TWI624727B - Photosensitive composition, method for producing the photosensitive composition, method for forming a film using the photosensitive composition, method for suppressing adhesion when the photosensitive composition is stored, photopolymerization initiator, and photopolymerization initiator production method - Google Patents

Abstract

A photosensitive composition capable of forming a film having excellent transparency and suppressing adhesion during storage, a method for producing the photosensitive composition, a method for forming a film using the photosensitive composition, and a photosensitive composition A photopolymerization initiator which is a photopolymerization initiator which is suitable for preparing a photosensitive composition which can form a film which is excellent in transparency and which has a film which is excellent in transparency and which is inhibited in adhesion during storage, and a method for producing the photopolymerization initiator.

[Solution] A photosensitive composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, using a specific structure of an oxime ester compound as (C) photopolymerization The content of the chloride ion of the initiator (C) photopolymerization initiator or the photosensitive composition is within a specified range.

Description

Photosensitive composition, method for producing the photosensitive composition, method for forming a film using the photosensitive composition, method for suppressing adhesion when the photosensitive composition is stored, photopolymerization initiator, and photopolymerization initiator Production method

The present invention relates to a photosensitive composition, a method for forming a film using the photosensitive composition, a method for suppressing adhesion when a photosensitive composition is stored, a photopolymerization initiator, and a method for producing a photopolymerization initiator.

In a display device like a liquid crystal display device, it is necessary for an insulating film-like material to efficiently transmit light emitted from a backlight-like light source. Therefore, in order to form an insulating film, a material which can form a film excellent in transparency is pursued.

Such a transparent insulating film is usually patterned on a substrate. A method of forming a patterned transparent insulating film is known, for example, using an alkali-soluble resin having an oxetane ring, a polymerizable polyfunctional compound, and a photopolymerization with an α-aminoalkylphenone. A method of a negative photosensitive composition of a starting agent (Patent Document 1 is incorporated by reference).

In recent years, with the increase in the number of productions of liquid crystal display displays, the production of color filters has also increased, and from the viewpoint of further productivity improvement, the pursuit of high-sensitivity photosensitive compositions capable of forming patterns with low exposure amounts has been pursued. Things.

However, the negative-type photosensitive composition described in Patent Document 1 is a person who is seeking further improvement in sensitivity.

In this case, the present applicant proposes a photosensitive tree composition containing a photopolymerization initiator represented by the following formula as a high-sensitivity photosensitive composition (Patent Document 2).

(wherein R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is A phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2012-173678

[Patent Document 2] JP-A-2013-148872

However, the inventors of the present invention have found that when the photosensitive composition described in Patent Document 2 is used, it is difficult to form a film having excellent transparency.

Further, it is required to suppress the viscosity increase over time in the entire photosensitive composition.

In view of the above, the present invention provides a photosensitive composition capable of forming a film having excellent transparency and suppressing the increase in viscosity during storage, a method for producing the photosensitive composition, and the use of the photosensitive property. The method for forming a film of a composition, the method for suppressing and increasing the viscosity of the photosensitive composition, and the photopolymerization initiator for preparing a photosensitive composition capable of forming a film having excellent transparency and suppressing the increase in viscosity during storage, It is an object of the production method of the photopolymerization initiator.

The present inventors have found that a photosensitive composition having (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator is used as a (C) ester having a specific structure. In the photopolymerization initiator, the content of the chloride ion of the (C) photopolymerization initiator or the photosensitive composition is within a predetermined range, and the above problems can be solved to complete the present invention. Specifically, the present invention provides the following.

The first aspect of the present invention is a photosensitive composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (C) a photopolymerization initiator is contained Description (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The compound represented by (C) the photopolymerization initiator has a chloride ion content of 10 to 510 ppm by mass, and (C) the ratio of the mass of the photopolymerization initiator to the solid content of the photosensitive composition is 1 ~20% by mass.

The second aspect of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (C) a photopolymerization initiator contains the following formula (1) : (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The compound represented by the present invention has a photosensitive composition of 0.1 to 30 ppm by mass based on the mass of the solid content.

A third aspect of the present invention is a method for forming a film comprising applying a photosensitive composition of a first aspect or a second aspect onto a substrate to form a coating film and exposing the coating film.

The fourth aspect of the present invention comprises preparing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (C) a photopolymerization initiator comprising the following formula (1) ): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In the photosensitive composition of the compound, the (C) photopolymerization initiator having a chloride ion content of 10 to 510 ppm by mass is used in combination with the solid content of the photosensitive composition in an amount of 1 to 20% by mass. A method of inhibiting adhesion when a sexual composition is stored.

According to a fifth aspect of the present invention, there is provided a (A) alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (C) a photopolymerization initiator comprising the following formula (1) ): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In the case of the photosensitive composition of the compound, the content of the chloride ion in the photosensitive composition is 0.1 to 30 ppm by mass based on the mass of the solid component.

The sixth aspect of the present invention has a chloride ion content of 10 to 510 ppm by mass and contains the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A photopolymerization initiator of the compound represented.

A seventh aspect of the present invention is a method for producing a photosensitive composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, which comprises the following formula (1) : (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. (C) Photopolymerization initiator which is a compound having a chloride ion content of 10 to 510 ppm by mass, and a photosensitive composition of 1 to 20% by mass based on the mass of the photosensitive composition .

An eighth aspect of the present invention is a method for producing a photosensitive composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, which comprises the following formula (1) : (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The (C) photopolymerization initiator of the compound represented by the method of producing a photosensitive composition in which the content of the chloride ion in the photosensitive composition is 0.1 to 30 ppm by mass based on the mass of the photosensitive composition.

The ninth aspect of the present invention is represented by the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A method for producing a photopolymerization initiator comprising a compound represented by a compound having a chloride ion content of 10 to 510 ppm by mass, which comprises one or more of the following 1) to 6): 1) The compound represented by the formula (1) is synthesized by a method comprising the step of performing a Friedel-Crafts reaction using aluminum chloride, and the content of the chloride ion of the compound represented by the formula (1) is 10 to 510. A method of adjusting the amount of use of aluminum chloride in the range of ppm by mass, and 2) a method of using a compound containing no chlorine atom in the synthesis of the compound represented by the formula (1), and 3) a compound represented by the formula (1) In the synthesis, a Friedel-Crafts deuteration reaction or a mercapto group, a method using an acid anhydride as a deuteration agent, and 4) a crude product of the compound represented by the formula (1) is selected from the group consisting of a method of purifying one or more methods in a group consisting of distillation, recrystallization, water washing, and column chromatography, and 5) a solution in which a crude product of the compound represented by the formula (1) is dissolved in a hydrophobic organic solvent a method of recovering the compound represented by the formula (1) from the washed solution after washing with water, and 6) by 1 The method selected from the above methods 1) to 5), after obtaining a refined product of the compound represented by the formula (1) having a chloride ion content of less than 10 ppm by mass, adding a chloride to the refined product, 1) A method in which the chloride ion content of the compound represented is adjusted to be in the range of 10 to 510 ppm by mass.

According to the present invention, it is possible to provide a photosensitive composition capable of forming a film having excellent transparency and suppressing adhesion during storage, a method for producing the photosensitive composition, a method for forming a film using the photosensitive composition, and a method for forming a film using the photosensitive composition. A photopolymerization initiator which is prepared by a method for suppressing and increasing the viscosity of a photosensitive composition, and a photopolymerization initiator which is suitable for preparation of a photosensitive composition capable of forming a film having excellent transparency and which is inhibited in adhesion during storage. Manufacturing method.

[Best Mode for Carrying Out the Invention] ≪Photosensitive composition≫

The photosensitive composition of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator.

(C) The photopolymerization initiator contains the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The compound represented.

The photosensitive composition meets the conditions of the following (I) or (II).

(I) (C) The photopolymerization initiator has a chloride ion content of 10 to 510 ppm by mass, and the ratio of the mass of the (C) photopolymerization initiator to the solid content of the photosensitive composition is 1 to 20% by mass.

(II) The content of the chloride ion of the photosensitive composition is 0.1 to 30 ppm by mass based on the mass of the solid content.

The content of the (C) photopolymerization initiator and the chloride ion in the photosensitive composition can be measured by ion chromatography according to the following method.

