Active energy ray curable composition for pattern formation

Abstract

To provide an active energy ray-curing type composition for pattern formation that is excellent in sensitivity, developability and pattern formability.SOLUTION: The active energy ray-curing type composition for pattern formation includes (A) component: a (meth)acrylate of an alkylene oxide adduct of alditol (exclusive of glycerol). As the component (A), a mixture of a compound having a (meth)acryloyl group produced by subjecting an alkylene oxide adduct of alditol (exclusive of glycerol) and a compound having one (meth)acryloyl group to transesterification reaction in the presence of a catalyst X and a catalyst Y as given below is preferable. The catalyst X: one or more kinds of compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof and phosphine or a salt or complex thereof; and a catalyst Y: a compound including zinc.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable composition for pattern formation, and belongs to the technical field. In this specification, "acryloyl group and / or methacryloyl group" is referred to as "(meth)acryloyl group", "acrylate and / or methacrylate" is referred to as "(meth)acrylate", and "acrylic acid and / or methacrylic acid" is referred to as "(meth)acrylic acid". [Background technology]

[0002] Conventionally, compositions containing (meth)acrylate compounds have been widely used as resists for use in etching resists, solder resists, and color resists for forming colored layers of color filters, etc. In these resists, (meth)acrylates having two or more (meth)acryloyl groups (hereinafter referred to as "polyfunctional (meth)acrylates") are used for the purpose of improving the sensitivity of the composition and the hardness of the cured product.

[0003] Many of the polyfunctional (meth)acrylates used in conventional resists are alkali-insoluble, which means that uncured (unexposed) areas tend to remain as film during development, making it difficult to obtain sufficient resolution.

[0004] Known active energy ray-curable pattern-forming compositions for color filters include compositions containing a polyfunctional (meth)acrylate having no carboxyl group, an alkali-soluble resin, a photopolymerization initiator, and an organic solvent (Patent Document 1). This invention increases the ratio of photocurable groups and acidic functional groups introduced into the alkali-soluble resin in order to improve the crosslink density and alkali solubility of the cured product. However, there is a limit to the amount of photocurable groups and acidic functional groups that can be introduced, and there is also a problem that the viscosity of the composition increases, impairing its suitability for coating.

[0005] In view of this, active energy ray-curable compositions have been proposed that contain an alkali-soluble carboxyl group-containing multifunctional (meth)acrylate obtained by reacting a hydroxyl group-containing multifunctional (meth)acrylate having a hydroxyl group and a plurality of (meth)acryloyl groups with an acid anhydride such as a carboxylic acid anhydride (Patent Documents 2, 3, and 4). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2000-105456 A [Patent Document 2] JP 2001-089416 A [Patent Document 3] JP 2001-091954 A [Patent Document 4] JP 2014-215515 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, the conventional active energy ray-curable compositions containing a carboxyl group-containing polyfunctional (meth)acrylate compound described in Patent Documents 2 to 4 have improved alkaline developability compared to active energy ray-curable compositions containing a polyfunctional (meth)acrylate that does not have a carboxyl group, but their solubility in an alkaline aqueous solution is still insufficient, and uncured residues are generated during development, so that further improvement in alkaline developability is required. The inventors of the present invention have conducted extensive research in order to find an active energy ray-curable composition for pattern formation that is excellent in sensitivity, developability and pattern formability. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have discovered that a composition containing a polyfunctional (meth)acrylate produced from a plant-derived alcohol and having both a hydroxyl group and an ether group in the molecule has excellent sensitivity, developability and pattern formability, and have completed the present invention. The present invention will be described in detail below. Effect of the Invention

[0009] The active energy ray-curable composition for pattern formation of the present invention is excellent in sensitivity, developability and pattern formability. Therefore, the composition of the present invention can be preferably used as a pattern forming agent for various applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention relates to an active energy ray-curable composition for pattern formation, comprising component (A): a (meth)acrylate of an alkylene oxide adduct of an alditol (excluding glycerol). In the following, "alditol (excluding glycerol)" may be simply referred to as "alditol". The component (A), the active energy ray-curable composition for pattern formation, and the method of use will be described below. In the following, the "active energy ray-curable composition for pattern formation" may be simply referred to as the "composition".

[0011] 1. Component (A) The component (A) is a (meth)acrylate of an alkylene oxide adduct of an alditol (excluding glycerol). In the present invention, an alkylene oxide adduct of alditol (hereinafter referred to as "AZ-RO") is used as the raw material compound of component (A). However, in the present invention, the alditol does not include glycerol.

[0012] 1-1.AZ-RO As the alditol, which is the raw material compound of AZ-RO, various compounds can be used. Specific examples of alditols include erythritol, threitol, ribitol, arabinitol, xylitol, allitol, sorbitol (glycitol), mannitol, iditol, galactitol, and talitol, and it is preferable to use the D-form, which is easily available. Among these compounds, erythritol, xylitol, sorbitol (glycitol), and mannitol are preferred because they are easily available industrially and the desired (meth)acrylates can be easily produced. It is more preferred to use the D-form, which is easily available, and D-sorbitol (D-glycitol) and D-mannitol are even more preferred. stomach. These compounds are derived from plants and have a low environmental impact. As the alditol, these compounds can be used alone or in combination of two or more kinds. Of these compounds, sorbitol is preferred as the alditol.

[0013] Examples of the alkylene oxide unit in AZ-RO include ethylene oxide, propylene oxide, tetramethylene oxide, and mixed units of these alkylene oxides. Among these, ethylene oxide is preferred because the resulting (meth)acrylate has excellent sensitivity. Regarding the number of moles of alkylene oxide added in AZ-RO, a compound having a large number of moles added is preferred because it is generally easy to handle and can reduce inhibition of radical polymerization in the presence of oxygen. The number of moles of alkylene oxide added in AZ-RO is preferably 1-20, and more preferably 2-15. By making the number of moles of alkylene oxide added 1 or more, AZ-RO dissolves only in hydrophilic solvents such as water and alcohol, and is less soluble in compounds having one (meth)acryloyl group in the transesterification reaction and in organic solvents, preventing the transesterification reaction from proceeding easily, and when the resulting (meth)acrylate is used as a component of a composition, it is possible to prevent a significant decrease in compatibility with other components. On the other hand, by making the number of moles of alkylene oxide added 20 or less, it is possible to increase the hardness of the cured product when the resulting (meth)acrylate is used as a component of a composition.

[0014] The component (A) is produced by (meth)acrylating AZ-RO. Methods for producing component (A) include a method of subjecting AZ-RO to an ester exchange reaction with a compound having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylate") in the presence of an ester exchange catalyst, and a method of subjecting AZ-RO to a dehydration esterification reaction with (meth)acrylic acid in the presence of an acid catalyst, with the ester exchange reaction being preferred.

[0015] 1-2.Preferable form of component (A) Component (A) is preferably a mixture of reaction products containing (meth)acrylate obtained by transesterification of AZ-RO with a monofunctional (meth)acrylate. Component (A) is a mixture of (meth)acrylates and by-products having different numbers of (meth)acryloyl groups.

[0016] Examples of the alkylene oxide unit in the component (A) include ethylene oxide, propylene oxide, tetramethylene oxide, and mixed units of these alkylene oxides, with ethylene oxide being preferred in terms of excellent sensitivity. Regarding the number of moles of alkylene oxide added in the component (A), a compound having a large number of moles added is preferred because it is generally easier to handle and can reduce inhibition of radical polymerization in the presence of oxygen. The number of moles of alkylene oxide added in the component (A) is preferably 1-20, and more preferably 2-15. By making the number of moles of alkylene oxide added 1 or more, AZ-RO dissolves only in hydrophilic solvents such as water and alcohol, and is less soluble in monofunctional (meth)acrylates and organic solvents in the transesterification reaction, which prevents the transesterification reaction from proceeding easily, and when the resulting (meth)acrylate is used as a component of a composition, it is possible to prevent a significant decrease in compatibility with other components. On the other hand, by making the number of moles of alkylene oxide added 20 or less, it is possible to increase the hardness of the cured product when the resulting (meth)acrylate is used as a component of a composition. Furthermore, as the component (A), AZ-RO is preferably a (meth)acrylate obtained from an alkylene oxide adduct of sorbitol.

[0017] The component (A) is preferably hydrophilic, and more preferably water-soluble. When the component (A) is hydrophilic or water-soluble, the composition has extremely high hydrophilicity before being irradiated with active energy rays, and therefore has high solubility in an alkaline aqueous solution and excellent alkaline developability. In the present invention, "hydrophilic" or "water-soluble" means that the solubility of component (A) in distilled water at a temperature of 22°C is 10% or more. The solubility is defined by the following formula, and means that when distilled water and component (A) are mixed and allowed to stand, the mixture is in a homogeneous liquid state, with no turbidity or layer separation observed. (A) Solubility of component in distilled water (%) = parts by weight of distilled water / (parts by weight of distilled water + parts by weight of component (A)) x 100

[0018] Therefore, the solubility of distilled water at 22° C. (hereinafter simply referred to as "water solubility") of component (A) is preferably 10% or more, more preferably 25% or more, and particularly preferably 40% or more. In the present invention, the hydroxyl groups of AZ-RO, which is a raw material compound of component (A), are subjected to an ester exchange reaction, preferably using catalysts X and Y, to obtain component (A) having a (meth)acryloyl group. By controlling the (meth)acrylate conversion rate of the hydroxyl groups and leaving the hydroxyl groups, component (A) can be made to exhibit extremely high solubility in water.

[0019] Furthermore, the component (A) is preferably a mixture having a saponification value of 150 to 450 mgKOH / g, more preferably 150 to 300 mgKOH / g, and particularly preferably 200 to 280 mgKOH / g. By making the saponification value of the component (A) 150 mgKOH / g or more, the hardness of the cured product of the composition containing the component (A) can be made high, and by making the saponification value 450 mgKOH / g or less, the component (A) can be made to have excellent hydrophilicity or water solubility. In the present invention, the saponification value means a value obtained by adding an ethanol solution of potassium hydroxide to a sample, heating the sample in a warm bath at 75°C for 30 minutes, allowing the sample to cool, and then titrating the base with an aqueous hydrochloric acid solution using a phenolphthalein solution as an indicator.

[0020] The hydroxyl value of component (A) is preferably at least 10 mgKOH / g, more preferably at least 100 mgKOH / g, and particularly preferably at least 150 mgKOH / g. The preferred upper limit of the hydroxyl value of component (A) is 600 mgKOH / g. By making the hydroxyl value 10 mgKOH / g or more, the component (A) can be made to have excellent hydrophilicity or water solubility. In the present invention, the hydroxyl value refers to the value obtained by adding a mixture of acetic anhydride and pyridine to a sample, heating the sample in a warm bath at 92°C for 1 hour, adding a small amount of water and heating the sample in a warm bath at 92°C for 10 minutes, allowing the sample to cool, and then titrating the acid with an ethanol solution of potassium hydroxide using a phenolphthalein solution as an indicator.

[0021] The component (A) is preferably a compound represented by the following general formula (5).

[0022] [ka]

[0023] [In formula (5), R 14 ~R 16 each independently represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms; R 14 ~R 16 When there are a plurality of each of X, they may be the same or different. 1 ~X 3 Each of X independently represents a hydrogen atom or a (meth)acryloyl group. 2 may be the same or different, and multiple R 15 may be the same or different, and multiple b's may be the same or different. a, b, and c each represent a positive number, and are not all 0 at the same time, and satisfy 0<(a+nb+c)≦80. n represents an integer of 2 to 4.

[0024] In the formula (5), n, which means the structure of an alditol skeleton, is an integer of 2 to 4, and a compound having a sorbitol skeleton where n=4 is preferred. Furthermore, X 2 When n is 2, 3, or 4, there is X in one molecule, respectively. 2 The compounds have 2, 3, and 4 X 2 There are 2 to 4 of X in one molecule, but multiple X 2 may be the same or different. Specifically, when n is 4, X 2 A compound with four X 2 may be a hydrogen atom or a (meth)acryloyl group.

