fluorenyl group as R ¹¹ is exemplified by, for example, an ethenyl group. In the above formula (P1), examples of the benzoquinone group as R ¹¹ include a benzamidine group and the like. In the above formula (P1), a C _1-6 alkyl group as R ¹² is exemplified by a methyl group, a hexyl group and the like. In the above formula (P1), examples of the substituent which may have a phenyl group in R ¹² include a methyl group, a methoxypropoxy group and the like.

In the above formula (P2), examples of the substituent which may have a phenyl group, a naphthyl group, a fluorenyl group or a thienyl group in R ¹⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. a C _1-4 alkyl group such as isobutyl, secondary butyl or tert-butyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, Butoxy, tertiary butoxy, 2,2-dimethyl-1,3- A C _1-4 alkoxy group such as a 4-methoxy group.

In the above formula (P3), examples of the C _1-2 alkyl group as R ¹⁶ include a methyl group and an ethyl group.

The solvent or solvent composition for producing a photoresist of the present invention is preferably a compound (1) represented by the following formula (1) or a compound (2) represented by the following formula (2). In addition, the compound (3) represented by the following formula (3) is used as the oxime ester-based photopolymerization initiator, and two or more of these may be used in combination.

The solvent or solvent composition for producing a photoresist of the present invention is used as the solvent A in the case of using the compound (2) represented by the above formula (2) or the compound (3) represented by the above formula (3). Preferably, it is 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone.

The solvent or solvent composition for producing a photoresist of the present invention, an oxime ester photopolymerization initiator at 20 ° C [for example, the above formula (1), (2) or (3) The solubility of the compound (1), (2) or (3)] is, for example, 4 parts by weight or more (about 4 to 90 parts by weight), preferably 5 parts by weight, per 100 parts by weight of the solvent or solvent composition. The above (about 5 to 90 parts by weight) is more preferably 6 parts by weight or more (about 6 to 90 parts by weight), still more preferably 8 parts by weight or more (about 8 to 90 parts by weight), and particularly preferably 10 parts by weight or more. (about 10 to 90 parts by weight). In addition, when the amount of the oxime ester photopolymerization initiator is used in combination of two or more kinds, it is the total amount of these.

[Photoresist manufacturing composition]

The composition for producing a photoresist according to the present invention is characterized by comprising the above-described oxime ester-based photopolymerization initiator and the above-mentioned solvent for solvent production or solvent composition.

The content of the oxime ester photopolymerization initiator in the composition for producing a photoresist of the present invention may be, for example, 4% by weight or more (about 4 to 90% by weight), preferably 5% by weight or more (5) More preferably, it is about 90% by weight or more, more preferably 6% by weight or more (about 6 to 90% by weight), still more preferably 8% by weight or more (about 8 to 90% by weight), and particularly preferably 10% by weight or more (10~) 90% by weight or so). In addition, when the content of the oxime ester-based photopolymerization initiator is used in combination of two or more kinds, it is the total amount of these.

The content of the solvent or solvent composition for producing a photoresist in the composition for producing a photoresist of the present invention can be, for example, 96% by weight or less (about 10 to 96% by weight), preferably 95% by weight or less (preferably 95% by weight or less) 10 to 95% by weight or so, more preferably 94% by weight or less (about 10 to 94% by weight), still more preferably 92% by weight or less (about 10 to 92% by weight), and particularly preferably 90% by weight or less (10) ~90% by weight or so).

The content of the solvent A in the composition for producing a photoresist of the present invention is For example, it may be 96% by weight or less (about 3 to 96% by weight), preferably 95% by weight or less (about 3 to 95% by weight), more preferably 94% by weight or less (about 3 to 94% by weight), and further It is preferably 92% by weight or less (about 3 to 92% by weight), and particularly preferably 90% by weight or less (about 3 to 90% by weight). In addition, when the content of the solvent A is used in combination of two or more kinds, it is the total amount of these.

As the oxime ester photopolymerization initiator, it is preferred to have the following formula (1) Represented as compound (1).

In addition, the oxime ester photopolymerization initiator contained in the composition for producing a photoresist of the present invention preferably has the following formula (2) Represented by the compound (2). In this case, the solvent A is preferably 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone.