(Ion chromatography measurement conditions)

Column: IonPac AS17-C (Thermo Scientific Dionex)

Dissolution: a mixed solution of water and acetonitrile

Injection volume: 1μL

The present inventors have examined the cause of the formation of a film having a low transparency, and the present inventors have found that when the chloride ion in the photosensitive composition, in particular, the content of the chloride ion in the (C) photopolymerization initiator is too large, It is easy to form a film with low transparency.

On the other hand, the present inventors have found that when the chloride ion in the photosensitive composition, in particular, the chloride ion content in the (C) photopolymerization initiator is too small, the time-lapse increase in the storage of the photosensitive composition is liable to occur. Sticking to an undesired situation.

That is, the chloride ion content in the photosensitive composition or (C) photopolymerization initiator is not as small as possible, but is in an appropriate range.

Hereinafter, the photosensitive composition satisfying the above condition (I) is described as the composition I, and the photosensitive composition satisfying the above condition (II) is described. For composition II. The composition I and the composition II will be described below.

<composition I>

The composition I contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator.

Further, in the composition I, (C) the photopolymerization initiator has a chloride ion content of 10 to 510 ppm by mass, and (C) the ratio of the mass of the photopolymerization initiator to the solid content of the composition I It is 1 to 20% by mass.

The necessary or optional components contained in the composition I are as follows.

[(A) alkali soluble resin]

The alkali-soluble resin is a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and a resin film having a thickness of 1 μm is formed on the substrate, and immersed in a 0.05% by mass aqueous KOH solution for 1 minute. In the case of a resin having a film thickness of 0.01 μm or more.

(A) The alkali-soluble resin is not particularly limited as long as it exhibits the above-mentioned alkali-soluble resin, and can be appropriately selected from conventional resins. The resin which is preferably (A) an alkali-soluble resin may, for example, be a resin having a Cardo structure (A1).

(A1) The resin having a Cardo structure is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferred.

In the above formula (a-1), X ^a is a group represented by the following formula (a-2).

In the above formula (a-2), R ^{a1 is} independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^{a2 is} independently a hydrogen atom or a methyl group, and W ^a is a single bond or a lower The base represented by the formula (a-3).

Further, in the above formula (a-1), Y ^{a is a} residue obtained by removing an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include anhydrous maleic acid, anhydrous succinic acid, anhydrous itaconic acid, anhydrous phthalic acid, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, and anhydrous methyl bridged methylenetetramine. Hydrogen phthalic acid, anhydrous chloric acid, methyltetrahydro anhydrous phthalic acid, anhydrous glutaric acid, and the like.

Further, in the above formula (a-1), Z ^{a is a} residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

Further, in the above formula (a-1), m is an integer of 0 to 20.

(A1) Mass average molecular weight of the resin having a Cardo structure (Mw: measured value in terms of polystyrene by colloidal osmosis chromatography (GPC). The same in the present specification). It is preferably 1000~40000, and 2000~30000 is better. By the above range, good developability is obtained, and sufficient heat resistance and film strength can be obtained.

Further, a copolymer which is excellent in mechanical strength or excellent in substrate adhesion, and (A2) a copolymer in which at least an unsaturated carboxylic acid (a1) is polymerized can also be suitably used as the (A) alkali-soluble resin.

(a1) The unsaturated carboxylic acid may, for example, be a monocarboxylic acid such as (meth)acrylic acid or crotonic acid; or a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, methyl fumaric acid or itaconic acid; Anhydrous of such dicarboxylic acids; Among these, (meth)acrylic acid and anhydrous maleic acid are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These (a1) unsaturated carboxylic acids may be used singly or in combination of two or more kinds.

The (A2) copolymer may also be a copolymer of (a1) an unsaturated carboxylic acid and (a2) an alicyclic epoxy group-containing unsaturated compound. (a2) The alicyclic epoxy group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. The monocyclic alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group. Further, a polycyclic alicyclic group may, for example, be a norborne base or an iso-ice. A base group, a tricyclic fluorenyl group, a tricyclic fluorenyl group, a tetracyclododecyl group, or the like. These (a2) alicyclic epoxy group-containing unsaturated compounds may be used singly or in combination of two or more kinds.

Specifically, the (a2) alicyclic epoxy group-containing unsaturated compound may, for example, be a compound represented by the following formulas (a2-1) to (a2-15). In the above, in order to have appropriate developability, the compounds represented by the following formulas (a2-1) to (a2-5) are preferred, and the compounds represented by the following formulas (a2-1) to (a2-3) are more preferable. good.

In the above formula, R ^a20 is a hydrogen atom or a methyl group, R ^a21 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a22 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and t is 0 to 10. Integer. R ^a21 is a linear or branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, a tetramethyl group, an ethyl group ethyl group, a pentamethyl group, and a hexamethyl group. . R ^a22 , for example, methyl, ethyl, propyl, tetramethyl, ethyl, ethyl, pentamethyl, hexamethyl, phenyl, cyclohexyl, -CH ₂ -Ph -CH ₂ - (Ph is a stretching phenyl group) is preferred.

In the (A2) copolymer, the above (a1) unsaturated carboxylic acid and the above (a2) alicyclic epoxy group-containing unsaturated compound may be bonded to the (a3) alicyclic group-containing unsaturated compound having no epoxy group. Copolymerization.

(a3) The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. The monocyclic alicyclic group may, for example, be a cyclopentyl group or a cyclohexyl group. Further, examples of the polycyclic alicyclic group include adamantyl group, norbornyl group, isobornyl group, tricyclodecyl group, tricyclodecyl group, tetracyclododecyl group and the like. These (a3) alicyclic unsaturated-containing compounds may be used singly or in combination of two or more kinds.

Specifically, the (a3) alicyclic group-containing unsaturated compound may, for example, be a compound represented by the following formulas (a3-1) to (a3-7). In the above, in order to have appropriate developability, the compound represented by the following formulas (a3-3) to (a3-8) is preferable, and the compound represented by the following formula (a3-3) or (a3-4) is more preferable. good.

In the above formula, R ^a23 is a hydrogen atom or a methyl group, R ^a24 is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^a24 is a single bond, a linear or branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, a tetramethyl group, an ethyl group, a methyl group, a hexamethyl group. The base is good. R ^{a25 is preferably} , for example, a methyl group or an ethyl group.

Further, the (A2) copolymer may be the above (a1) unsaturated carboxylic acid, the (a2) alicyclic epoxy group-containing unsaturated compound, and the above (a3) alicyclic group-containing unsaturated compound, and (a4) an epoxy group-containing unsaturated compound copolymerized without an alicyclic group.

(a4) The epoxy group-containing unsaturated compound may, for example, be glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate or 3,4-epoxy butyl (methyl). (A) epoxy (meth) acrylate epoxy alkyl esters such as acrylate, 6,7-epoxyheptyl (meth) acrylate; α-ethyl methacrylate, α-n-propyl An α-alkyl acrylate epoxyalkyl ester such as glycidyl acrylate, α-n-butyl glycidyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester or the like; Among these, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and 6, 7 are derived from the viewpoints of copolymerization reactivity, strength of the resin after curing, and the like. An epoxyheptyl (meth) acrylate is preferred. These (a4) epoxy group-containing unsaturated compounds may be used singly or in combination of two or more kinds.

Further, the (A2) copolymer may be further copolymerized with other compounds than the above. Examples of such other compounds include (meth) acrylates, (meth) acrylamides, and allyl esterification. Compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds may be used alone or in combination of two or more.

Examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and t-octyl. Linear or branched alkyl (meth) acrylate such as benzyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethyl hydroxy propyl (methyl) Acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, mercapto (meth) acrylate;

Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dioxane. (meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl (Methyl) acrylamide and the like.

Examples of the allyl ester compound include allyl acetate, allyl hexanoate, allyl octylate, allyl laurate, allyl palmitate, allyl stearyl ester, Allyl esters such as allyl benzoate, allyl acetate, allyl lactate, etc.; allyloxyethanol; and the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl ether. Chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyl Ethyl vinyl ether, diethylene glycol vinyl ether, dimethyl amino ethyl vinyl ether, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl ethylene An alkyl vinyl ether such as an ether or a tetrahydrofurfuryl vinyl ether; a vinyl phenyl ether, a vinyl tolyl ether, a vinyl chlorophenyl ether, a vinyl-2,4-dichlorophenyl ether, a vinyl aryl ether such as vinyl naphthyl ether or vinyl decyl ether; and the like.