[0025] R 14 ~R 16 are each independently a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms. Examples of the aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group and a branched aliphatic hydrocarbon group. Specific examples of the linear aliphatic hydrocarbon group include an ethylene group, a 1,3-propylene group (a trimethylene group), and a 1,4-butylene group (a tetramethylene group). Specific examples of the branched aliphatic hydrocarbon group include a 1,2-propylene group (isopropylene group) and a 1,1-dimethylethylene group (isobutylene group). R 14 ~R 16 Of these functional groups, an ethylene group is preferred. R 14 ~R 16 Of these functional groups, an ethylene group is preferred. Furthermore, R 15 When n is 2, 3, or 4, each molecule contains R 15 The compounds have 2, 3, and 4 R 15 There are 2 to 4 R in one molecule, but 15 may be the same or different. 15 It is preferable that the functional groups are the same as each other.

[0026] a, b and c represent the average number of moles of oxyalkylene units present on the hydroxyl groups of the alditol. a, b and c each represent a positive number, and cannot all be 0 at the same time. a+nb+c means the total number of moles of oxyalkylene units added in the alditol molecule (the average number of moles of alkylene oxide added relative to the total number of alditols). a+nb+c satisfies the following formula. 0<(a+nb+c)≦80 The lower limit of a+nb+c is preferably 1 or more. It is more preferable that a+nb+c is 2≦(a+nb+c)≦10. By setting it in this range, synthesis becomes easy and it is advantageous in terms of economy, and compatibility with other components becomes good, so that the degree of freedom in compounding design is increased, and a composition with excellent sensitivity can be obtained. When n is 2, 3, or 4, the compound has 2, 3, or 4 b's in one molecule, respectively. There are 2 to 4 b's in one molecule, and the multiple b's may be the same or different from each other.

[0027] As the (meth)acrylate, an acrylate is preferred because of the reactivity during the transesterification reaction and the high sensitivity of the component (A).

[0028] 1-3. Manufacturing method of component (A) As a method for producing the component (A), as described above, a method in which AZ-RO is subjected to an ester exchange reaction with a monofunctional (meth)acrylate in the presence of an ester exchange catalyst is preferred. Furthermore, the method for producing the component (A) is preferably a method in which AZ-RO is subjected to a transesterification reaction with a monofunctional (meth)acrylate in the presence of catalysts X and Y described below. Catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure, a salt thereof, or a complex thereof, an amidine, a salt thereof, or a complex thereof, a compound having a pyridine ring, a salt thereof, or a complex thereof, and a phosphine, a salt thereof, or a complex thereof. Catalyst Y: A compound containing zinc. A preferred method for producing the component (A) will now be described.

[0029] 1-3-1.AZ-RO AZ-RO is described in detail above.

[0030] 1-3-2. Monofunctional (meth)acrylate The monofunctional (meth)acrylate used as a raw material for the component (A) is a compound having one (meth)acryloyl group in the molecule, and examples thereof include compounds represented by the following general formula (1).

[0031] [ka]

[0032] In formula (1), R1 R represents a hydrogen atom or a methyl group. 2 represents an organic group having 1 to 50 carbon atoms.

[0033] R in the above general formula (1) 2 Preferred specific examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group; alkoxyalkyl groups, such as a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-methoxybutyl group; and dialkylamino groups, such as an N,N-dimethylaminoethyl group, an N,N-diethylaminoethyl group, an N,N-dimethylaminopropyl group, and an N,N-diethylaminopropyl group. R in the above general formula (1) 2 In addition to the above, specific examples of the functional groups include those described in JP2017-39916A, JP2017-39917A, and WO2017 / 033732A.

[0034] In the present invention, these monofunctional (meth)acrylates can be used alone or in any combination of two or more. Among these monofunctional (meth)acrylates, alkyl (meth)acrylates having an alkyl group with 1 to 8 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl acrylate, or N,N-dimethylaminoethyl (meth)acrylate are preferred, and in particular, (meth)acrylates having an alkyl group with 1 to 4 carbon atoms, or alkoxyalkyl (meth)acrylates having an alkyl group with 1 to 2 carbon atoms, which show good reactivity with AZ-RO and are easily available, are preferred. Furthermore, alkoxyalkyl(meth)acrylates having an alkyl group with 1 to 2 carbon atoms, which promote the dissolution of AZ-RO and exhibit extremely good reactivity, are more preferred, and 2-methoxyethyl(meth)acrylate is particularly preferred. Furthermore, as the monofunctional (meth)acrylate, acrylate is particularly preferred due to its excellent reactivity.

[0035] The ratio of AZ-RO and monofunctional (meth)acrylate used in the production method of component (A) is not particularly limited, but the ratio of monofunctional (meth)acrylate used to 1 mole of hydroxyl group of AZ-RO is preferably 0.4 to 10.0 moles, more preferably 0.6 to 5.0 moles. By making the ratio of monofunctional (meth)acrylate used 0.4 moles or more, it is possible to suppress side reactions. In addition, by making the ratio of monofunctional (meth)acrylate used 10.0 moles or less, it is possible to increase the amount of component (A) produced, thereby improving productivity.

[0036] Catalyst As the transesterification catalyst in the production method of the component (A), the following catalysts X and Y are used in combination because they enable the production of a (meth)acrylate in high yield. Catalyst X: One or more compounds selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or their salts or complexes (hereinafter referred to as "azabicyclo compounds"), amidines or their salts or complexes (hereinafter referred to as "amidine compounds"), compounds having a pyridine ring or their salts or complexes (hereinafter referred to as "pyridine compounds"), and phosphines or their salts or complexes (hereinafter referred to as "phosphine compounds"). Catalyst Y: A compound containing zinc. Catalyst X and catalyst Y will be described below.

[0037] 1-3-3-1. Catalyst X The catalyst X in the method for producing the component (A) is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds, and phosphine compounds. These compounds are preferred because of their excellent catalytic activity. Among the above-mentioned compounds, the catalyst X is preferably one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, and pyridine compounds. These compounds have excellent catalytic activity and can preferably produce the component (A). In addition, they form a complex with the catalyst Y described below during and after the reaction, and the complex can be easily removed from the reaction solution after the reaction is completed by a simple method such as adsorption. In particular, the azacyclo compound can be more easily removed by filtration, adsorption, etc., because the complex with the catalyst Y is poorly soluble in the reaction solution. On the other hand, although the phosphine-based compound has excellent catalytic activity, it is difficult to form a complex with the catalyst Y, or when a complex is formed, it is easily soluble in the reaction solution, and most of the phosphine-based compound or complex remains dissolved in the reaction solution after the reaction is completed, making it difficult to remove from the reaction solution by a simple method such as filtration or adsorption. For this reason, the phosphine-based catalyst remains in the final product, which may cause storage stability problems such as turbidity or precipitation of the catalyst during storage of the product, or thickening or gelation over time.

[0038] Specific examples of azabicyclo-based compounds include various compounds that are cyclic tertiary amines having an azabicyclo structure, salts of the amines, or complexes of the amines. Preferred compounds include quinuclidine, 3-hydroxyquinuclidine, 3-quinuclidinone, 1-azabicyclo[2.2.2]octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane, hereinafter referred to as "DABCO"). In addition to the above, specific examples of the azabicyclo-based compound include the compounds described in JP2017-39916A, JP2017-39917A, and WO2017 / 033732A.

[0039] Specific examples of amidine compounds include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo[4.3.0]non-5-ene (hereinafter referred to as "DBN"), N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and phthalimide DBU.

[0040] Specific examples of pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N,N-dimethyl-4-aminopyridine (hereinafter referred to as "DMAP"). In addition to the above, specific examples of the pyridine-based compound include the compounds described in JP2017-39916A, JP2017-39917A, and WO2017 / 033732A.

[0041] Examples of the phosphine-based compound include compounds having a structure represented by the following general formula (2).

[0042] [ka]

[0043] [In formula (2), R 3 , R 4 and R 5 R each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. 3 , R 4 and R 5may be the same or different.

[0044] Specific examples of the phosphine compound include triphenylphosphine, tris(4-methoxyphenyl)phosphine, tri(p-tolyl)phosphine, tri(m-tolyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl)phosphine, and tricyclohexylphosphine. In addition to the above, specific examples of the phosphine-based compound include the compounds described in JP2017-39916A, JP2017-39917A, and WO2017 / 033732A.

[0045] In the present invention, these catalysts X can be used alone or in any combination of two or more. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferred, and 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP are particularly preferred because they show good reactivity with most polyhydric alcohols and are easily available.

[0046] The proportion of catalyst X used in the production method of component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol, and more preferably 0.0005 to 0.2 mol, of catalyst X per mol of hydroxyl group of AZ-RO. By using 0.0001 mol or more of catalyst X, the yield of the target reaction product containing (meth)acrylate can be increased, and by using 0.5 mol or less, the production of by-products and coloring of the reaction liquid can be suppressed, and the purification step after completion of the reaction can be simplified.

[0047] 1-3-3-2. Catalyst Y Catalyst Y is a compound containing zinc. As the catalyst Y, various compounds containing zinc can be used, but organic acid zinc and zinc diketone enolate are preferred because of their excellent reactivity. Examples of the organic zinc acid include zinc dibasic acids such as zinc oxalate and compounds represented by the following general formula (3).

[0048] [ka]

[0049] [In formula (3), R 6 and R 7 R each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. 6 and R 7 may be the same or different. The compound of formula (3) is R 6 and R 7 are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkenyl group having 1 to 20 carbon atoms. 6 and R 7 In the above formula, the linear or branched alkyl group having 1 to 20 carbon atoms or the linear or branched alkenyl group having 1 to 20 carbon atoms is a functional group that does not have a halogen atom such as fluorine or chlorine, and the catalyst Y having such a functional group is preferred because it can produce the target reaction product containing the (meth)acrylate in high yield.

[0050] An example of the zinc diketone enolate is a compound represented by the following general formula (4).

[0051] [ka]

[0052] [In formula (4), R 8 , R 9 , R 10 , R 11 , R 12 and R 13R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. 8 , R 9 , R 10 , R 11 , R 12 and R 13 may be the same or different.

[0053] Specific examples of the zinc-containing compound represented by the above general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octoate, zinc neodecanoate, zinc laurate, zinc myristate, zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate. Furthermore, when hydrates, solvates, or complexes with catalyst X exist for these zinc-containing compounds, the hydrates, solvates, and complexes with catalyst X can also be used as catalyst Y in the production method for component (A).

[0054] Specific examples of the zinc-containing compound represented by the general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, zinc bis(2,6-dimethyl-3,5-heptanedionato), zinc bis(2,2,6,6-tetramethyl-3,5-heptanedionato), and zinc bis(5,5-dimethyl-2,4-hexanedionato), etc. When these zinc-containing compounds have hydrates or solvates or complexes with catalyst X, the hydrates and solvates and complexes with catalyst X can also be used as catalyst Y in the method for producing component (A).

[0055] As the organic acid zinc and zinc diketone enolate in the catalyst Y, the above-mentioned compounds can be used directly, but these compounds can also be generated in the reaction solution and used. For example, a zinc compound such as metallic zinc, zinc oxide, zinc hydroxide, zinc chloride, or zinc nitrate (hereinafter referred to as a "raw zinc compound") is used as a raw material, and in the case of an organic acid zinc compound, the raw zinc compound is reacted with an organic acid. In the case of a zinc diketone enolate, the raw zinc compound is reacted with a 1,3-diketone.

[0056] In the present invention, these catalysts Y can be used alone or in any combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferred, and zinc acetate, zinc acrylate, and zinc acetylacetonate are more preferred because they exhibit good reactivity with most polyhydric alcohols and are easily available.