In addition, the oxime ester photopolymerization initiator contained in the composition for producing a photoresist of the present invention preferably has the following formula (3) Represented as compound (3). In this case, the solvent A is preferably 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone.

The solvent A contained in the composition for producing a photoresist of the present invention is preferably 4 times by weight or more based on the solubility of the oxime ester-based photopolymerization initiator. The amount of the solvent A to be used is, for example, 0.1 to 100 times by weight, preferably 1 to 50 times by weight, more preferably 1.5 to 25 times, based on the oxime ester photopolymerization initiator. weight). In addition, when the amount of use of the oxime ester-based photopolymerization initiator and the solvent A is used in combination of two or more kinds, the total amount is the total amount.

The composition for producing a photoresist according to the present invention may contain the solvent B as described above in the solvent or solvent composition for producing a photoresist. By using in combination with the solvent B, not only a high concentration oxime ester-based photopolymerization initiator, but also coating properties, pigment dispersibility, dye solubility, epoxy resin ‧ acrylic resin dissolution of the photoresist manufacturing composition can be further improved Sex, dryness, safety, etc.

In the composition for producing a photoresist, for example, the coating property is further improved, and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, and B are used. Glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol Butane, dipropylene 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-butyl ether (mono, di, tri) alkanediol Monoalkyl ether; 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 Methyl 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, dipropylene glycol methyl ethyl ether, dipropylene glycol (mono, di)alkylene glycol dialkyl ethers such as n-propyl ether or dipropylene glycol methyl n-butyl ether; 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 (mono- and di-alkane) such as monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, or dipropylene glycol butyl ether acetate Glycol alkyl ether acetate; ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, or dipropylene glycol diacetate (mono, di) alkanediol Acetate; or an alkoxycarboxylate such as methyl methoxypropionate or ethyl ethoxypropionate is effective as solvent B.

In addition, to more improve pigment dispersibility, and washed with propylene glycol monomethyl ether acetate, etc. The C _3-6 alkylene glycol mono alkyl ether acetate; or 3-methoxybutanol acetate, etc. C _{3- 6} alkanediol alkyl ether acetate or the like is effective as the solvent B system.

In addition, to more enhance the solubility of the dye, and the like with propylene glycol monomethyl ether mono C _3-6 alkylene glycol mono alkyl ether; C _3-6 alkyl glycol alkyl ether acetate, propylene glycol monomethyl ether acetate, etc. Single C _3-6 alkanediol monoether ether such as 3-methoxybutanol; C _3-6 alkanediol alkyl ether acetate such as 3-methoxybutanol acetate; a hydroxycarboxylic acid ester such as an ester or ethyl lactate; a hydroxycarboxylic acid diester such as methyl lactate or ethyl lactate; n-propanol, isopropanol, n-butanol, secondary butyl alcohol, and the like. C _3-6 alcohol such as butyl alcohol, n-pentanol, n-hexanol or 2-hexanol; or 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, etc. The C _3-6 alkanediol or the like is effective as the solvent B system.

In addition, in order to further improve the solubility of epoxy resin ‧ acrylic resin, and use ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, two Glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol monoethyl ether, two (mono, di-, tri) alkanediol monoalkyl ethers such as propylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether; 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 Ethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl n-butyl ether, etc. , b) alkanediol dialkyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol single Ether Acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol single Propyl 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 (mono and di)alkylene glycol alkyl ether acetates such as methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate; (mono, di) alkanediol diacetate such as diol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate; cyclopentanone, cyclohexanone a cyclic ketone such as 4-oxoisophorone; β-butyrolactone, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, α-ethenyl- a lactone such as γ-butyrolactone; a cyclic ether such as tetrahydrofuran, tetrahydrofurfuryl alcohol or tetrahydrofurfuryl acetate; a guanamine such as dimethylformamide; or a pyridine such as pyridine or methylpyridine. An aromatic acetate such as phenyl acetate; or An amine such as diethylamine or triethylamine is effective as the solvent B system.