Examples of the vinyl esters include vinyl butyl ester, vinyl isobutyl ester, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl hexanoate, and ethylene. Chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetonitrile acetate, vinyl Lactic acid ester, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate, and the like.

Examples of the styrenes include styrene; methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, and hexyl. An alkane such as styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl methyl styrene Alkoxystyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; chlorostyrene, dichlorostyrene, trichlorostyrene , tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro- a halogenated styrene such as 3-trifluoromethylstyrene; Wait.

The proportion of the constituent unit derived from the above (a1) unsaturated carboxylic acid in the (A2) copolymer is preferably from 1 to 50% by mass, more preferably from 5 to 45% by mass.

Further, when the (A2) copolymer contains a constituent unit derived from the above (a2) alicyclic epoxy group-containing unsaturated compound and a constituent unit derived from the above (a4) epoxy group-containing unsaturated compound, (A2) copolymerization The ratio of the ratio of the constituent unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound to the ratio of the constituent unit derived from the above (a4) epoxy group-containing unsaturated compound is 71% by mass or more. Preferably, 71 to 95% by mass is preferred, and 75 to 90% by mass is more preferably. In particular, the proportion of the constituent unit derived from the above (a2) alicyclic epoxy group-containing unsaturated compound in the (A2) copolymer is preferably 71% by mass or more, and more preferably 71 to 80% by mass. By setting the ratio of the constituent unit derived from the above (a2) alicyclic epoxy group-containing unsaturated compound to the above range, the stability of the composition I over time can be further improved.

Further, when the (A2) copolymer contains a constituent unit derived from the (a3) alicyclic unsaturated compound, the (A3) alicyclic unsaturated compound derived from the (a3) copolymer The proportion of the constituent units is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

The mass average molecular weight of the (A2) copolymer is preferably from 2,000 to 200,000, more preferably from 3,000 to 30,000. In the above range, there is a tendency that the balance between the film forming ability of the composition I and the developability after exposure is easily obtained.

In addition, it is preferable to use (A3) a constituent unit containing at least (a1) an unsaturated carboxylic acid and a constituent unit having a site which can be polymerized with a photopolymerizable monomer (B) to be described later. The copolymer or (A4) has at least a constituent unit derived from the above (a1) unsaturated carboxylic acid, and the (a2) alicyclic epoxy group-containing unsaturated compound and/or (a4) epoxy group-containing compound A constituent unit of a saturated compound and a resin having a copolymer of a constituent unit which can be polymerized with a photopolymerizable monomer (B) to be described later. (A) When the alkali-soluble resin contains the (A3) copolymer or the (A4) copolymer, the film formed by using the composition I can be improved in adhesion to the substrate and the mechanical strength after curing of the composition I. .

The (A3) copolymer and the (A4) copolymer may be (meth) acrylates, (meth) acrylamides, olefins described as other compounds in the (A2) copolymer. A copolymerization of a base ester compound, a vinyl ether, a vinyl ester, or a styrene.

In terms of a constituent unit having a site capable of polymerizing with the (B) photopolymerizable monomer, it is preferred to have an ethylenically unsaturated group as a constituent unit of a portion polymerizable with the (B) photopolymerizable monomer. In the copolymerization of such a constituent unit, the (A3) copolymer may be at least a part of the carboxyl group contained in the polymer containing the constituent unit derived from the (a1) unsaturated carboxylic acid, and the above (a2) The alicyclic epoxy group-containing unsaturated compound and/or the (a4) epoxy group-containing unsaturated compound are reacted to prepare. Further, the (A4) copolymer may have a constituent unit derived from the above (a1) unsaturated carboxylic acid, and a ring-containing epoxy group-containing unsaturated compound and/or (a4) ring-containing ring derived from (a2). Copolymerization of constituent units of oxy unsaturated compounds At least a portion of the epoxy group in the compound is prepared by reacting with (a1) an unsaturated carboxylic acid.

The ratio of the constituent unit derived from the (a1) unsaturated carboxylic acid in the (A3) copolymer is preferably from 1 to 50% by mass, more preferably from 5 to 45% by mass. The proportion of the constituent unit of the (A3) copolymer having a site capable of polymerizing with the (B) photopolymerizable monomer is preferably from 1 to 45% by mass, more preferably from 5 to 40% by mass. When the (A3) copolymer contains each constituent unit in such a ratio, the composition I which can form a film excellent in adhesion to the substrate can be easily obtained.

The ratio of the constituent unit derived from the (a1) unsaturated carboxylic acid in the (A4) copolymer is preferably from 1 to 50% by mass, more preferably from 5 to 45% by mass. (A4) The proportion of the constituent unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound and/or the (a4) epoxy group-containing unsaturated compound in the copolymer is preferably 55 mass% or more. 71% by mass or more is more preferable, and 71 to 80% by mass is particularly preferable.

The ratio of the constituent unit having a site capable of polymerizing with the (B) photopolymerizable monomer in the (A4) copolymer is preferably from 1 to 45% by mass, more preferably from 5 to 40% by mass. When the (A4) copolymer contains each constituent unit in such a ratio, the composition I which can form a film excellent in adhesion to the substrate can be easily obtained.

The mass average molecular weight of the (A3) copolymer and the (A4) copolymer is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. In the above range, there is a tendency that the balance between the film forming ability of the composition I and the developability after exposure is easily obtained.

The content of the alkali-soluble resin (A) is preferably from 40 to 85% by mass, more preferably from 45 to 75% by mass, based on the solid content of the composition I. In addition, when the total amount of the (A) alkali-soluble resin and the content of the (B) photopolymerizable monomer and the content of the (C) photopolymerization initiator are 100 parts by mass, the alkali-soluble resin (A) is composed. It is preferable that the content of the (B) photopolymerizable monomer in the material I is 5 to 50 parts by mass in the composition I.

[(B) Photopolymerizable monomer]

Among the photopolymerizable monomers, there are monofunctional monomers and polyfunctional monomers.

The monofunctional monomer may, for example, be (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) propylene. Indoleamine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, anhydrous maleic acid, itaconic acid, anhydrous itaconic acid, citraconic acid, anhydrous citraconic acid, crotonic acid, 2- Acrylamide-2-methylpropane sulfonic acid, tert-butyl propylene decyl sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy butyl ( Methyl) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene decyloxy-2-hydroxypropyl phthalate, glycerol mono Methyl) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate Glycidol Base (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivative Semi-(meth) acrylate and the like. These monofunctional monomers may be used alone or in combination of two or more.

On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di( Methyl) acrylate, polypropylene glycol di(meth) acrylate, butanediol di(meth) acrylate, neopentyl diol di(meth) acrylate, 1,6-hexane diol di ( Methyl) acrylate, trimethylolpropane tri(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2 - bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxyl -3-(Methyl)propenyl methoxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene Diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, amine group Ethyl formate (meth) acrylate (ie toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-hydroxyethyl (methyl) propyl a reactant of an enoate, a methyl bis(meth) acrylamide, a (meth) acrylamide methyl ether, a condensate of a polyol and N-hydroxymethyl (meth) acrylamide, etc. A polyfunctional monomer or triacrylformal or the like. These polyfunctional monomers may be used singly or in combination of two or more kinds.

(B) The photopolymerizable monomer, when the total amount of the (A) alkali-soluble resin and the content of (B) the photopolymerizable monomer and the content of the (C) photopolymerization initiator are 100 parts by mass, The content of the (B) photopolymerizable monomer in the composition I is preferably from 5 to 50 parts by mass, more preferably from 6 to 40 parts by mass. (B) When the content of the photopolymerizable monomer is within such a range, it is easy to form a film excellent in adhesion to the substrate.

Further, from the viewpoint of the adhesion of the formed film to the substrate, the content of the (B) photopolymerizable monomer is preferably as small as possible. Further, when the content of the (B) photopolymerizable monomer is lowered, the resin having an unsaturated double bond as in (A1) as the ( A ) alkali-soluble resin or (A3) or (A4) has the same ability and (B) The resin of the constituent unit of the site where the photopolymerizable monomer is polymerized can improve the mechanical strength of the film.