[0057] The proportion of catalyst Y used in the production method of component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 moles of catalyst Y, and more preferably 0.0005 to 0.2 moles, per mole of total hydroxyl groups of AZ-RO. By using 0.0001 moles or more of catalyst Y, the yield of the target reaction product containing (meth)acrylate can be increased, and by using 0.5 moles or less, the production of by-products and coloring of the reaction liquid can be suppressed, and the purification step after completion of the reaction can be simplified.

[0058] 1-3-4. Preferred manufacturing method for component (A) The component (A) is produced by subjecting AZ-RO to an ester exchange reaction with a monofunctional (meth)acrylate in the presence of the catalysts X and Y. AZ-RO (meth)acrylate was a compound that was difficult to produce by conventional dehydration esterification or transesterification. In contrast, the production method used in the present invention makes it possible to produce AZ-RO (meth)acrylate without any problems, and the resulting (meth)acrylate is almost free of coloration and has a low proportion of high molecular weight compounds. While there are no particular limitations on the ratio of catalyst X to catalyst Y used in the production method of component (A), it is preferable to use 0.005 to 10.0 mol, and more preferably 0.05 to 5.0 mol, of catalyst X per 1 mol of catalyst Y. By using 0.005 mol or more, the yield of the target reaction product containing (meth)acrylate can be increased, and by using 10.0 mol or less, the production of by-products and coloration of the reaction liquid can be suppressed, and the purification step after completion of the reaction can be simplified.

[0059] As a combination of catalyst X and catalyst Y used in combination in the present invention, a combination in which catalyst X is an azabicyclo-based compound and catalyst Y is a compound represented by the above general formula (3) is preferred, and further, a combination in which the azabicyclo-based compound is DABCO and the compound represented by the above general formula (3) is zinc acetate and / or zinc acrylate is particularly preferred. This combination not only produces a reaction product containing (meth)acrylate in good yield, but also has excellent color tone (less yellowish) after the reaction is completed, making it suitable for use in coating applications where colorless transparency is important. Furthermore, this combination of catalysts is relatively inexpensive, making it an economically advantageous production method.

[0060] The catalysts X and Y used in the present invention may be added from the beginning or midway of the reaction, and the desired amounts may be added all at once or in portions.

[0061] The reaction temperature in the production method of component (A) is preferably 40° C. to 180° C., and more preferably 60° C. to 160° C. By setting the reaction temperature at 40° C. or higher, the reaction rate can be increased, and by setting the reaction temperature at 180° C. or lower, thermal polymerization of (meth)acryloyl groups in the raw materials and products can be suppressed, coloration of the reaction liquid can be suppressed, and the purification step after completion of the reaction can be simplified.

[0062] The reaction pressure in the production process for the component (A) is not particularly limited as long as the predetermined reaction temperature can be maintained, and the reaction may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).

[0063] In the production method of the component (A), as the transesterification reaction proceeds, a monohydric alcohol derived from the monofunctional (meth)acrylate is produced as a by-product. When a portion of the hydroxyl groups of AZ-RO (for example, about 50 mol%) is converted to (meth)acrylate, the monohydric alcohol is allowed to coexist in the reaction solution to reach an equilibrium state, and the catalyst is then adsorbed and removed or deactivated. Thereafter, the monohydric alcohol and the raw material monofunctional (meth)acrylate are distilled off, thereby making it possible to stably produce a product with a controlled acrylate rate. On the other hand, when the hydroxyl groups of AZ-RO are actively converted to (meth)acrylates, it is preferable to discharge the monohydric alcohol from the reaction solution to further promote the progress of the transesterification reaction.

[0064] In the method for producing the component (A), the reaction can be carried out without using a solvent, but a solvent may be used if necessary. Specific examples of the solvent include hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamylbenzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin, and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, ethers such as dimethyl cellosolve, diglyme, triglyme, and tetraglyme; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and benzophenone; carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; ureas or derivatives thereof; phosphine oxides such as tributylphosphine oxide, ionic liquids such as imidazolium salts, piperidinium salts, and pyridinium salts; silicone oil; and water. Among these solvents, at least one solvent selected from the group consisting of hydrocarbons, ethers, carbonate compounds, and ionic liquids is preferred. These solvents may be used alone or in any combination of two or more to be used as a mixed solvent.

[0065] In the method for producing component (A), an inert gas such as argon, helium, nitrogen, or carbon dioxide may be introduced into the reaction solution in order to maintain the color tone of the reaction solution in a good condition, but an oxygen-containing gas may be introduced into the reaction solution in order to prevent polymerization of the (meth)acryloyl group. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. The oxygen-containing gas may be introduced by dissolving it in the reaction solution or by blowing it into the reaction solution (so-called bubbling).

[0066] In the production method of the component (A), it is preferable to add a polymerization inhibitor to the reaction liquid for the purpose of preventing polymerization of the (meth)acryloyl group. Specific examples of the polymerization inhibitor include organic polymerization inhibitors such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert-butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; inorganic polymerization inhibitors such as copper chloride, copper sulfate, and ferrous sulfate; and organic salt-based polymerization inhibitors such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt. The polymerization inhibitor may be added singly or in any combination of two or more kinds, and may be added from the beginning or midway of the production process of component (A). The desired amount may be added all at once or in portions. The polymerization inhibitor may also be added continuously via a rectification column. The proportion of the polymerization inhibitor added in the reaction solution is preferably 5 to 30,000wtppm, more preferably 25 to 10,000wtppm. By making the proportion 5wtppm or more, the polymerization inhibitor effect can be fully exhibited, and by making the proportion 30,000wtppm or less, coloring of the reaction solution can be suppressed, the purification process after the reaction can be simplified, and a decrease in the curing speed of the obtained (A) component can be prevented.

[0067] The reaction time in the production method of the component (A) varies depending on the type and amount of catalyst used, the reaction temperature, the reaction pressure, etc., but is preferably 0.1 to 150 hours, and more preferably 0.5 to 80 hours.

[0068] The method for producing component (A) can be carried out by any of batch, semi-batch and continuous methods. In one example of the batch method, AZ-RO, monofunctional (meth)acrylate, catalyst and polymerization inhibitor are added to a reactor, and the reaction liquid is stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction liquid. Thereafter, the monohydric alcohol by-produced as the transesterification reaction proceeds is extracted from the reactor at a predetermined pressure to produce the desired component (A).

[0069] It is preferable to carry out a separation and purification procedure on the reaction product obtained by the production method of the component (A) since this allows the desired reaction product containing the (meth)acrylate to be obtained with high purity. Examples of the separation and purification operations include adsorption, crystallization, filtration, distillation, and extraction, and it is preferable to combine these. Examples of the adsorption operation include adsorption of the catalyst by an adsorbent, and examples of the adsorbent include aluminum silicate. Examples of the crystallization operation include cooling crystallization and concentration crystallization. Examples of the filtration operation include pressure filtration, suction filtration, and centrifugal filtration. Examples of the distillation operation include single distillation, fractional distillation, molecular distillation, and steam distillation. Examples of the extraction operation include solid-liquid extraction and liquid-liquid extraction. In the separation and purification operation, a solvent may be used, and further, a neutralizing agent for neutralizing the catalyst and / or polymerization inhibitor used in the present invention, an acid and / or an alkali for decomposing or removing by-products, activated carbon for improving color tone, and diatomaceous earth for improving filtration efficiency and filtration rate may be used.

[0070] 2. Curable composition for pattern formation The present invention relates to a curable composition for pattern formation comprising the component (A). As a method for producing the composition, a method including a step of producing a mixture (A) of compounds having a (meth)acryloyl group obtained by subjecting AZ-RO and a monofunctional (meth)acrylate to an ester exchange reaction in the presence of the catalysts X and Y is preferable. According to this production method, the component (A) can be obtained in a high yield, and therefore, it is excellent in terms of cost and productivity. In addition, the component (A) obtained by this production method is preferable because it has a low viscosity and is easy to handle due to a small amount of side-reaction high molecular weight products, and further has high sensitivity, hardness of the cured product, and excellent alkali developability. This step may be carried out in accordance with the above-mentioned method for producing the component (A). Furthermore, when other components described below are added, component (A) and the other components may be stirred and mixed.

[0071] When mixing the components, they may be stirred while being heated as necessary. The temperature when stirring and mixing while being heated is preferably in the range of 40 to 90°C.

[0072] The viscosity of the composition may be appropriately set depending on the application and purpose of use. The viscosity of the composition is preferably 1 to 100,000 mPa·s, and more preferably 5 to 50,000 mPa·s. By setting the viscosity within this range, the composition can have excellent leveling properties when applied, and the cured product can have excellent appearance. In the present invention, the viscosity refers to a value measured at 25° C. using an E-type viscometer (cone-plate type viscometer).

[0073] The composition of the present invention can be used in any form, such as a solventless composition that does not contain an organic solvent, a solvent-based composition that contains an organic solvent, or an aqueous composition in which component (A) is dissolved or dispersed in water. In the aqueous composition in which component (A) is dispersed in water, a commonly used emulsifier or a reactive emulsifier described below can be used as the dispersant.

[0074] When the composition of the present invention uses the component (A) as the main component, the content of the component (A) in the composition is preferably 20 to 100% by weight, and more preferably 30 to 100% by weight, relative to 100% by weight of the total amount of the curable components, in order to achieve high sensitivity, hardness, and excellent alkaline developability. The term "curable component" refers to a group of compounds having an ethylenically unsaturated group, and means component (A), a compound having an ethylenically unsaturated group other than component (A) described below [component (C)], component (A), and component (C). In addition, when an alkali-soluble resin [component (E)] described below is blended and component (E) has an ethylenically unsaturated group, the term means component (A), component (C), and component (E).

[0075] The composition of the present invention contains the above-mentioned component (A) as an essential component, but various other components can be blended depending on the purpose. Specific preferred examples of the other components include a photopolymerization initiator (hereinafter referred to as "component (B)"), a compound having an ethylenically unsaturated group other than the component (A) (hereinafter referred to as "component (C)"), water and / or an organic solvent (hereinafter referred to as "component (D)"), an alkali-soluble resin (hereinafter referred to as "component (E)"), an antioxidant, an ultraviolet absorber, a silane coupling agent, a surface modifier, and a polymerization inhibitor. These components will be described below. As for the other components described later, the exemplified compounds may be used alone or in combination of two or more.

[0076] 2-1.(B) Component The component (B) is a photopolymerization initiator. In the composition of the present invention, particularly when ultraviolet light and visible light are used as the active energy rays, it is preferred from the viewpoints of ease of curing and cost that the composition further contains a component (B). When the composition of the present invention is used as an electron beam-curable composition, it is possible to cure it by electron beam without containing component (B), but it can also be blended in a small amount as necessary to improve sensitivity.

[0077] As the component (B) in the present invention, various known photopolymerization initiators can be used, and as the component (B), a photoradical polymerization initiator is preferable. Specific examples of component (B) include acetophenone-based compounds such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, diethoxyacetophenone, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one; Benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; α-ketoester compounds such as methylbenzoyl formate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester of oxyphenylacetic acid and 2-(2-hydroxyethoxy)ethyl ester of oxyphenylacetic acid; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene-based compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfinyl)propan-1-one; Oxime ester photoinitiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; and camphorquinone, etc.

[0078] Among these, acetophenone-based compounds, benzophenone-based compounds, and phosphine oxide-based compounds are preferred, and acetophenone-based compounds are particularly preferred because good sensitivity can be easily obtained in air even when the cured film is applied in a thin film having a thickness of several μm or less.

[0079] The content of component (B) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, and particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable components. Within the above range, the sensitivity of the composition is excellent, and the chemical resistance of the obtained cured film is excellent.

[0080] 2-2.(C) Component The component (C) is a compound having an ethylenically unsaturated group other than the component (A). As the ethylenically unsaturated group of the component (C), a (meth)acryloyl group is preferred, and an acryloyl group is more preferred, because this gives the composition excellent sensitivity.