In addition, in order to further improve the drying property, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl n-butyl ether and the like (single and di) C _3-6 alkane are used. a diol C _1-2 alkyl C _3-4 alkyl ether; or a (cyclo)alkane of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, cyclohexyl acetate or the like A base acetate or the like is effective as the solvent B system. The solvent B exemplified above may be used singly or in combination of two or more.

[Examples]

The invention is specifically illustrated by the following examples, but the invention is not limited thereto.

<individual system>

In the first embodiment, the compound (1) (manufactured by Daicel Co., Ltd. synthesized by the method described in JP-A-2006-516246) was used as an oxime ester photopolymerization initiator, and it was used at 20 ° C. 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone (DMTHP) was prepared as a solvent to prepare a starter concentration as shown in Table 1 (4% by weight to 15% by weight). The solution was shaken in a hand-shake container for about 1 minute, and visually confirmed whether or not it was dissolved.

In addition, in the case of the dissolution state, the case where the insoluble matter could not be confirmed by visual observation was regarded as "○: dissolution", and the case where the insoluble matter was confirmed was regarded as "x: insoluble". The same is true below.

Examples 2 to 3, Comparative Example 1

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

Example 4

Compound (2) (manufactured by BASF) was used as an oxime ester photopolymerization initiator, and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidine was used at 20 ° C. The ketone (DMTHP) was prepared as a solvent to prepare a solution having a concentration of the initiator (20% by weight to 40% by weight) as shown in Table 2, and the mixture was gently shaken in a hand for about 1 minute, and then visually confirmed to be soluble.

Examples 5 to 6 and Comparative Examples 2 to 3

The solvent was changed to the solvent shown in Table 2, and the solubility in the oxime ester photopolymerization initiator was evaluated in the same manner as in Example 4.

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

<Mixed solvent system> Example 7

The compound (1) is used as an oxime ester photopolymerization initiator, and the solvent A (Sol. A) which is a good solubility of the oxime ester photopolymerization initiator is 1,3-dimethyl 3-methoxy-3,4,5,6-tetrahydro-2(1H)pyrimidinone, and 3-methoxyl which is known as a coating material and is excellent in pigment dispersibility (Sol. B), which is generally used for electronic materials. The butanol acetate was mixed in a ratio of 80:20 by weight. Then, the oxime ester photopolymerization initiator [compound (1)] was adjusted to a concentration of the initiator (4% by weight to 7% by weight) as shown in Table 3 in the above-mentioned mixed solvent at 20 ° C. The solution was gently shaken in a hand for about 1 minute, and then visually confirmed whether or not it was dissolved.

Examples 8 to 14 and Comparative Examples 4 to 7

In the same manner as in Example 7, the solvent described in the following Table 3 was mixed at a weight ratio described in Table 3, and the oxime ester photopolymerization initiator [Compound (1)] was prepared as a record in an environment of 20 ° C. The solution of the initiator concentration (4% by weight to 7% by weight) in Table 3 was visually confirmed to be soluble.

1,3BGDA: 1,3-butylene glycol diacetate (manufactured by Daicel)

ANON: cyclohexanone (made by Kanto Chemical Co., Ltd.)

Example 15

Using the compound (2) as an oxime ester photopolymerization initiator, 1,3-dimethyl-3,4,5, which is a solvent A (Sol. A), which is excellent in solubility as an oxime ester photopolymerization initiator, 6-tetrahydro-2(1H)pyrimidinone, and 3-methoxybutanol acetate which is a solvent (Sol. B) which is generally used for electronic materials and has good coatability and pigment dispersibility is 80: A ratio of 20 (weight ratio) is mixed. Then, the oxime ester photopolymerization initiator [compound (2)] was adjusted to a solution of the initiator concentration (5 wt% to 30 wt%) described in Table 4 under the above-mentioned mixed solvent in an environment of 20 °C. After mixing for about 1 minute by hand shaking the container, it was visually confirmed whether or not it was dissolved.

Examples 16 to 20 and Comparative Examples 8 to 9

In the same manner as in Example 15, the solvent described in the following Table 4 was mixed at a weight ratio described in Table 4, and an oxime ester photopolymerization initiator [compound (2)] was prepared in an environment of 20 ° C. The solution of the initiator concentration (5 wt% to 30 wt%) in Table 4 was visually confirmed to be soluble.