[(C) Photopolymerization initiator]

The composition I contains an oxime ester compound of the following configuration as (C) a photopolymerization initiator. As the photopolymerization initiator, the composition I can be made excellent in sensitivity by using the oxime ester compound having the structure represented by the following formula (1).

(R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula (1), R ¹ is not particularly limited as long as it does not inhibit the object of the present invention, and is appropriately selected from various organic groups. A suitable example when R ¹ is an organic group may, for example, be an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyloxy group, or may have a phenyl group of a substituent, a phenoxy group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzhydryloxy group which may have a substituent, may have a substitution Phenylalkyl group, naphthyl group which may have a substituent, naphthyloxy group which may have a substituent, naphthylmethyl group which may have a substituent, naphthyloxycarbonyl group which may have a substituent, naphthalene which may have a substituent a mercaptooxy group, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an amine group, an amine group which may be substituted by one or two organic groups, a morpholin-1-yl group, and Piperazin-1-yl, halogen, nitro, and cyano. When m is an integer from 2 to 4, R ¹ may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent which the substituent further has.

When R ¹ is an alkyl group, the number of carbon atoms is preferably from 1 to 20, and the number of carbon atoms is preferably from 1 to 6. Further, when R ¹ is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ¹ is an alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentylene group. Base, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-fluorenyl, iso Sulfhydryl, n-fluorenyl, and isodecyl. Further, when R ¹ is an alkyl group, the alkyl group may have an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include, for example, a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a propyloxy group B. Oxyethyl, methoxypropyl and the like.

When R ¹ is an alkoxy group, it is preferably 1 to 20 carbon atoms and more preferably 1 to 6 carbon atoms. Further, when R ¹ is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ¹ is an alkoxy group include, for example, a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, or a sec- Butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy , n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isodecyloxy, n-decyloxy, and Isodecyloxy and the like. Further, when R ¹ is an alkoxy group, the alkoxy group may have an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include, for example, a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. Propyloxyethoxyethoxy, methoxypropyloxy and the like.

When R ¹ is a cycloalkyl group or a cycloalkoxy group, it is preferably 3 to 10 carbon atoms and more preferably 3 to 6 carbon atoms. Specific examples of the case where R ¹ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the case where R ¹ is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. Wait.

When R ¹ is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, it is preferably 2 to 20 carbon atoms and more preferably 2 to 7 carbon atoms. Specific examples of the case where R ¹ is a saturated aliphatic fluorenyl group include, for example, an ethyl fluorenyl group, a propyl fluorenyl group, an n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, an n-pentyl fluorenyl group, and a 2,2-dimethyl propyl group. Sulfhydryl, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodedecyl, n-tride Base, n-tetradecyl, n-pentadecanyl, and n-hexadecanyl. Specific examples of the case where R ¹ is a saturated aliphatic mercaptooxy group include, for example, an ethenyloxy group, a propenyloxy group, an n-butenyloxy group, a 2-methylpropoxy group, and an n-pentyloxy group. , 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-fluorenyloxy, n-decyloxy , n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-nonyldecyloxy, and n-ten Hexamethyloxy and the like.

When R ¹ is an alkoxycarbonyl group, it is preferably 2 to 20 carbon atoms and more preferably 2 to 7 carbon atoms. Specific examples of the case where R ¹ is an alkoxycarbonyl group include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, and an isobutyl group. Alkoxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxy Carbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n- A mercaptooxycarbonyl group, an isodecyloxycarbonyl group, an n-fluorenyloxycarbonyl group, an isodecyloxycarbonyl group or the like.

When R ¹ is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, and the number of carbon atoms is preferably 7 to 10. Further, when R ¹ is a naphthylalkyl group, the number of carbon atoms is preferably from 11 to 20, and the number of carbon atoms is preferably from 11 to 14. Specific examples of the case where R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ¹ is a naphthylalkyl group include, for example, α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. base. When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or the naphthyl group.

When R ¹ is a heterocyclic group, the heterocyclic group is a 5-member or 6-membered monocyclic ring containing one or more N, S, O or a heterocyclic group in which the monocyclic ring or the monocyclic ring is condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is up to 3. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, and the like. Pyridazine, benzofuran, benzothiophene, anthracene, isoindole, pyridazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquine Porphyrin, quinazoline, pyridazine, porphyrin, and quinoxaline. When R ¹ is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ¹ is an amine group which may be substituted by one or two organic groups, a suitable example of the organic group may, for example, be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a carbon atom. a saturated aliphatic fluorenyl group of 2 to 20, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, may have a substituent The naphthyl group, a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group. Specific examples of such suitable organic groups are the same as R ¹ . Specific examples of the amine group which may be substituted by one or two organic groups may, for example, be a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group or a di-n-propylamine. Base, isopropylamino group, n-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group , n-decylamino, n-decylamino, phenylamino, naphthylamino, ethionylamino, propylamine, n-butylamino, n-pentamethyleneamine, N-hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzhydrylamino, alpha-naphthylmethylamino, and beta-naphthyl Mercaptoamine and the like.

The substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ¹ further have a substituent, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic mercaptooxy group having 2 to 7 carbon atoms, and a single alkyl group having 1 to 6 carbon atoms An alkylamino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ¹ further have a substituent, the number of the substituents is not limited to the range of the object of the present invention, and is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ¹ have a complex substituent, the plural substituents may be the same or different.

R ¹ is a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 carbon atoms, from the viewpoints of chemical stability, little steric hindrance, and easy synthesis of an oxime ester compound. The group of the saturated aliphatic fluorenyl group of ~7 is preferably a group, the alkyl group having 1 to 6 carbon atoms is more preferable, and the methyl group is particularly preferable.

R ^{1 is} bonded to the position of the phenyl group, and the phenyl group bonded to R ¹ has a position in which the bonding bond of the main skeleton of the phenyl group and the oxime ester compound is 1 position, and when the position of the methyl group is 2 positions, 4 or 5 is better and 5 is better. Further, m is preferably an integer of 0 to 3, an integer of 0 to 2 is more preferable, and 0 or 1 is particularly preferable.

R ² is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. Further, when R ² is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

The substituent of the phenyl group or the carbazolyl group in R ² is not particularly limited insofar as it does not inhibit the object of the present invention. Examples of the suitable substituent which the phenyl group or the carbazolyl group may have on the carbon atom include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to 10 carbon atoms. a cycloalkyl group, a cycloalkyloxy group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a saturation of 2 to 20 carbon atoms. An aliphatic fluorenyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzamyl group which may have a substituent, and a benzene which may have a substituent An oxycarbonyl group, a benzylideneoxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, A naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group having a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group, an amine group which may be substituted by 1, or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, , Nitro, cyano and the like.

When R ² is a carbazolyl group, examples of a suitable substituent which the carbazolyl group may have on the nitrogen atom include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon. a saturated aliphatic fluorenyl group having 2 to 20 atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, and a phenoxy group which may have a substituent a carbonyl group, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, may have a substitution The group has a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

Specific examples of the substituent which the phenyl group or the carbazolyl group may have, with respect to an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyloxy group A phenylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group which may be substituted by one or two organic groups are the same as R ¹ .

In R ² , examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group which the substituent of the phenyl group or the carbazolyl group has a substituent include, for example, a carbon number of 1 to 6 An alkyl group; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic group having 2 to 7 carbon atoms; Alkoxy; phenyl; naphthyl; benzhydryl; naphthylmethyl; via an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl a selected group of substituted benzamidine groups; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholine- 1-yl; piperazin-1-yl; halogen; nitro; cyano. When the phenyl group, the naphthyl group, and the heterocyclic group which the substituent of the phenyl group or the carbazolyl group further has a substituent, the number of the substituents is not limited to the range of the object of the present invention, and is not limited to ~4 is better. When the phenyl group, the naphthyl group, and the heterocyclic group have a complex substituent, the plural substituents may be the same or different.

In the case of R ² , the group represented by the following formula (2) or (3) is preferable, and the group represented by the following formula (2) is more preferable, and the formula (2) is the following formula (2). The base represented by A and the basis of A being S are particularly preferred.

(R ⁴ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, and A is S or O, and n is an integer of 0 to 4).