[0081] Examples of component (C) include a compound having one (meth)acryloyl group in the molecule, a compound having two (meth)acryloyl groups (hereinafter referred to as "bifunctional (meth)acrylates"), and a compound having three or more (meth)acryloyl groups (hereinafter referred to as "trifunctional or higher (meth)acrylates").

[0082] Examples of compounds having one ethylenically unsaturated group in the molecule include (meth)acrylates having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylates") and (meth)acrylamides having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylamides"). Specific examples of monofunctional (meth)acrylates include: Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; Polyol mono(meth)acrylates such as trimethylolpropane mono(meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, ditrimethylolpropane mono(meth)acrylate and dipentaerythritol mono(meth)acrylate: Monofunctional (meth)acrylates having an alicyclic group, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; Monofunctional (meth)acrylates having a cyclic ether group, such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, and 3-ethyl-3-oxetanylmethyl (meth)acrylate; Aromatic monofunctional (meth)acrylates such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxy (meth)acrylate, and p-cumylphenol ethylene (meth)acrylate; Monofunctional (meth)acrylates having a maleimide group, such as (meth)acrylolyloxyethylhexahydrophthalimide; (Meth)acryloylmorpholine; and Examples of the monofunctional (meth)acrylates include those having an alkoxyalkyl group, such as alkyl carbitol (meth)acrylates, such as ethyl carbitol (meth)acrylate and 2-ethylhexyl carbitol (meth)acrylate.

[0083] Specific examples of monofunctional (meth)acrylamides include N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, N-sec-butyl (meth)acrylamide, Nt-butyl (meth)acrylamide, and Nn-hexyl (meth)acrylamide; N-hydroxyalkyl (meth)acrylamides such as N-hydroxyethyl (meth)acrylamide; and Examples of N,N-dialkyl(meth)acrylamides include N,N-dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide and N,N-dihexyl(meth)acrylamide.

[0084] Specific examples of the bifunctional (meth)acrylate include aliphatic diol di(meth)acrylates such as butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate; Di(meth)acrylates of trihydric or higher polyols, such as glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate; Di(meth)acrylates of these polyol alkylene oxide adducts; and Di(meth)acrylates having an isocyanuric acid skeleton, such as di(meth)acrylates of isocyanuric acid ethylene oxide adducts; and Di(meth)acrylates of alkylene oxide adducts of bisphenol A, and di(meth)acrylates of alkylene oxide adducts of bisphenols such as bisphenol F etc. can be mentioned. In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

[0085] Specific examples of the tri- or higher functional (meth)acrylate include poly(meth)acrylates of polyols such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri- or tetra(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, and dipentaerythritol tri-, tetra-, penta- or hexa(meth)acrylate; Di(meth)acrylates of these polyol alkylene oxide adducts; and Examples of the tri(meth)acrylate include tri(meth)acrylates having an isocyanuric acid skeleton, such as tri(meth)acrylate of an ethylene oxide adduct of isocyanuric acid. etc. can be mentioned. In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

[0086] In addition to these, (meth)acrylic oligomers such as epoxy (meth)acrylate and urethane (meth)acrylate can also be used as the (meth)acrylate depending on the purpose.

[0087] Of these compounds exemplified as the component (C), any compound can be used depending on the purpose. Particularly preferred compounds for increasing the sensitivity of the composition include polyfunctional (meth)acrylates such as pentaerythritol (meth)acrylate and dipentaerythritol (meth)acrylate, as well as polyfunctional urethane (meth)acrylates in which the residual hydroxyl groups of these polyfunctional (meth)acrylates are urethane-converted with polyisocyanate.

[0088] The content of the component (C) may be appropriately determined depending on the purpose. When the composition of the present invention is used for the above-mentioned pattern formation and the like, when the component (A) is used as the main component, it is preferably contained in an amount of 80% by weight or less, more preferably 70% by weight or less, based on 100% by weight of the total curable components. The preferred lower limit is 20% by weight or more, based on 100% by weight of the total curable components. By containing the component (C) in an amount of 20% by weight or more, it is possible to improve the alkali developability, and by containing the component (C) in an amount of 80% by weight or less, it is possible to impart good chemical resistance to the cured film.

[0089] 2-3.(D) Component The composition of the present invention may contain water and / or an organic solvent as the component (D) for the purpose of improving the coatability onto a substrate, etc.

[0090] Specific examples of the organic solvent in component (D) include alcohol compounds such as methanol, ethanol, isopropanol, and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatic compounds such as benzene, toluene, and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone. Among these, alkylene glycol monoether compounds and ketone compounds are preferred, and alkylene glycol monoether compounds are more preferred.

[0091] The content of the (D) component is preferably 10 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, and even more preferably 50 to 300 parts by weight, relative to 100 parts by weight of the total amount of the curable components. When the content is within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily coated by a known coating method described below.

[0092] 2-4.(E) Component The component (E) in the present invention is not particularly limited so long as it acts as a binder for the component (A) and is soluble in the developer used in the development processing step, particularly preferably in an alkaline developer. Examples of the component (E) include addition polymers, polyesters, epoxy resins, and polyethers, and addition polymers obtained by polymerizing ethylenically unsaturated monomers are preferred. As component (E), an alkali-soluble resin having a carboxyl group is preferred, and in particular, a copolymer (hereinafter referred to as a "carboxyl group-containing copolymer") of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as a "carboxyl group-containing unsaturated monomer") and an ethylenically unsaturated monomer copolymerizable therewith (hereinafter referred to as a "copolymerizable unsaturated monomer") is preferred.

[0093] Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; unsaturated polyvalent carboxylic acids or anhydrides thereof having a valence of three or more; mono[(meth)acryloyloxyalkyl]esters of polyvalent carboxylic acids having a valence of two or more such as mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate; and mono(meth)acrylates of polymers having a carboxy group and a hydroxyl group at both ends such as ω-carboxypolycaprolactone mono(meth)acrylate. Of these carboxyl group-containing unsaturated monomers, mono(2-acryloyloxyethyl) succinate and mono(2-acryloyloxyethyl) phthalate are commercially available under the trade names Aronix M-5300 and M-5400 (Toagosei Co., Ltd.), respectively. The carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more kinds.

[0094] The copolymerizable unsaturated monomer may be any monomer that can be copolymerized with the carboxyl group-containing unsaturated monomer, and aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated imides, and macromonomers having a mono(meth)acryloyl group at the end are preferred.

[0095] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 2-vinylbenzyl methyl ether, 3-vinylbenzyl methyl ether, 4-vinylbenzyl methyl ether, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, and 4-vinylbenzyl glycidyl ether.

[0096] Examples of unsaturated carboxylate esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxypropyl (meth)acrylate, 5-hydroxypropyl (meth)acrylate, 6-hydroxypropyl (meth)acrylate, 7-hydroxypropyl (meth)acrylate, 8-hydroxypropyl (meth)acrylate, 9-hydroxypropyl (meth)acrylate, 10-hydroxypropyl (meth)acrylate, 11-hydroxypropyl (meth)acrylate, 12-hydroxypropyl (meth)acrylate, 13-hydroxypropyl (meth)acrylate, 14-hydroxypropyl (meth)acrylate, 15-hydroxypropyl (meth)acrylate, 16-hydroxypropyl (meth)acrylate, 17-hydroxypropyl (meth)acrylate, 18-hydroxypropyl (meth)acrylate, 19-hydroxypropyl (meth)acrylate, 20-hydroxypropyl (meth)acrylate, 21-hydroxypropyl (meth)acrylate, 22-hydroxypropyl (meth)acrylate, 23-hydroxypropyl (meth)acrylate, 24-hydroxypropyl (meth)acrylate, 25-hydroxypropyl (meth)acrylate, 26-hydroxypropyl (meth)acrylate, 27-hydroxypropyl (meth)acrylate, 28-hydroxypropyl (meth)acrylate, 29-hydroxypropyl (meth)acrylate, 30-hydroxypropyl (meth)acrylate, 31-hydroxypropyl (meth)acrylate, 32-hydroxypropyl (meth)acrylate, 33-hydroxypropyl (meth)acrylate, 34-hydroxypropyl (meth)acrylate, 35-hydroxypropyl (meth)acrylate, 36-hydroxypropyl (meth)acrylate, 37-hydroxypropyl (meth)acrylate, 38-hydroxypropyl (meth)acrylate, 39-hydroxy -Hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 2, 6] decan-8-yl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and glycerol mono(meth)acrylate.

[0097] The unsaturated imides include maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0098] Examples of macromonomers having a mono(meth)acryloyl group at the end include those having a polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

[0099] In addition to the above, examples of the copolymerizable unsaturated monomer include imide (meth)acrylates such as 2-(3,4,5,6-tetrahydrophthalimido)ethyl (meth)acrylate and 2-(2,3-dimethylmaleimido)ethyl (meth)acrylate; unsaturated carboxylic acid amino alkyl esters such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth)acrylate, and 3-dimethylaminopropyl (meth)acrylate; and unsaturated carboxylic acids such as glycidyl (meth)acrylate. vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as (meth)acrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as (meth)acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl(meth)acrylamide; and aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene. These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

[0100] The carboxyl group-containing copolymer is preferably a copolymer of a carboxyl group-containing unsaturated monomer component containing (meth)acrylic acid as an essential component and optionally further containing at least one compound selected from the group consisting of mono(2-(meth)acryloyloxyethyl) succinate and ω-carboxypolycaprolactone mono(meth)acrylate, and at least one selected from the group consisting of styrene, methyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, allyl(meth)acrylate, benzyl(meth)acrylate, glycerol mono(meth)acrylate, N-phenylmaleimide, polystyrene macromonomer, and polymethyl methacrylate macromonomer (hereinafter referred to as "carboxyl group-containing copolymer (α)").

[0101] Specific examples of the carboxyl group-containing copolymer (α) include (meth)acrylic acid / methyl (meth)acrylate copolymer, (meth)acrylic acid / benzyl (meth)acrylate copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymer, (meth)acrylic acid / glycidyl (meth)acrylate copolymer, (meth)acrylic acid / glycidyl (meth)acrylate / styrene copolymer, (meth)acrylic acid / methyl (meth)acrylate / polystyrene macromonomer copolymer, (meth)acrylic acid / methyl (meth)acrylate / polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid / benzyl (meth)acrylate / polystyrene macromonomer copolymer, (meth)acrylic acid / benzyl (meth)acrylate / polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / polystyrene macromonomer copolymer, Examples of the copolymer include monomer copolymers, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / polymethyl methacrylate macromonomer copolymers, methacrylic acid / styrene / benzyl (meth)acrylate / N-phenylmaleimide copolymers, (meth)acrylic acid / mono[2-(meth)acryloyloxyethyl]succinate / styrene / benzyl (meth)acrylate / N-phenylmaleimide copolymers, (meth)acrylic acid / mono[2-(meth)acryloyloxyethyl]succinate / styrene / allyl (meth)acrylate / N-phenylmaleimide copolymers, (meth)acrylic acid / styrene / benzyl (meth)acrylate / glycerol mono(meth)acrylate / N-phenylmaleimide copolymers, and (meth)acrylic acid / ω-carboxypolycachloractone mono(meth)acrylate / styrene / benzyl (meth)acrylate / glycerol mono(meth)acrylate / N-phenylmaleimide copolymers.

[0102] The copolymerization ratio of the carboxyl-containing unsaturated monomer in the carboxyl-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, by making the copolymerization ratio 5% by weight or more, the solubility of the resulting composition in an alkaline developer can be improved, while by making it 50% by weight or less, the solubility in an alkaline developer can be made appropriate, and when developing with an alkaline developer, the spacer layer or pixels can be prevented from falling off from the substrate and the film roughness of the spacer surface can be prevented.