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

MBA: 3-methoxybutanol acetate (manufactured by Daicel)

MMPGAC: propylene glycol monomethyl ether acetate (made by Daicel)

ANON: cyclohexanone (made by Kanto Chemical Co., Ltd.)

Tables 1 and 3 show that solvent A (Sol. A) alone (Examples 1-3) and solvent A (Sol. A) and solvent B (Sol. B) mixed solvent (Examples 7 to 14) It is more excellent in solubility of the compound (1) than the mixed solvent of cyclohexanone and cyclohexanone used in the past (Comparative Examples 1, 4 to 7). Further, as shown in Table 2 and Table 4, solvent A (Sol. A) alone (Examples 4 to 6) and solvent A (Sol. A) and solvent B (Sol. B) were mixed solvents (Example 15). ~20) is more excellent in the solubility of the compound (2) than the mixed solvent of cyclohexanone and cyclohexanone used in the past (Comparative Examples 2, 3, 8, and 9).

[Industrial availability]

The solvent or solvent composition for producing a photoresist of the present invention is capable of efficiently producing a photoresist by dissolving an oxime ester photopolymerization initiator at a high concentration.

Claims (13)

A solvent or a solvent composition for producing a photoresist, which is a solvent for dissolving an oxime ester photopolymerization initiator of the compound (1) represented by the following formula (1) or the compound (2) represented by the following formula (2) Or solvent composition, It contains solvent A, and the solvent A has at least one selected from the group consisting of the following formula (A) (In the above formula, 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 each) A compound of the group of compounds. The solvent or solvent composition for producing a photoresist according to the first aspect of the invention, wherein the compound (1) represented by the formula (1) or the compound (2) represented by the formula (2) at 20 ° C is used. The solubility of the ester photopolymerization initiator is 4 parts by weight or more based on 100 parts by weight of the solvent or solvent composition. The solvent or solvent composition for producing a photoresist according to the first aspect of the invention, wherein the oxime ester photopolymerization initiator is the compound (1) represented by the formula (1). The solvent or solvent composition for producing a photoresist according to the first aspect of the invention, wherein the oxime ester photopolymerization initiator is the compound (2) represented by the formula (2), and the solvent A is 1,3-dimethyl -3,4,5,6-tetrahydro-2(1H)pyrimidinone. A solvent or a solvent composition for producing a photoresist, which is a solvent or a solvent composition for dissolving an oxime ester photopolymerization initiator of the compound (3) represented by the following formula (3). It contains solvent A, which is 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidinone. The solvent or solvent composition for the manufacture of photoresist for the fifth application of the patent scope The solubility of the oxime ester photopolymerization initiator of the compound (3) represented by the formula (3) at 20 ° C is 4 parts by weight or more based on 100 parts by weight of the solvent or solvent composition. The solvent or solvent composition for producing a photoresist according to any one of claims 1 to 6, further comprising at least one solvent B compatible with the solvent A. The solvent or solvent composition for producing a photoresist according to Item 7 of the patent application, which contains 30% by weight or more of the solvent A. A solvent or solvent composition for producing a photoresist according to claim 8 of the invention, which contains 50% by weight or more of the solvent A. A composition for producing a photoresist, which comprises a phthalate-based photopolymerization initiator containing the compound (1) represented by the following formula (1) or the compound (2) represented by the following formula (2), and the scope of the patent application The solvent or solvent composition for producing a photoresist according to any one of items 1 to 4, A composition for producing a photoresist, which comprises an oxime ester photopolymerization initiator containing the compound (3) represented by the following formula (3), and a solvent for producing a photoresist according to the fifth or sixth aspect of the patent application or Solvent composition The composition for producing a photoresist according to claim 10, wherein the oxime ester photopolymerization initiator is the compound (1). The composition for producing a photoresist according to claim 10, wherein the oxime ester photopolymerization initiator is the compound (2), and the solvent A is 1,3-dimethyl-3, 4, 5, 6-Tetrahydro-2(1H)pyrimidinone.