(R ⁵ and R ⁶ are each a monovalent organic group).

When the composition I is used to form a pattern, there is a case where coloring occurs in the pattern due to heating in the post-exposure baking step at the time of pattern formation. However, in the composition I, when the oxime ester compound represented by the formula (1) in which R ² is a group represented by the above formula (2) and A is a group of S is used as the (C) photopolymerization initiator, it can be suppressed. Patterning due to heating.

When R ⁴ in the formula (2) is an organic group, it can be selected from various organic groups without impairing the object of the present invention. In the formula (2), a suitable example of the case where R ⁴ is an organic group may, for example, be an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic group having 2 to 7 carbon atoms. Sulfhydryl; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic mercaptooxy group having 2 to 7 carbon atoms; phenyl; naphthyl group; benzamyl group; naphthylmethyl group; a benzamidine group substituted with a group selected from the group consisting of an alkyl group of 1 to 6 , a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; and an alkyl group having 1 to 6 carbon atoms; a monoalkylamine group; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group;

In R ⁴ , a benzylidene group; a naphthylmethyl group; a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Substituted benzinyl; nitro is preferred, benzamidine; naphthylmethyl; 2-methylphenylcarbonyl; 4-(piperazin-1-yl)phenylcarbonyl; 4-(phenyl The phenylcarbonyl group is more preferred.

Further, in the formula (2), n is preferably an integer of 0 to 3, an integer of 0 to 2 is more preferable, and 0 or 1 is particularly preferable. n is 1, R ⁴ position of bonding, R ⁴ are bonded to the phenyl group with respect -A- bonded to bonding bond to para preferred.

R ⁵ in the formula (3) can be selected from various organic groups without impairing the object of the present invention. A suitable example of R ^{5 is} , for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkoxycarbonyl group, phenyl group which may have a substituent, benzamyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms And a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, may have a substituent a heterocyclic group, a heterocyclic carbonyl group which may have a substituent, and the like.

In R ⁵ , an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

R ⁶ in the formula (3) is not particularly limited as long as it does not inhibit the object of the present invention, and can be selected from various organic groups. Specific examples of a suitable base of R ⁶ include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. As the group of R ⁶ in the above, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

The substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ⁴ , R ⁵ or R ⁶ further have a substituent, and examples thereof include an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. Alkoxy group, saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms, having 1 carbon atom a monoalkylamino group of an alkyl group of ~6, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyanogen Base. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ⁴ , R ⁵ or R ⁶ have a substituent, the number of the substituents is not limited to the range of the object of the present invention, and is 1 to 4 good. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ⁴ , R ⁵ or R ⁶ have a complex substituent, the plural substituents may be the same or different.

R ³ in the formula (1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ³ , a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

The oxime ester compound represented by the formula (1) can be synthesized, for example, according to the following route 1 when p is 0. Specifically, the aromatic compound represented by the following formula (1-1) and the halocarbonyl compound represented by the following formula (1-2) are deuterated by a Friedel-Crafts reaction to obtain the following The ketone compound represented by the formula (1-3) is obtained by deuteration of the obtained ketone compound (1-3) with a hydroxylamine to obtain an anthracene compound represented by the following formula (1-4), followed by formula (1). -4) an acid anhydride represented by the following formula (1-5) ((R ³ CO) ₂ O) or an acid halide represented by the following formula (1-6) (R ³ COHal, Hal) For halogen). When the reaction is carried out, an oxime ester compound represented by the following formula (1-7) can be obtained. Further, in the following formula (1-2), HaL is a halogen, and the following formulae (1-1), (1-2), (1-3), (1-4), and (1-7) , R ¹ , R ² , R ³ , and m are the same as formula (1).

<path 1>

The oxime ester compound represented by the formula (1) can be synthesized, for example, according to the following route 2 when p is 1. Specifically, the ketone compound represented by the following formula (2-1) is nitrite represented by the following formula (2-2) in the presence of hydrochloric acid (RONO, R is an alkyl group having 1 to 6 carbon atoms) ). The reaction is carried out to obtain a ketoxime compound represented by the following formula (2-3), and then a ketone oxime compound represented by the following formula (2-3) and an acid anhydride represented by the following formula (2-4) ((R) ³ CO) ₂ O) or an acid halide represented by the following formula (2-5) (R ³ COHal, Hal is a halogen). When the reaction is carried out, an oxime ester compound represented by the following formula (2-6) can be obtained. Further, in the following formulae (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , and m are the same formula. (1).

<path 2>

Further, in the oxime ester compound represented by the formula (1), when p is 1, and R ¹ is a methyl group and is bonded to the methyl group of the benzene ring bonded to R ¹ , and R ^{1 is} bonded to the para position, For example, a compound represented by the following formula (2-7) can be synthesized by deuteration and deuteration in the same manner as in the route 1. Further, in the following formula (2-7), R ^{2 is the} same as the formula (1).

Further, the method for synthesizing the oxime ester compound represented by the formula (1) is not limited to the above method.

However, in the synthesis method of a conventional oxime ester compound which is applicable to the production of the oxime ester compound represented by the formula (1), aluminum chloride which is a Lewis acid for the Friedel-Crafts reaction is used as an acid. A reagent for generating chloride ions such as hydrochloric acid or a carboxylic acid chloride as a deuterating agent.

Therefore, when the oxime ester compound represented by the formula (1) is produced without depending on the content of the chloride ion, an oxime ester compound containing a large amount of chloride ions is obtained.

On the other hand, as described above, the content of the chloride ion of the photopolymerization initiator in the composition I and (C) is 10 to 510 ppm by mass, preferably 10 to 500 ppm by mass, more preferably 10 to 400 ppm by mass. Therefore, in general (C) photopolymerization initiator, it is necessary to adjust the chloride ion content within a specified range.

For the above reasons, by adjusting the chloride ion content in the (C) photopolymerization initiator to adjust the chloride ion content of the mass of the solid component of the composition I, it is expressed by the synthesis formula (1). In the case of the oxime ester compound, it is preferred to carry out at least one method selected from the following 1) to 3) to lower the chloride ion content in the (C) photopolymerization initiator.

1) Reduce the amount of aluminum chloride used to the desired extent of the Friedel-Crafts reaction.

2) As far as possible, an acid containing no chlorine atom (for example, an aliphatic carboxylic acid such as acetic acid, sulfuric acid, nitric acid, or phosphoric acid) is used as the acid.

3) In the Friedel-Crafts deuteration reaction or the deuteration of a mercapto group, a carboxylic anhydride rather than a carboxylic acid chloride is used as a deuteration agent.

Further, the (C) photopolymerization initiator can be purified to reduce the content of chloride ions.

The (C) photopolymerization initiator for purifying the chloride ion content can be purified by distillation, recrystallization, water washing, or column chromatography, and the (C) photopolymerization initiator can be dissolved. A known method such as washing with a solution of a hydrophobic organic solvent.

(C) When the photopolymerization initiator is refined until the content of the chloride ion is less than 10 ppm by mass, chloride may be added to the (C) photopolymerization initiator to (C) The chloride ion content of the photopolymerization initiator is adjusted in the range of 10 to 510 ppm by mass. Further, in the specification and the patent application of the present application, "chloride" means a chloride ion and an ionic compound ionically bonded to a cation.

According to this method, it is easy to prepare a (C) photopolymerization initiator containing a desired amount of chloride ions.

In this case, as the chloride, a metal chloride such as sodium chloride, potassium chloride, iron chloride, calcium chloride, or magnesium chloride, or ammonium chloride, tetramethylammonium chloride, or tetraethyl chloride may be used. A salt of an organic cation such as ammonium or pyridinium chloride with a chloride ion or an aqueous solution of hydrochloric acid. The chloride may be used in combination of two or more kinds.

Therefore, the (C) photopolymerization initiator which is composed of the compound represented by the formula (1) and has a chloride ion content of 10 to 510 ppm by mass is preferably one containing a method selected from the following 1) to 6). A manufacturing method of the above method is produced.