[0103] As the component (E) in the present invention, an alkali-soluble resin having an ethylenically unsaturated group in the side chain is preferred since it is excellent in that the crosslink density of the obtained cured film is improved and the coating film strength, heat resistance, and chemical resistance are improved. The alkali-soluble resin having an ethylenically unsaturated group in the side chain is preferably an alkali-soluble resin having a carboxyl group, such as the above-mentioned carboxyl group-containing copolymer to which an unsaturated compound having an epoxy group (hereinafter referred to as an "epoxy-based unsaturated compound") is added. Examples of the epoxy-based unsaturated compound include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and cyclohexene oxide-containing (meth)acrylate. The addition reaction may be carried out according to a conventional method, and the copolymer may be produced by adding an epoxy-based unsaturated compound to a carboxyl group-containing copolymer in an organic solvent or without a solvent. The conditions for the addition reaction may be appropriately selected from the reaction temperature, reaction time, and catalyst according to each reaction.

[0104] The Mw of the component (E) is preferably from 3,000 to 300,000, and more preferably from 5,000 to 100,000. Additionally, the number average molecular weight (hereinafter referred to as "Mn") is preferably from 3,000 to 60,000, and more preferably from 5,000 to 25,000. In the present invention, Mw and Mn refer to values ​​of molecular weight measured by GPC (elution solvent: tetrahydrofuran) converted into polystyrene equivalent. In the present invention, by using the component (E) having such specific Mw and Mn, an active energy ray-curable composition having excellent developability can be obtained, which makes it possible to form a pattern having sharp pattern edges and also makes it difficult for residues, background stains, film residues, etc. to occur on the substrate and light-shielding layer in unexposed areas during development. The ratio of Mw to Mn (Mw / Mn) of the component (E) is usually 1 to 5, and preferably 1 to 4. The component (E) can be used alone or in combination of two or more types.

[0105] The ratio of component (A) and component (E) is preferably 10-100% by weight of component (A) and 0-90% by weight of component (E) based on their total amount, and more preferably 20-100% by weight of component (A) and 0-80% by weight of component (E). If the ratio of component (E) is less than 10% by weight, the crosslink density decreases, and the coating strength, heat resistance, and chemical resistance tend to decrease. The ratio of the (A) component and the (E) component in the composition is preferably 10 to 50% by weight as the total amount of the (A) component and the (E) component in the composition. By making this ratio 10% by weight or more, it is possible to prevent the film thickness after pre-baking from becoming thin, while by making it 50% by weight or less, it is possible to make the viscosity of the composition appropriate, prevent poor coatability, and prevent the film thickness after pre-baking from becoming thick.

[0106] 2-5. Other ingredients not mentioned above As described above, other components besides the above include antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers, and polymerization inhibitors.

[0107] 1) Antioxidants The antioxidant is added for the purpose of improving the heat resistance and durability of the cured film. Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenol-based antioxidant include hindered phenols such as di-t-butylhydroxytoluene. Commercially available antioxidants include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation. Examples of phosphorus-based antioxidants include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphites, triaryl phosphites, etc. Commercially available derivatives of these include Adeka STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010, manufactured by Adeka Corporation. Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation. These antioxidants may be used alone or in combination of two or more. Preferred combinations of these antioxidants include a combination of a phenol-based antioxidant and a phosphorus-based antioxidant, and a combination of a phenol-based antioxidant and a sulfur-based antioxidant. The content of the antioxidant may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of the curable components. By setting the content to 0.1 parts by weight or more, the durability of the composition can be improved, while by setting it to 5 parts by weight or less, the sensitivity and adhesion can be improved.

[0108] 2) Ultraviolet absorbers The ultraviolet absorber is added for the purpose of improving the light resistance of the cured film. Examples of the ultraviolet absorbent include triazine-based ultraviolet absorbents such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479, and benzotriazole-based ultraviolet absorbents such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130, both manufactured by BASF. The content of the ultraviolet absorber may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the total amount of the curable components. By setting the content to 0.01% by weight or more, the light resistance of the cured film can be improved, while by setting the content to 5% by weight or less, the sensitivity of the composition can be improved.

[0109] 3) Pigments and dyes Examples of the pigment include organic pigments and inorganic pigments. Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, and pyrazolone red; soluble azo pigments such as lithol red, heliobordeaux, pigment scarlet, and permanent red 2B; derivatives of vat dyes such as alizarin, indanthrone, and thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; and isoindigo. isoindolinone organic pigments such as perinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange; thioindigo organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow, isoindoline organic pigments such as isoindoline yellow, and other pigments such as flavanthrone yellow, acylamide yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet. Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, titanium black, and synthetic iron black. Carbon black, which is an example of the filler, can also be used as an inorganic pigment. As the dye, various conventionally known compounds can be used.

[0110] 4) Silane coupling agents The silane coupling agent is added for the purpose of improving the interfacial adhesive strength between the cured film and the substrate. There are no particular limitations on the silane coupling agent as long as it can contribute to improving the adhesion to the substrate.

[0111] Specific examples of the silane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0112] The blending ratio of the silane coupling agent may be appropriately set depending on the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the total amount of the curable components. By making the blending ratio 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by making it 10 parts by weight or less, the change in adhesive strength over time can be prevented.

[0113] 5) Surface modifiers A surface modifier may be added to the composition of the present invention for the purpose of improving the leveling property during application. Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, an agent for imparting smoothness, and an agent for imparting antifouling property. These known surface modifiers can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.Specific examples include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. Furthermore, for the purpose of improving the durability of the lubrication property, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may be used.

[0114] The content of the surface modifier is preferably 0.01 to 1.0 part by weight per 100 parts by weight of the total amount of the curable components. When in this range, the surface smoothness of the coating film is excellent.

[0115] 3. Method of using the active energy ray-curable composition for pattern formation The active energy ray-curable composition for pattern formation of the present invention can be used for various applications. Examples of the composition include photosensitive lithographic printing plates, resists such as etching resists and solder resists, columnar spacers in the production of liquid crystal panels, coloring compositions for forming pixels or black matrices in color filters, and protective films for color filters.

[0116] The composition of the present invention can be used, for example, by applying the composition to a substrate and then irradiating the substrate with active energy rays. When the composition contains component (D) (water and / or an organic solvent), it is preferable to apply the composition to a substrate, heat the composition to evaporate component (D), and then irradiate the composition with active energy rays. Furthermore, heating may also be carried out after irradiation with active energy rays.

[0117] As the substrate, various substrates can be used so long as they are used for pattern formation applications, and examples of the substrate include metals such as silicon, aluminum, iron, nickel, and copper; glass; plastics such as polyethylene terephthalate, polyimide, and polycarbonate; and composite substrates such as glass epoxy substrates.

[0118] The active energy includes an electron beam, ultraviolet light, and visible light. The light source for irradiating visible light and ultraviolet light may be appropriately selected depending on the photopolymerization initiator used, and examples of the light source include a high-pressure mercury lamp, a metal halide lamp, and an LED. The conditions for irradiating the active energy may be appropriately set depending on the components used and the purpose. The heating method and conditions for the heating after the irradiation with active energy rays may be those of the usual method.

[0119] The applications of the etching resist, the solder resist, the columnar spacer (hereinafter simply referred to as "spacer") and the colored composition will be described below.

[0120] 3-1. Etching resist When the composition of the present invention is used as an etching resist, it can be used in the form of either a liquid resist or a dry film resist. When used as a liquid resist, the composition may be applied to a substrate and then irradiated with active energy rays, as described above. When the composition of the present invention is used as an etching resist, the composition may be applied to a substrate and then irradiated with active energy rays, as described above. In the case where the composition contains the component (D), it is preferable to apply the composition to a substrate, heat the composition to evaporate the component (D), and then irradiate the composition with active energy rays.

[0121] Examples of a coating device used when applying the composition to a substrate include a spin coater, a roll coater, and a curtain coater. The film thickness may be appropriately set depending on the purpose, but is preferably 1 to 100 μm, particularly 5 to 50 μm.

[0122] Examples of the substrate include the above-mentioned metal, glass, and plastic substrates, as well as composite substrates such as a glass epoxy substrate. When forming a resist on a printed wiring board, it is preferable to form the resist after polishing the copper surface and before an oxide film is formed on the copper foil surface, since this provides higher adhesion. Furthermore, the adhesion is further improved if the resist is formed after the copper surface is oxidized or roughened to form irregularities.

[0123] When the composition contains the component (D), after the composition is applied or printed, the component (D) in the composition is evaporated by heating. In this case, examples of the heating device include an oven and a hot plate. The heating conditions may be appropriately set depending on the type of composition used and the purpose, and the preferred heating temperature is 70° C. to 120° C., and the preferred heating time is 5 to 30 minutes.

[0124] The coating film obtained above is irradiated with active energy rays through a photomask or the like having a specific pattern formed thereon. Examples of active energy rays used for curing the composition include electron beams and ultraviolet rays, and ultraviolet rays are preferably used because inexpensive equipment can be used. The irradiation conditions for the active energy rays may be in accordance with the usual method. The irradiation conditions may be appropriately set depending on the type and purpose of the composition used, and are preferably 10 to 5,000 mJ / cm. 2 , more preferably 50 to 500 mJ / cm 2 It is.

[0125] After the irradiation with the active energy rays, the uncured portions are subjected to alkaline development. The dilute alkaline aqueous solution used for development may be appropriately selected depending on the type and purpose of the composition used, and may be, for example, a 0.5 to 2% by weight aqueous solution of sodium carbonate. The development conditions may be appropriately set depending on the type of composition used and the purpose. The development temperature is preferably 15 to 50° C., particularly preferably 20 to 40° C., and the development time is preferably 15 to 180 seconds, particularly preferably 30 to 120 seconds.

[0126] When the composition of the present invention is used as a dry film resist, it is used in the form of a film or sheet containing the composition of the present invention (hereinafter referred to as "AE-curable film"). An example of a method for producing an AE-cured film is to apply the composition of the present invention to a release-treated substrate, and in the case where the composition contains component (D), to dry the composition to form a dry coating film, and then to laminate another release-treated substrate to the applied coating film.

[0127] As the release-treated substrate, a substrate that has been subjected to release treatment with a polymer (hereinafter referred to as a "release film") can be used. Examples of the polymer include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polyimides, polycarbonates, epoxy resins, polyurethanes, polylactic acid, polyethylene, polypropylene, cycloolefin polymers, acrylic resins, methacrylic resins, polystyrene, methacrylic / styrene, polyvinyl acetate, polyvinyl alcohol, triacetyl cellulose, cellulose acetate butyrate, hydroxypropyl cellulose, and polyethersulfone. Examples of the release treatment include a silicone treatment, a long-chain alkyl treatment, and a fluorine treatment. Specific examples of the release film include PET film and OPP film which have been subjected to release treatment such as silicone treatment, long-chain alkyl treatment, and fluorine treatment.

[0128] We will explain an example of using an AE curing film laminated with two release sheets. Immediately before use, the release sheet is released from the AE curable film, and the dried coating film is brought into close contact with a substrate (1) such as a copper-clad laminate used for pattern formation. The other release sheet is then released, and the dried coating film is brought into close contact with another substrate (2) such as a photomask on which a specific pattern has been formed. After that, active energy rays are irradiated from the side of the substrate (2). Thereafter, the uncured portions are subjected to alkaline development according to the method described above.

[0129] 3-2. Solder resist The composition of the present invention can be preferably used as a solder resist, particularly as an alkali-developable type solder resist for photographic processing.

[0130] In the case of the solder resist, either a liquid resist or a dry film resist can be used. Methods for using the composition (coating method, active energy ray irradiation, development method) include the same methods as those for the liquid resist and dry film resist in the etching resist.

[0131] In this case, after irradiation with active energy rays and development, sufficient curing can be carried out by heating or irradiation with active energy rays in order to further improve various physical properties. The heating method and conditions may be appropriately set depending on the type and purpose of the composition used. The heating temperature is preferably 100 to 250°C, particularly preferably 130 to 230°C, and the heating time is preferably 5 minutes to 5 hours, particularly preferably 30 minutes to 2 hours. The irradiation conditions for the active energy rays may be in accordance with the usual method. The irradiation conditions may be appropriately set depending on the type and purpose of the composition used, and are preferably 10 to 5,000 mJ / cm. 2 , more preferably 500 to 3,000 mJ / cm 2 It is.

[0132] 3-3.Spacer The spacer is formed of a cured film of the composition by photolithography. The spacer can be formed in any size and at any location on the liquid crystal panel substrate, but is generally formed in the black matrix region, which is the light-shielding portion of the color filter, or on the TFT electrode. The spacer may be formed according to a conventional method, for example, by applying the composition of the present invention to a substrate such as glass in a thickness necessary to form a cell gap, heating (hereinafter abbreviated as "pre-bake") to dry the coating, and then carrying out exposure, development, and post-heating (hereinafter abbreviated as "post-bake") steps to form the spacer.

[0133] When applying the composition onto the substrate, the composition is applied to a thickness slightly larger than the design value of the cell gap, taking into consideration film loss and deformation due to development, post-baking, etc. Specifically, the film thickness after pre-baking is preferably 5 to 10 μm, more preferably 6 to 7 μm. Examples of the coating method include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (slit coating), and generally, spin coating and die coating are used.

[0134] After the composition is applied onto the substrate, it is pre-baked at a temperature of 50 to 150° C. for about 5 to 15 minutes.

[0135] The prebaked coating surface is irradiated with light through a mask having a predetermined pattern for forming spacers. The light used is preferably ultraviolet light or visible light, and light with a wavelength of 240 nm to 410 nm obtained from a high-pressure mercury lamp, a metal halide lamp, or the like is used. The light irradiation conditions depend on the type of light source, the absorption wavelength of the photopolymerization initiator used, the thickness of the coating film, etc., but the light irradiation amount is generally 50 to 600 mJ / cm. 2 It is preferable that the light irradiation amount is 50 mJ / cm. 2 If it is smaller than this, curing will be insufficient and the exposed part will easily fall off during development. On the other hand, if the light irradiation amount is 600 mJ / cm2 If it is larger than this, it tends to be difficult to obtain a fine spacer pattern.

[0136] After the coating surface is irradiated with light, the unexposed areas are removed with a developer. The developer may be an aqueous solution of an alkaline compound. Examples of the alkaline compound include potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, ammonia, tetramethylammonium hydroxide, etc. In order to accelerate the development speed, the developer may contain an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropanol, or benzyl alcohol, or various surfactants. The developing method may be any of a puddle method, a dipping method, a spray method, etc. After development, the pattern portion is washed with water for 0.5 to 1.5 minutes and dried with compressed air or the like to obtain a spacer pattern.

[0137] The obtained spacer pattern is post-baked in a temperature range of 150 to 350° C. using a heating device such as a hot plate or an oven to obtain the liquid crystal panel spacer of the present invention. Post-baking allows residual solvent and moisture absorbed during development to evaporate, and also improves the heat resistance of the spacer. The thickness of the spacer varies depending on the cell gap setting of the liquid crystal panel, but is generally designed to be 3 to 5 μm after post-baking.

[0138] 3-4. Coloring composition When the composition of the present invention is used as a coloring composition, a pigment and a pigment dispersant are further blended. These components will be described below.

[0139] The pigment is not particularly limited, and various organic or inorganic pigments can be used. In addition to the above-mentioned organic pigments, more specific examples of the organic pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists), i.e., compounds assigned the following Color Index (CI) numbers. Yellow pigments such as CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, etc.; red pigments such as CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 177, CI Pigment Red 254, etc.; blue pigments such as CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, etc.; green pigments such as CI Pigment Green 7, CI Pigment Green 36, etc.; CI Pigment Violet 23, CI Pigment Violet 23:19, etc. In addition, it is possible to use high-brightness G pigments such as phthalocyanines with a high bromination rate, which have been difficult to disperse in the past, such as Monastral Green 6YC and 9YC (manufactured by Avecia Corporation), and high-color purity G pigments made of heterogeneous metal phthalocyanine pigments whose central metal is a metal other than copper, such as Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn.

[0140] Specific examples of the inorganic pigment include those mentioned above. In the present invention, the pigments may be used alone or in combination of two or more kinds.

[0141] The pigment dispersion liquid can impart excellent dispersibility to various pigments that are commonly used in color filters for liquid crystal display devices among these pigments, and specifically, the pigment dispersion liquid can be suitably used when preparing a pigment dispersion liquid containing at least one pigment selected from the group consisting of CI Pigment Yellow 150, CI Pigment Green 36, CI Pigment Green 7, CI Pigment Yellow 138, CI Pigment Yellow 83, CI Pigment Blue 15:6, CI Pigment Violet 23, CI Pigment Red 177, CI Pigment Red 254, and CI Pigment Yellow 139, the above phthalocyanine pigments having a high bromination rate, and the above heterometal phthalocyanine pigments.

[0142] The pigment dispersant is not particularly limited, and various pigment dispersants can be used. Specific examples of the pigment dispersant that can be used include amide compounds such as nonanoamide, decanamide, dodecanamide, N-dodecylhexamide, N-octadecylpropioamide, N,N-dimethyldodecanamide, and N,N-dihexylacetamide; amine compounds such as diethylamine, diheptylamine, dibutylhexadecylamine, N,N,N',N'-tetramethylmethanamine, triethylamine, tributylamine, and trioctylamine; monoethanolamine, diethanolamine, triethanolamine, and triethanolamine; Examples of such amines include amines having a hydroxy group, such as nipecotamide, N,N,N',N'-(tetrahydroxyethyl)-1,2-diaminoethane, N,N,N'-tri(hydroxyethyl)-1,2-diaminoethane, N,N,N',N'-tetra(hydroxyethylpolyoxyethylene)-1,2-diaminoethane, 1,4-bis(2-hydroxyethyl)piperazine and 1-(2-hydroxyethyl)piperazine. Other examples include compounds such as nipecotamide, isonipecotamide, and nicotinamide.

[0143] Further examples include (co)polymers of unsaturated carboxylates such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts and (partial) alkylamine salts of (co)polymers of unsaturated carboxylates such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylates such as hydroxyl-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; and amides obtained by reaction of poly(lower alkylene imine) with a polyester containing free carboxyl groups and salts thereof.

[0144] In addition, examples of commercially available dispersants include Shigenox-105 (trade name, manufactured by Hakkol Chemical Co., Ltd.), Disperbyk-101, -130, -140, -170, -171, -182, and -2001 (all manufactured by BYK Japan Co., Ltd.), EFKA-49, -4010, and -9009 (all manufactured by EFKA CHEMICALS Co., Ltd.), Solsperse 12000, 13240, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, and 33500 (all manufactured by Zeneka Co., Ltd.), PB821, and PB822 (all manufactured by Ajinomoto Co., Ltd.).

[0145] The pigment dispersant is used in an amount of preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, per 100 parts by weight of the pigment.

[0146] If necessary, the coloring composition may further contain an ultraviolet blocking agent, an ultraviolet absorbing agent, a surface conditioner (leveling agent) and other components.

[0147] The coloring composition may be produced by directly mixing the component (A), the pigment, the pigment dispersant, and other components as necessary, with the component (E) (organic solvent) and dispersing the mixture using a known dispersing machine. However, since this may result in insufficient pigment dispersion, a method in which a pigment dispersion is prepared in advance is preferred.

[0148] According to this method, a photosensitive coloring composition with excellent pigment dispersibility can be easily obtained. In this method, particularly when the (F) component (binder) is blended, a pigment dispersion liquid is prepared in advance by mixing and dispersing the pigment, the pigment dispersant, and, if necessary, a part of the (F) component in a solvent for dispersing (hereinafter referred to as a "dispersion solvent"). On the other hand, a clear resist liquid is prepared by mixing and dissolving or dispersing the (A) component and, if necessary, the (F) component and other components in a solvent for dilution (hereinafter referred to as a "dilution solvent"). Then, the obtained pigment dispersion liquid and the clear resist liquid are mixed, and a dispersion treatment is performed if necessary, so that a coloring composition with excellent pigment dispersibility can be easily obtained. According to this method, the dispersion solvent and the dilution solvent can be selected separately, so that the range of solvent selection is also widened.

[0149] When the pigment dispersion is not prepared in advance, the pigment, pigment dispersant, and, if necessary, alkali-soluble resin are first added to an organic solvent and thoroughly mixed and stirred to disperse the pigment, and then the remaining components, such as the carboxyl group-containing polyfunctional acrylate, are added and mixed. This not only prevents the pigment dispersibility from being hindered by other blended components during the pigment dispersion process, but also provides excellent stability.

[0150] The colored composition thus obtained is applied to a support to form a coating film, which is then dried. After that, the coating film is irradiated with light in a predetermined pattern to selectively harden a portion of the coating film. The coating film is then developed with an alkaline liquid, post-baked, and further thermally hardened to obtain a colored coating film having a predetermined pattern.

[0151] The light used is preferably ultraviolet light or visible light, and light with a wavelength of 240 nm to 410 nm obtained from a high-pressure mercury lamp or a metal halide lamp is used. The irradiation energy required for curing is usually 10 to 500 mJ / cm. 2 In the exposure step, the surface of the coating film is irradiated with laser light or with light through a mask, so that predetermined locations of the coating film can be selectively exposed and cured.

[0152] Moreover, the heat curing is usually carried out by drying at 50 to 200° C. using a vacuum dryer, an oven, a hot plate, or other heat applying device, and then heating at a temperature of about 120 to 250° C. for curing.

[0153] The cured portion of the coating film has a structure in which the pigment is uniformly dispersed in a matrix formed by a network of crosslinked bonds formed by the photocuring reaction and heat curing reaction according to the present invention.

[0154] This coloring composition has excellent sensitivity and has an increased crosslinking density, which allows it to harden uniformly throughout the interior, so that it is less likely to form a reverse tapered shape during development, and a forward tapered pattern with sharp edges and excellent surface smoothness can be formed.

[0155] In addition, the colored composition of the present invention has a high crosslink density, and impurities are trapped in the matrix, which is well solidified to the inside during curing, and are unlikely to be eluted into the liquid crystal layer, so that a colored cured film having high electrical reliability can be obtained. In particular, when the colored layer of a liquid crystal panel is produced using this colored composition, the voltage of the display section can be stably maintained, and the electrical reliability is high.

[0156] Furthermore, the coloring composition can disperse a pigment at a high concentration finely and uniformly, and has high coloring properties, so that a thin colored pattern having a high color density can be formed, and the color reproduction range is wide.

[0157] The coloring composition can be used to form various colored coating films, but is particularly suitable for forming colored layers constituting the details of a color filter, that is, pixels and black matrices. EXAMPLES

[0158] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" means parts by weight and "%" means % by weight. The abbreviations in the examples have the following meanings. ·MCA: 2-Methoxyethyl acrylate MEL: 2-Methoxyethanol ·DABCO: Triethylenediamine ·MEHQ: Hydroquinone monomethyl ether TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl DEHA: N,N-diethylhydroxylamine

[0159] 1. Manufacturing Example 1) Manufacturing Example 1 [Production of component (A): Production of 38 mol % acrylate of sorbitol with 6 mol ethylene oxide adduct (hydroxyl value 734)] A 3-liter flask equipped with a stirrer, a thermometer, a gas inlet tube, a rectification column, and a cooling tube was charged with 200 g (2.6 moles as hydroxyl groups) of an ethylene oxide adduct of sorbitol (manufactured by Aoki Oil Industries Co., Ltd., hydroxyl value 734 mg KOH / g (13.1 meq / g), average ethylene oxide addition number 6.28, peroxide concentration 0.7 wtppm), 613 g (4.7 moles) of MCA, 0.88 g (0.0078 moles) of DABCO as catalyst X, 3.26 g (0.0157 moles) of zinc acrylate as catalyst Y, 0.25 g of MEHQ, and 0.05 g of TEMPOL, and the flask was heated and stirred at an internal temperature of 125° C. to 130° C. for 10 hours to carry out an ester exchange reaction while bubbling an oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) into the liquid. During this time, MCA containing MEHQ and TEMPOL was added at any time to the reaction liquid via the rectification column.