Selected from

1) A compound represented by the formula (1) is synthesized by a method comprising the step of performing a Friedel-Crafts reaction using aluminum chloride, and the content of the chloride ion of the compound represented by the formula (1) becomes A method of adjusting the amount of aluminum chloride used in the range of 10 to 510 ppm by mass, 2) a method of using an acid not containing a chlorine atom in the synthesis of the compound represented by the formula (1), and 3) a formula (1) Representation of the synthesis of compounds in Friedel- a Kraffitz deuteration reaction or a deuteration of a mercapto group, a method using an acid anhydride as a deuteration agent, and 4) a crude product of the compound represented by the formula (1), which is selected from the group consisting of distillation, recrystallization, water washing, and column a method of purifying one or more methods in a group consisting of a chromatographic method, and 5) washing a solution obtained by dissolving a crude product of the compound represented by the formula (1) in a hydrophobic organic solvent, and then recovering from the washed solution. The method of the compound represented by the formula (1), and 6) the method represented by the formula (1) in which the content of the chloride ion is less than 10 mass ppm by one or more methods selected from the methods of the above 1) to 5) After the fine product of the compound, a method of adding a chloride to the refined product, and adjusting the chloride ion content of the compound represented by the formula (1) to a range of 10 to 510 ppm by mass, or one or more methods.

Particularly suitable compounds among the oxime ester compounds represented by the formula (1) include, for example, the following PI-1 to PI-42.

(C) The photopolymerization initiator may contain a photopolymerization initiator other than the oxime ester compound represented by the formula (1) as necessary. Specific examples of the other photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyl). Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one , bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl -2-dimethylamino group- 1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazole-3- ,]1-(o-acetylindenyl), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide , 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid methyl, 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid butyl, 4-di Methylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, o-benzylidene benzoic acid methyl, 2,4-diethylthioxanthone, 2-chloro Thioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thiazepine, 2-chlorothiazepine, 2,4-diethylthiazepine, 2-methylthiazepine, 2-isopropylthioindole, 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylfluorene, or Nitrogen diisobutyronitrile, benzhydryl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzene Thiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer , 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-( P-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4 '-Dimethylamino benzophenone (ie, methyl ketone), 4,4'-bisdiethylamino benzophenone (ie ethyl methyl ketone), 4,4'-dichloro Benzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl Ether, benzoin isobutyl ether, benzoin butyl Ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p -tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha, alpha-dichloride -4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, Dibenzosuberone, pentyl-4-dimethylamine Benzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-double -(9-acridinyl)propane, p-methoxytriazine, 2,4,6-parade(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloro Methyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2 -(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl) Vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloro) Methyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl) -4,6- (trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-three Chloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)benzene Base-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloro Methyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine or the like. Among these, it is preferred to use a lanthanide photopolymerization initiator on the sensitivity side. These photopolymerization initiators may be used singly or in combination of two or more kinds.

(C) The photopolymerization initiator contains the oxime represented by the formula (1) When the photopolymerization initiator other than the ester compound is used, the content of the other photopolymerizable compound is not particularly limited as long as it does not inhibit the object of the present invention. In this case, the content of the other photopolymerization initiator is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less based on the total amount of the (C) photopolymerization initiator.

In the composition I, the content of the (C) photopolymerization initiator is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, more preferably 3 to 6% by mass, more preferably the mass of the solid content of the composition I. . By the above range, a film having sufficient heat resistance and chemical resistance can be formed, and at the same time, the coating film forming ability can be improved and the photohardening failure can be suppressed.

[Other ingredients]

Various additives may be added to the composition I as necessary. Specifically, for example, a solvent, a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing aid, a filler, a adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and a thermal polymerization inhibitor , defoamers, surfactants, etc.

The solvent used in the composition I may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, or diethyl ether. Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, three Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol mono-n-propyl (poly)alkylene glycol monoalkyl ethers such as ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether acetates such as acid esters; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate Classes; 2-hydroxy-2-methylpropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3 -ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate , n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate Base ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-sided oxybutanoic acid Other esters such as ethyl ester; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Amines and the like. These solvents may be used singly or in combination of two or more.

In the above solvent, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl group are used. Ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxybutyl acetate, preferably propylene glycol monomethyl ether acetate 3-methoxybutyl acetate is particularly preferred. The content of the solvent is appropriately determined depending on the use of the composition I. However, the total amount of the solid content of the composition I is about 50 to 900 parts by mass.

The thermal polymerization inhibitor used in the composition I may, for example, be hydroquinone or hydroquinone monoethyl ether. Further, examples of the antifoaming agent include compounds such as an anthrone or a fluorine-based compound, and examples of the surfactant include compounds such as anionic, cationic, and nonionic.

[Manufacturing Method of Composition I]

The composition I contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator. The composition I may contain any of the above components as necessary.

When the composition I is produced, the above components may be mixed at the same time or may be sequentially mixed in any order.

Further, when the composition I is produced, the compound represented by the above formula (1) is contained, and the content of the chloride ion is 10 to 510 ppm by mass. The solid content of the (C) photopolymerization initiator relative to the composition I is 1 ~20% by mass.

The composition I was prepared by mixing all of the above components with a stirrer. Further, the prepared composition I may be filtered using a filter until it becomes uniform.

The chloride ion content of the composition I is relative to the solid mass, 0.1 to 30 mass ppm is preferred, 0.1 to 29.5 mass ppm is more preferable, and 0.1 to 29 mass ppm is more preferable.

The prepared composition I can also be brought into contact with the anion exchange resin to lower the chloride ion content of the composition I.

Further, a small amount of sodium chloride, potassium chloride, iron chloride, calcium chloride, magnesium chloride, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, aqueous hydrochloric acid or the like may be added to the composition I in a small amount. Chloride, adjusting the chloride ion content of composition I. At this time, the chloride can be used in a state of being diluted with an appropriate solvent.

<Composition II>

The composition II is the same as the composition I, and contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator.

Further, the chloride ion content of the composition II is preferably 0.1 to 30 mass ppm, more preferably 0.1 to 29.5 mass ppm, and more preferably 0.1 to 29 mass ppm, based on the mass of the solid component.

The necessary or optional components contained in the composition II are explained below.

[(A) alkali soluble resin]

In the composition II, as the alkali-soluble resin (A), the same resin as the alkali-soluble resin described in the composition I can be used.

Further, the content of the (A) alkali-soluble resin in the composition II was also the same as that of the composition I.

As described above, regarding the composition II, it is necessary to adjust the mass of the chloride ion content relative to the solid content of the composition II within a specified range. Inside.

(A) When the mass of the chloride ion content relative to the solid content of the composition II is adjusted by adjusting the chloride ion content in the alkali-soluble resin, the chloride ion content in the (A) alkali-soluble resin is lowered. It is better.

As a method for purifying the (A) alkali-soluble resin for lowering the chloride ion content, recrystallization, water washing, or column chromatography purification may be employed, and (A) a solution in which the alkali-soluble resin is dissolved in a hydrophobic organic solvent may be used. Known methods such as washing.

[(B) Photopolymerizable monomer]

In the composition II, as the (B) photopolymerizable monomer, the same monomer as the photopolymerizable monomer described in the composition I can be used.

Further, the content of the (B) photopolymerizable monomer in the composition II is also the same as that of the composition I.

As described above, regarding the composition II, it is necessary to adjust the chloride ion content to the mass of the solid content of the composition I within a specified range.

By adjusting the chloride ion content in the (B) photopolymerizable monomer to adjust the mass of the chloride ion content relative to the solid content of the composition I, the chloride ion content in the (B) photopolymerizable monomer is The lower one is better.

As a method for purifying the photopolymerizable monomer (B) for lowering the chloride ion content, distillation, recrystallization, water washing, column chromatography purification, (B) photopolymerizable monomer may be dissolved in hydrophobicity. A known method such as washing with a solution of an organic solvent.

[(C) Photopolymerization initiator]

In the composition II, as the (C) photopolymerization initiator, the same compound as the photopolymerization initiator described in the composition I can be used.

However, if the chloride ion content of the composition II is within the specified range, the chloride ion content of the (C) photopolymerization initiator is not necessarily in the range of 10 to 510 ppm by mass.

However, the chloride ion content of the (C) photopolymerization initiator is preferably from 10 to 510 ppm by mass, more preferably from 10 to 500 ppm by mass, even more preferably from 10 to 400 ppm by mass.

(C) Purification of the photopolymerization initiator can be carried out by the same method as that described in the composition I.