[0160] The rate of acrylate of hydroxyl groups by the transesterification reaction was determined from the amount of MEL produced by liquid chromatography (hereinafter referred to as "LC") and was found to be 37 mol %. The quantification of MEL was performed by the internal standard method using a high-performance liquid chromatograph equipped with a differential refractive index detector (column: Atlantis (Part No. 186003748, column inner diameter 4.6 mm, column length 250 mm) manufactured by Nihon Waters K.K., solvent: pure water or 10% by volume isopropanol aqueous solution). Acrylation rate (mol%) = moles of MEL produced as a by-product with the progress of ester exchange reaction / (moles of alcohol used as raw material × number of alcoholic hydroxyl groups in the alcohol molecule used as raw material) × 100

[0161] The reaction solution was cooled to room temperature, and then filtered under pressure to separate the solid matter. 31 g of aluminum silicate (Kyowa Chemical Industry Co., Ltd., Kyoward 700SEN-S (trade name), hereinafter referred to as "K700") was added to the filtrate and stirred at an internal temperature of 95°C to 100°C for 1 hour to adsorb the catalyst dissolved in the filtrate. Thereafter, the reaction solution was cooled to an internal temperature of 40°C or less, 3.2 g of calcium hydroxide was added, and the mixture was further stirred at room temperature for 3 hours, after which the solid matter was separated by pressure filtration. The obtained filtrate was placed in a flask equipped with a stirrer, a thermometer, a gas inlet tube, a cooling tube for distillation, and a tube for reducing pressure, and stirred for 13 hours at an internal temperature of 90 to 100°C and a pressure of 0.01 to 200 mmHg while bubbling dry air into the flask, thereby distilling off the unreacted MCA and the by-product MEL. The liquid in the flask was cooled to room temperature, 0.076 parts (0.0008 moles) of DEHA was added, and the mixture was stirred for 1 hour at normal pressure and at an internal temperature of 75°C to 85°C. Then, pressure filtration was performed to obtain 239 g of filtrate. The acrylate mixture obtained in Production Example 1 is hereinafter referred to as Sb-EOA-1.

[0162] Electrospray ionization mass spectrometry (hereinafter referred to as "ESI-MS") of Sb-EOA-1 confirmed that it contained an acrylate of an ethylene oxide adduct of sorbitol as a major component. The amount of MCA remaining in Sb-EOA-1 was measured by gas chromatography (hereinafter referred to as "GC") to be 200 ppm or less, and no odor was detected at all. The viscosity, water solubility, hydroxyl value, Hazen color unit (hereinafter referred to as "APHA"), Mw, and saponification value of Sb-EOA-1 were measured according to the methods described below. The results are shown below. Viscosity (25°C): 10.93 Pa s, water solubility: 75% or more, hydroxyl value: 276 mg KOH / g, APHA: 92, Mw: 1,206, saponification value: 222 mg KOH / g, number of acryloyl groups added q: 2.3, acrylate ratio 38 mol% The number q of added acryloyl groups was calculated according to the method described in JP-A-4-136041.

[0163] ◆Peroxide concentration measurement conditions Isopropyl alcohol, glacial acetic acid, and an aqueous solution of potassium iodide were added to the alkylene oxide adduct of sorbitol, and the mixture was heated in a water bath at 85°C for 3 minutes to generate iodine. The treated solution was then removed from the water bath, and the iodine was titrated with sodium thiosulfate before the temperature of the treated solution dropped below 40°C. The active oxygen concentration was calculated from the titration amount, which was used as the peroxide concentration.

[0164] ◆ESI-MS measurement conditions Measurement method: Flow injection method Sample pretreatment: Prepare a 500μg / mL solution in acetonitrile Equipment: Quattro Premier (Waters) + AcQuity UPLC (Waters) ·Injection volume: 2μL ·Eluent flow rate: 0.3mL / min Eluent composition: 10mM acetic acid NH4 / acetonitrile = 50 / 50 (solution ratio, 0min → 1min) Capillary voltage: 3.0kV Cone voltage: 10V Source temperature: 120℃ Desolvation temperature: 400℃ Desolvation gas volume: 800L / h Cone gas volume: 50L / h Mass analysis range: m / z = 180 to 1200 (SCAN mode) Ionization mode: ESI+

[0165] ◆Gas chromatographic measurement conditions ·Equipment: GC-17A manufactured by Shimadzu Corporation Detector: FID detector Carrier gas: Helium Column: Inert Cap (film thickness 0.5 μm, 0.32 mm ID x 60 m) Injection temperature: 200℃ ·FID temperature: 250℃ Column temperature: After holding at 120℃ for 5 minutes, increase the temperature to 240℃ at a rate of 10℃ / min and hold for 25 minutes. ·Injection volume: 0.2μL The content of MEL was determined by the internal standard method in terms of weight percent.

[0166] ◆Viscosity measurement conditions The viscosity was measured at 25°C using an E-type viscometer.

[0167] Solubility measurement The obtained component (A) and distilled water were placed in a screw tube at a mixing ratio of 5%, 10%, 15%, 20%, 25%, 50% and 75% at 22°C, mixed for 2 hours using a mix rotor, and then allowed to stand for 24 hours. After standing, the mixture was carefully observed with the naked eye to check for turbidity or layer separation, and for uniformity. The mixing ratio (%) is defined by the following formula, and the mixing ratio (%) at which no turbidity or layer separation was observed after standing for 24 hours and a homogeneous liquid was maintained was regarded as the solubility (%). Mixing ratio (%) = parts by weight of distilled water / (parts by weight of distilled water + parts by weight of component (A)) x 100

[0168] ◆Hydroxyl value measurement conditions A mixture of acetic anhydride and pyridine was added to the sample and the sample was heated in a hot bath at 92°C for 1 hour. A small amount of water was then added and the sample was heated in a hot bath at 92°C for 10 minutes. After cooling, the acid was titrated with an ethanol solution of potassium hydroxide using a phenolphthalein solution as an indicator to determine the hydroxyl value.

[0169] ◆APHA APHA was measured using a color difference meter (Petroleum Product Color Tester OME-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0170] GPC measurement conditions Equipment: Waters GPC system name 1515 2414 717P RI Detector: RI detector Column: Guard column: Showa Denko KFG (8μm 4.6×10mm), main column: 2 types: Waters styragel HR 4E THF (7.8×300mm) + styragel HR 1THF (7.8×300mm) Column temperature: 40℃ Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min Calibration curve: A calibration curve was created using standard polystyrene. The detected peaks with molecular weights of 400 or more were not divided but were regarded as one peak to calculate Mw.

[0171] Saponification value measurement conditions The sample was added with an ethanol solution of potassium hydroxide and heated in a hot bath at 75°C for 30 minutes. After cooling, the base was titrated with an aqueous hydrochloric acid solution using a phenolphthalein solution as an indicator to determine the saponification value.

[0172] 2) Manufacturing Example 2 [Production of component (A): Production of 51 mol % acrylate of sorbitol with 6 mol ethylene oxide adduct (hydroxyl value 180)] In a flask similar to that in Production Example 1, 600 g (7.8 moles as hydroxyl groups) of ethylene oxide adduct of sorbitol [manufactured by Aoki Oil Industries Co., Ltd., hydroxyl value 730 mgKOH / g], 1829 g (14.1 moles) of MCA, 0.77 g (0.0069 moles) of DABCO as catalyst X, 2.86 g (0.0138 moles) of zinc acrylate as catalyst Y, 2.09 g of MEHQ, and 0.24 g of TEMPOL were charged, and while bubbling oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) into the liquid, the mixture was heated and stirred at an internal temperature of 120°C to 130°C for 9 hours, while the pressure in the reaction system was adjusted to a range of 200 to 400 mmHg, and a mixture of MEL and MCA by-produced as the transesterification reaction proceeded was extracted from the reaction system via a rectification column and a cooling tube to carry out the transesterification reaction. During this time, MCA containing MEHQ and TEMPOL was added at any time to the reaction liquid via the rectification column. The rate of acrylate of hydroxyl groups by the transesterification reaction was determined from the amount of MEL produced by liquid chromatography and was found to be 51 mol %. After cooling the reaction solution, 140 g of aluminum silicate (K700) was added and stirred for 1 hour at an internal temperature of 95° C. to 100° C. to adsorb the catalyst. Thereafter, the reaction solution was cooled to an internal temperature of 40° C. or less, 1.0 g of calcium hydroxide was added and further stirred at room temperature for 2 hours, after which the solid matter was separated by pressure filtration. The obtained filtrate was placed in the same flask as in Production Example 1, and stirred for 13 hours while bubbling dry air at the same internal temperature and pressure range as in Production Example 1, to distill off unreacted MCA and the by-product MEL. The flask liquid was cooled to room temperature, 0.56 parts (0.0063 moles) of DEHA was added, and the mixture was stirred for 2 hours at normal pressure and at an internal temperature of 75°C to 85°C. Then, pressure filtration was performed to obtain 776 g of filtrate. The acrylate mixture obtained in Production Example 2 is hereinafter referred to as Sb-EOA-2.

[0173] The amount of MCA remaining in Sb-EOA-2 was measured by gas chromatography and found to be less than 100 ppm, and no odor was detected. The viscosity, water solubility, hydroxyl value, APHA, Mw, saponification value and number of added acryloyl groups q of Sb-EOA-2 were measured according to the above-mentioned methods, and the results are shown below. Viscosity (25°C): 2.63 Pa s, water solubility: 50%, hydroxyl value: 180 mg KOH / g, APHA: 86, Mw: 1096, saponification value: 288 mg KOH / g, number of acryloyl groups added q: 3.3, acrylate ratio 51 mol%

[0174] 3) Manufacturing Example 3 [Production of component (A): Production of 80 mol % acrylate of 18 mol ethylene oxide adduct of sorbitol (hydroxyl value 18)] Into a flask similar to that in Production Example 1, 660 g (4.0 moles as hydroxyl groups) of an ethylene oxide adduct of sorbitol (manufactured by Aoki Oil Industries Co., Ltd., hydroxyl value 340 mgKOH / g (6.1 meq / g), average ethylene oxide addition number 18.34, peroxide concentration 0.3 ppm), 1561 g (12.0 moles) of MCA, 1.78 g (0.0159 moles) of DABCO as catalyst X, and 6.59 g (0.0 The mixture was heated and stirred for 24 hours at an internal temperature of 120°C to 130°C while bubbling oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) into the liquid, while adjusting the pressure in the reaction system to 200 to 400mmHg. As the transesterification reaction proceeded, a mixture of MEL and MCA, which were by-produced, was extracted from the reaction system through a rectification column and a cooling tube, and the transesterification reaction was carried out. During this time, MCA containing MEHQ and TEMPOL was added to the reaction liquid from time to time through the rectification column. The rate of acrylate of hydroxyl groups by the transesterification reaction was determined from the amount of MEL produced by liquid chromatography and was found to be 80 mol %. After cooling the reaction solution, 196 g of aluminum silicate (K700) was added and stirred for 1 hour at an internal temperature of 95° C. to 100° C. to adsorb the catalyst. Thereafter, the reaction solution was cooled to an internal temperature of 40° C. or less, 1.3 g of calcium hydroxide was added and further stirred at room temperature for 2 hours, after which the solid matter was separated by pressure filtration. The obtained filtrate was placed in the same flask as in Production Example 1, and stirred for 13 hours while bubbling dry air at the same internal temperature and pressure range as in Production Example 1, to distill off unreacted MCA and the by-product MEL. The flask liquid was cooled to room temperature, 0.43 parts (0.0048 moles) of DEHA was added, and the mixture was stirred for 2 hours at normal pressure and at an internal temperature of 75°C to 85°C. Then, pressure filtration was performed to obtain 769 g of filtrate. The acrylate mixture obtained in Production Example 3 is hereinafter referred to as Sb-EOA-3.