The content of the (C) photopolymerization initiator in the composition II is not particularly limited insofar as it does not inhibit the object of the present invention. The content of the (C) photopolymerization initiator in the composition II is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and 3% to 6% by mass, more preferably the mass of the solid content of the composition II. good.

[Other ingredients]

Composition II and composition I may contain other components. The type and content of the other components in the composition II are the same as those of the composition I.

[Manufacturing Method of Composition II]

As described above, the composition II is the same as the composition I, and contains (A) a base. A soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator. The composition II may contain any of the above components as necessary.

When the composition II is produced, the above components may be mixed at the same time or may be sequentially mixed in any order.

Further, when the composition II is produced, the (C) photopolymerization initiator containing the compound represented by the above formula (1) can be used.

Further, when the composition II is produced, the content of the chloride ion in the composition II is 0.1 to 30 ppm by mass based on the mass of the solid content of the composition II.

The composition II was prepared by mixing all of the above components with a stirrer. Further, the prepared composition II can be filtered to be uniform using a filter.

The chloride ion content of the composition II is preferably 0.1 to 30 ppm by mass, preferably 0.1 to 29.5 ppm by mass, more preferably 0.1 to 29 ppm by mass, based on the mass of the solid component.

The method of adjusting the chloride ion content of the composition II is not particularly limited.

The prepared composition II can be contacted with an anion exchange resin to reduce the chloride ion content of the composition II.

A chloride ion content of the composition I may be adjusted by adding a small amount of chloride such as sodium chloride, potassium chloride, ammonium chloride, aqueous hydrochloric acid, calcium chloride or magnesium chloride to the composition II. At this time, the chloride can be used in a suitable solvent dilution state.

<Method of Forming Film>

The method of forming the film using the photosensitive composition is not particularly limited except for the use of the above-described composition I or composition II. The film can be formed according to a conventional film formation method using a photosensitive composition.

The method of forming a film typically includes forming a coating film on which a photosensitive composition of a first aspect or a second aspect is applied onto a substrate, and exposing the coating film.

A method of forming a coating film on a substrate by using a photosensitive composition, for example, a contact transfer type coating device or a spin coater such as a roll coater, a reverse coater, or a bar coater (rotary type) A method of a non-contact type coating device such as a coating device or a curtain coater.

The coated photosensitive composition is dried to form a coating film as necessary. The drying method is not particularly limited, and for example, (1) drying at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, and (2) standing at room temperature for several hours to several days The method, (3) a method of removing the solvent by immersing in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, the coating film is exposed to an active energy ray such as ultraviolet rays or excimer laser light. The coating film is usually patterned more often. In order to form a patterned film, the coating film is exposed through a negative mask.

The amount of energy rays to be irradiated varies depending on the composition of the photosensitive composition, and is preferably, for example, about 30 to 2000 mJ/cm ² . As described above, by using the photosensitive composition of the present invention, the sensitivity can be improved to improve the productivity of the transparent insulating film.

When exposure is performed through a negative mask, after exposure, the exposed coating film is developed with a developing solution to form a film patterned into a desired shape.

The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The developer may, for example, be an organic one such as monoethanolamine, diethanolamine or triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or a quaternary ammonium salt.

Then, it is preferable to perform post-exposure baking on the film after exposure or after exposure and development at about 200 to 250 °C.

According to the method described above, a film is formed by using the photosensitive composition, and a film having a film thickness standard deviation of less than 25 and a small film thickness distribution can be formed.

The film formed as described above is excellent in transparency and is suitable for various uses such as a transparent insulating film.

<Method for suppressing adhesion increase when storing photosensitive composition>

When the photosensitive composition containing the (A) alkali-soluble resin and (B) the photopolymerizable monomer and the (C) photopolymerization initiator containing the oxime ester compound represented by the formula (1) is prepared, chlorine is used. The (C) photopolymerization initiator having a compound ion content of 10 to 510 ppm by mass is used in an amount of 1 to 20% by mass based on the mass of the photosensitive composition, and the viscosity increase during storage of the photosensitive composition is suppressed.

Further, the above-mentioned (A) alkali-soluble resin and (B) photopolymerizable monomer and the oxime ester compound represented by the formula (1) are prepared. (C) When the photosensitive composition of the photopolymerization initiator is used, the content of the chloride ion in the photosensitive composition is 0.1 to 30 ppm by mass relative to the solid content, thereby suppressing the viscosity increase during storage of the photosensitive composition. .

<Photopolymerization initiator>

The photopolymerization initiator containing the oxime ester compound represented by the above formula (1) and having a chloride ion content of 10 to 510 ppm by mass, preferably 10 to 500 ppm by mass, more preferably 10 to 400 ppm by mass, may be used. The formation of a photosensitive composition which is excellent in transparency and which is suppressed in viscosity during storage is prepared.

[Examples]

The present invention will be more specifically described by the following examples, but the scope of the invention is not limited to the examples.

In the examples and comparative examples, as the (C) photopolymerization initiator, an oxime ester compound ((E)-2-(ethyloxyimino)-1-(4-(phenyl)) having the following structure was used. Thio)phenyl)-2-o-tolyl ethyl ketone). The (C) photopolymerization initiator used in the examples and the comparative examples was prepared by the following method.

First, the following compound was obtained according to the method of Synthesis Example 8 described in JP-A-2013-148872 (PI-H, (E)-2-(ethyloxyimino) described in JP-A-2013-148872 1-(4-(phenylthio)phenyl)-2-o-tolyl ethyl ketone). Next, the obtained compound was recrystallized, and the water washing treatment was repeated to obtain a purified product substantially used in Comparative Example 1. A compound that does not contain chloride ions.

For the purified compound used in Comparative Example 1, a chloride was appropriately added as an additive of the type described in Table 1, and a compound containing the chloride ion in the amount shown in Table 1 was prepared and used in each of the examples.

In Examples 1 to 10 and Comparative Examples 1 to 5, the alkali-soluble resin 65 having the following structure (mass ratio I-1: I-2: II-1: III-1 was 25:20:14:41) was used. Parts by mass and dipentaerythritol hexaacrylate (photopolymerization) 35 parts by mass of the photopolymerization initiator prepared according to Table 1, 5 parts by mass of the photopolymerization initiator, dissolved in diethylene glycol methyl ethyl ether and propylene glycol monomethyl group in such a manner that the solid content concentration is 24% by mass A mixed solvent of ether acetate (mass ratio: 55:45) was used to prepare a photosensitive composition.

Alkali-soluble resin, photopolymerizable monomer, mixed solvent of diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate (mass ratio 55:45), all using chloride ion content of less than 1 mass Ppm.

Using the obtained photosensitive composition, the transmittance of the formed film, the film thickness uniformity, and the storage stability were evaluated by the following methods. The results of these assessments are shown in Table 2.

<Film transmittance>

The photosensitive composition prepared in each of the above Examples and Comparative Examples was spin-coated on a glass substrate by a spin coater (three-dimensional spin coater IH-360S, manufactured by Sanken Co., Ltd.), and the coating film was allowed to stand at 100 ° C. The film was dried for 100 seconds to form a photosensitive resin layer. Then, the exposure resin (MPA600FA, manufactured by Canon Co., Ltd.) was changed to expose the photosensitive resin layer by changing the exposure amount of 50 mJ/cm ² . Thereafter, post-exposure baking was performed at 230 ° C for 20 minutes. The film thickness after post-exposure baking was 3 μm. The film thickness of the pattern was measured using a stylus type surface shape measuring instrument (Dektak 3st, manufactured by Aike Co., Ltd.).

The transmittance of the formed cured film at a wavelength of 400 nm was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).

<Film thickness uniformity>

Using a photosensitive composition of each case which was stored at 25 ° C for one month, the film formed in the same manner as the transmittance evaluation was used, and the film thickness (Å) in 25 (equal intervals) between the both ends of the diameter of the ruthenium substrate was used. The surface shape measuring device (Dektak 3st, manufactured by Aikei Co., Ltd.) was measured, and the standard deviation (σ) of the film thickness at 25 points was determined, and the film thickness uniformity was evaluated based on the following criteria.

Here, the "standard deviation (σ)", the smaller the value, the smaller the distribution in the film thickness, indicating that a resist film having a high film thickness uniformity is obtained.

(assessment basis)

○: The standard deviation (σ) is less than 25.

×: The standard deviation (σ) is 25 or more.

<Save stability>

The viscosity V ₀ of the photosensitive composition immediately after the preparation was measured. Next, the viscosity V ₁ of the photosensitive composition stored at 25 ° C for one month was measured. The storage stability of the k-photosensitive composition was evaluated from the values of V _{0 and} the value of V ₁ in accordance with the following criteria.

(assessment basis)

○: V ₁ /V _{0 is} less than 1.1

×: V ₁ /V ₀ is 1.1 or more

Table 2 shows that the specific amount of the (C) photopolymerization initiator containing a chloride ion content of 10 to 510 ppm by mass or the chloride ion content of the composition is 0.1 to 30 ppm by mass relative to the solid content. The photosensitive composition can form a film having a high transmittance of 98% or more and has excellent storage stability.

According to Comparative Example 1, it is understood that (C) the photopolymerization initiator or the chloride ion content in the photosensitive composition is too small, and the photosensitive composition is likely to increase during storage. sticky.

In Comparative Examples 2 to 5, it was found that (C) the photopolymerization initiator or the photosensitive composition had too much chloride ion content, and only a film having a transmittance of about 95% of transmittance was formed.

Claims (17)

A photosensitive composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, wherein the (C) photopolymerization initiator contains the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a compound represented by a phenyl group or a carbazolyl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the chloride ion of the above (C) photopolymerization initiator The content is 10 to 510 ppm by mass, and the ratio of the mass of the (C) photopolymerization initiator to the solid content of the photosensitive composition is 1 to 20% by mass. A photosensitive composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, and the (C) photopolymerization initiator contains the following formula (1) ): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a compound represented by a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the content of the chloride ion is relative to the mass of the solid component. 0.1 to 30 mass ppm. The photosensitive composition according to claim 2, wherein the (C) photopolymerization initiator has a chloride ion content of 10 to 510 ppm by mass. The photosensitive composition according to any one of the above claims 1 to 3, wherein the R ² in the formula (1) is the following formula (2) or the following formula (3): (In the formula (2), R ⁴ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, and A is S or O, and n is an integer of 0 to 4, In (3), each of R ⁵ and R ⁶ is a group represented by a monovalent organic group. A method for forming a film, comprising the formation of a coating film obtained by applying the photosensitive composition according to any one of claims 1 to 3 to a substrate, and exposing the coating film. The method for forming a film according to claim 5, wherein the standard deviation of the film thickness of the formed film is less than 25. A method for suppressing and increasing adhesion when a photosensitive composition is stored, which comprises preparing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and the (C) light The polymerization initiator contains the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. When the photosensitive composition of the compound represented by the phenyl group of the group or the carbazole group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the photosensitive composition is blended with the photosensitive composition. The solid content of the solid content is 1 to 20% by mass of the chloride ion content of 10 to 510 ppm by mass of the above (C) photopolymerization initiator. A method for suppressing and increasing adhesion when a photosensitive composition is stored, characterized in that it contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and the aforementioned (C) light The polymerization initiator contains the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. When the photosensitive composition of the compound represented by the phenyl group or the carbazole group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the photosensitive composition The content of the compound ion is 0.1 to 30 ppm by mass based on the mass of the solid content. A photopolymerization initiator characterized by containing a chloride ion in an amount of 10 to 510 ppm by mass and having the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. A compound represented by a phenyl group of the group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A method for producing a photosensitive composition, which comprises a method for producing a photosensitive composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, characterized in that it contains the following Description (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a compound represented by a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is relative to the solid content of the photosensitive composition. The (C) photopolymerization initiator is used in combination with 1 to 20% by mass of a chloride ion in an amount of 10 to 510 ppm by mass. The method for producing a photosensitive composition according to claim 10, wherein the content of the chloride ion in the photosensitive composition is 0.1 to 30 ppm by mass based on the mass of the solid content of the photosensitive composition. The method for producing a photosensitive composition according to claim 11, wherein the photosensitive property is adjusted by a method of bringing the photosensitive composition into contact with an anion exchange resin and/or a method of adding a chloride to the photosensitive composition. The amount of chloride ions in the composition. The method for producing a photosensitive composition according to claim 12, wherein the content of the chloride ion in the photosensitive composition is adjusted by bringing the photosensitive composition into contact with the anion exchange resin. A method for producing a photosensitive composition, which comprises a method for producing a photosensitive composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator; Take the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. The aforementioned (C) photopolymerization initiator of a compound represented by a phenyl group or a carbazole group which may have a substituent, and a compound represented by R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which makes the aforementioned photosensitivity The content of the chloride ion in the composition is 0.1 to 30 ppm by mass based on the mass of the solid content of the photosensitive composition. The method for producing a photosensitive composition according to claim 14, wherein the photosensitive property is adjusted by a method of bringing the photosensitive composition into contact with an anion exchange resin and/or a method of adding a chloride to the photosensitive composition. The amount of chloride ions in the composition. The method for producing a photosensitive composition according to claim 15, wherein the content of the chloride ion in the photosensitive composition is adjusted by contacting the photosensitive composition with an anion exchange resin. A method for producing a photopolymerization initiator which is represented by the following formula (1): (R ¹ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, m is an integer of 0 to 4, p is 0 or 1, and R ² is a substitutable group. a compound represented by a phenyl group or a carbazolyl group which may have a substituent, and R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the content of the chloride ion is 10 to 510 ppm by mass. The characteristics include one or more of the following methods selected from 1) to 6): 1) synthesizing the above formula (1) by a method comprising the step of performing a Friedel-Crafts reaction using aluminum chloride a compound represented by the method, wherein the amount of the chloride ion used in the compound represented by the formula (1) is in the range of 10 to 510 ppm by mass, and 2) A method of synthesizing the compound represented by the above formula (1), and using the acid containing no chlorine atom in the deuteration to obtain the photopolymerization initiator having a chloride ion content of 10 to 510 ppm by mass, and 3) The compound represented by the above formula (1) is synthesized by a method comprising a Friedel-Crafts deuteration reaction or a thiol group, in the Fried - a Kraffs deuteration reaction or a mercapto group, using an acid anhydride as a deuteration agent to obtain a photopolymerization initiator of a chloride ion content of 10 to 510 ppm by mass, and 4) 1) The crude product of the compound shown is purified by one or more methods selected from the group consisting of distillation, recrystallization, water washing, and column chromatography to obtain a chloride ion content of 10 to 510. a method of mass ppm of the photopolymerization initiator described above, 5) a solution in which a crude product of the compound represented by the above formula (1) is dissolved in a hydrophobic organic solvent, and washed with water, and the above formula (1) is recovered from the washed solution. And a method of obtaining the above-mentioned photopolymerization initiator having a chloride ion content of 10 to 510 ppm by mass, and 6) a method selected from the group consisting of 1a) to 5a below. In the above method, after obtaining a refined product of the compound represented by the above formula (1) having a chloride ion content of less than 10 ppm by mass, a chloride is added to the refined product to obtain a compound represented by the above formula (1). The method of adjusting the chloride ion content to a range of 10 to 510 mass ppm, 1a) a method comprising the step of performing a Friedel-Crafts reaction using aluminum chloride, synthesizing the compound represented by the above formula (1), and adjusting the amount of aluminum chloride used to cause chlorine of the compound represented by the above formula (1) a method in which the content of the compound ion is in the range of less than 10 ppm by mass, 2a) a compound represented by the above formula (1) is synthesized by a method including deuteration, and an acid containing no chlorine atom is used in the deuteration. Method, 3a) synthesizing the compound represented by the above formula (1) by a method comprising a Friedel-Crafts deuteration reaction or a sulfhydryl group, in which the Friedel-Crafts deuteration reaction Or a sulfhydryl group, a method of using an acid anhydride as a hydrating agent, and 4a) a crude product of the compound represented by the above formula (1), which is selected from the group consisting of distillation, recrystallization, water washing, and column chromatography. a method of purifying one or more methods in the group of the constituents, and 5a) washing the solution of the crude product of the compound represented by the above formula (1) in a solution of a hydrophobic organic solvent, and then recovering the above formula from the washed solution ( 1) Method of the compound represented.