[0175] The amount of MCA remaining in Sb-EOA-3 was measured by gas chromatography and found to be less than 700 ppm, and no odor was detected. The viscosity, water solubility, hydroxyl value, APHA, Mw, saponification value and number of added acryloyl groups q of Sb-EOA-3 were measured according to the above-mentioned methods, and the results are shown below. Viscosity (25°C): 0.47 Pa s, water solubility: 75% or more, hydroxyl value: 18 mg KOH / g, APHA: 181, Mw: 1698, saponification value: 227 mg KOH / g, number of acryloyl groups added q: 5.1, acrylate ratio 80 mol%

[0176] 4) Manufacturing Example 4 [Production of component (E) (alkali-soluble resin)] A 5L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 226.8 parts of methyl methacrylate (hereinafter referred to as "MMA"), 134.4 parts of acrylonitrile (hereinafter referred to as "AN"), 122.0 parts of methacrylic acid (hereinafter referred to as "MAA"), 142.8 parts of isobutyl methacrylate and 1,281 parts of ethyl acetate, and stirred at 75 revolutions per minute while bubbling nitrogen at a flow rate of 50 ml / min. The temperature was raised to 67 ° C. and maintained for 1 hour. Then, a solution of 2,2'-azobis (2,4-dimethylvaleronitrile) (hereinafter referred to as "AMBN") and 11 parts of ethyl acetate was added, reacted for 30 minutes, and the internal temperature was raised to 70 ° C. Thereafter, a solution containing 340.2 parts of MMA, 201.6 parts of AN, 183.0 parts of MAA, 214.2 parts of isobutyl methacrylate, 2.8 parts of AMBN, and 494.0 parts of ethyl acetate was added dropwise over 4 hours, and the mixture was allowed to react at an internal temperature of 70°C for 8 hours. Thereafter, 207 parts of ethyl acetate for dilution was added, the external temperature was set to 80° C., and boiling point aging (internal temperature 78° C.) was carried out for 4 hours to obtain an alkali-soluble resin solution containing an alkali-soluble resin (e1). The solids concentration of this alkali-soluble resin solution was 35.0%, the viscosity at 25°C was 25,000 mPa·s, and the weight average molecular weight (Mw) of the alkali-soluble resin (e1) was 90,100 and the acid value was 138 mgKOH / g (solids equivalent).

[0177] 2. Examples 1 to 3 and Comparative Examples 1 to 3 (Active energy ray curable composition for pattern formation) 1) Preparation of the composition Compositions were obtained by using the component (A) obtained in Production Examples 1 to 3 and the components indicated by the following abbreviations, and stirring and mixing them at 40° C. in the proportions shown in Table 1. The numbers in Table 1 indicate the number of parts. Component (A) Sb-EOA-1: Acrylate obtained in Production Example 1 Sb-EOA-2: Acrylate obtained in Production Example 3 Sb-EOA-3: Acrylate obtained in Production Example 4 (C) Component M-240: Tetraethylene glycol diacrylate, hydroxyl value: 5 mg KOH / g) (manufactured by Toagosei Co., Ltd., product name: Aronix M-240) M-402: Mixture of dipentaerythritol pentaacrylate and hexaacrylate, hydroxyl value: 33 mg KOH / g) (manufactured by Toagosei Co., Ltd., product name: Aronix M-402) Components (D) and (E) 114.3 parts of the ethyl acetate solution (solid content: 35.0%) containing the alkali-soluble resin (e1) obtained in Production Example 4 was used. (B) Component Om907: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins, trade name: Omnirad 907D) DETX: 2,4-diethylthioxanthone (manufactured by Lambson Japan, product name: Speedcure DETX)

[0178] [Table 1]

[0179] 2) Evaluation of the composition (1) Sensitivity The obtained compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were used to coat a cut release film manufactured by Fujimori Kogyo Co., Ltd. (Film Vina HTA, film thickness: 75 μm) with a bar coater to a film thickness of 25 μm, and after drying at 80°C for 5 minutes, a release film manufactured by Fujimori Kogyo Co., Ltd. (Film Vina KF, film thickness: 50 μm) was laminated to obtain a resist film specimen. Next, the film bina KF was peeled off and removed from the obtained test specimen, and the dried coating was thermally laminated (70°C, 0.1 MPa, lamination speed 1 m / min) using a roll laminator onto a double-sided copper-clad FR-4 substrate (0.3 mm thick) that had been buffed. Next, the film bina HTA was peeled off, and a 21-step tablet for measuring sensitivity was attached to the dried coating, and exposed to 200 mJ / cm under vacuum using an Oak Seisakusho high-pressure mercury lamp exposure machine. 2 It was exposed. Next, development was performed using a spray developer (30°C, 1 wt% sodium bicarbonate aqueous solution). The development time was the same as that determined in (2) Alkaline developability. The exposure amount equivalent to 12 steps of the step tablet, expressed by the following formula based on the maximum number of steps of the step tablet at which the dried coating film after development remained completely, was taken as the sensitivity. Sensitivity (mJ / cm 2 )=200×{1.414^(12-step tablet number)}

[0180] (2) Alkaline developability Using the obtained compositions of Examples 1 to 3 and Comparative Examples 1 and 2, resist film specimens were obtained in the same manner as in the evaluation of sensitivity. Next, the film bina KF was peeled off and removed from the obtained test specimen, and the dried coating was thermally laminated (70°C, 0.1 MPa, lamination speed 1 m / min) using a roll laminator onto a double-sided copper-clad FR-4 substrate (0.3 mm thick) that had been buffed. Next, the film binder HTA was peeled off, and development was performed directly using a spray developing device (30°C, 1 wt% aqueous sodium bicarbonate solution). The time until the dried coating film was completely dissolved was defined as the alkaline developability.

[0181] (3) Limiting resolution The obtained compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were used to obtain resist film specimens. Next, the film bina KF was peeled off and removed from the obtained test specimen, and the dried coating was thermally laminated (70°C, 0.1 MPa, lamination speed 1 m / min) using a roll laminator onto a double-sided copper-clad FR-4 substrate (0.3 mm thick) that had been buffed. Next, the film bina HTA was peeled off, and a negative pattern with lines / spaces of [1] 40μm / 80μm, [2] 50μm / 100μm, [3] 60μm / 120μm, [4] 70μm / 140μm, [5] 80μm / 160μm, [6] 90μm / 180μm, and [7] 100μm / 200μm was attached to the dried coating, and exposed under vacuum with a high-pressure mercury lamp exposure machine manufactured by Oak Seisakusho. The exposure amount was the one obtained in (1) Sensitivity. Next, (2) the time obtained in the alkaline developability test was used as the developing time, and alkaline development was carried out under the same conditions as (2) above, to form a pattern. The resulting pattern was observed under a microscope, and the minimum line width at which the line / space pattern was formed without any skips or residual development was taken as the resolution. The smaller this value, the higher the resolution, indicating superiority of the resist material. The results are shown in Table 2.

[0182] [Table 2]

[0183] (3) Evaluation results As is clear from the results of Examples 1 to 3 in Table 2, the compositions of the present invention were excellent in alkaline developability, sensitivity, and resolution. On the other hand, the composition of Comparative Example 1, which did not contain the component (A), had very poor alkaline developability and also reduced resolution, while the composition of Comparative Example 2 was poor in sensitivity and alkaline developability. [Industrial Applicability]

[0184] The composition of the present invention can be used in various applications as a pattern-forming agent, for example, for photosensitive lithographic printing plates, resists such as etching resists and solder resists, columnar spacers in the production of liquid crystal panels, coloring compositions for forming pixels or black matrices in color filters, and protective films for color filters.

Claims

1. Component (A): An active energy ray-curable composition for pattern formation, comprising a (meth)acrylate of an alkylene oxide adduct of an alditol (excluding glycerol), wherein the component (A) is a di(meth)acrylate of an alkylene oxide adduct of sorbitol.

2. 2. The active energy ray-curable composition for pattern formation according to claim 1, wherein the component (A) is a compound represented by the following general formula (5): 【Chemistry 1】 [In formula (5), R 14 ~R 16 each independently represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms; R 14 ~R 16 When there are a plurality of each of X, they may be the same or different. 1 ~X 3 Each of X independently represents a hydrogen atom or a (meth)acryloyl group. 2 may be the same or different, and multiple R 15 may be the same or different from each other, and the multiple b's may be the same or different from each other. a, b, and c each represent a positive number, and are not all 0 at the same time, and satisfy 0<(a+nb+c)≦80. n is 4.

3. 3. The active energy ray-curable composition for pattern formation according to claim 1, wherein the component (A) has a solubility in distilled water at a temperature of 22° C. of 10% or more.

4. 4. The active energy ray-curable composition for pattern formation according to claim 1, wherein the component (A) has a saponification value of 150 to 450 mgKOH / g.

5. 5. The active energy ray-curable composition for pattern formation according to claim 3, wherein the compound having one (meth)acryloyl group is an alkoxyalkyl (meth)acrylate.

6. The active energy ray-curable composition for pattern formation according to any one of claims 1 to 2, further comprising a component (B): a photopolymerization initiator in addition to the component (A).

7. The active energy ray-curable composition for pattern formation according to any one of claims 1 to 6, further comprising a component (C): a compound having an ethylenically unsaturated group other than the component (A), in addition to the component (A).

8. The active energy ray-curable composition for pattern formation according to any one of claims 1 to 7, further comprising a component (D): water and / or an organic solvent in addition to the component (A).

9. The active energy ray-curable composition for pattern formation according to any one of claims 1 to 8, further comprising a component (E): an alkali-soluble resin in addition to the component (A).

10. A dry film resist comprising a coating of the active energy ray-curable composition for pattern formation according to any one of claims 1 to 9 formed on a plastic film or sheet.

11. A method for producing an active energy ray-curable composition for forming a pattern, comprising the step of producing a mixture (A) of compounds having a (meth)acryloyl group by subjecting an alkylene oxide adduct of alditol (excluding glycerol) to an ester exchange reaction with a compound having one (meth)acryloyl group in the presence of the following catalysts X and Y, wherein the component (A) has a solubility in distilled water at a temperature of 22° C. of 10% or more. Catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure, or a salt or complex thereof, an amidine, or a salt or complex thereof, a compound having a pyridine ring, or a salt or complex thereof, and a phosphine, or a salt or complex thereof. Catalyst Y: A compound containing zinc.

12. The method for producing an active energy ray-curable composition for pattern formation according to claim 11, wherein the component (A) is a compound represented by the following general formula (5): 【Chemistry 2】 [In formula (5), R 14 ~R 16 each independently represents a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms; R 14 ~R 16 When there are a plurality of each of X, they may be the same or different. 1 ~X 3 Each of X independently represents a hydrogen atom or a (meth)acryloyl group. 2 may be the same or different, and multiple R 15 may be the same or different, and the multiple b's may be the same or different. a, b, and c each represent a positive number, and are not all 0 at the same time, and satisfy 0<(a+nb+c)≦80. n represents an integer of 2 to 4.

13. The method for producing an active energy ray-curable composition for pattern formation according to any one of claims 11 to 12, wherein the component (A) has a saponification value of 150 to 450 mgKOH / g.

14. The method for producing an active energy ray-curable composition for pattern formation according to any one of claims 11 to 13, wherein the compound having one (meth)acryloyl group is an alkoxyalkyl (meth)acrylate.

15. The method for producing an active energy ray-curable composition for pattern formation according to any one of claims 11 to 14, wherein the catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure, a salt thereof, or a complex thereof, an amidine, a salt thereof, or a complex thereof, and a compound having a pyridine ring, or a salt thereof, or a complex thereof.

16. The method for producing an active energy ray-curable composition for pattern formation according to any one of claims 11 to 15, wherein the catalyst Y is an organic acid zinc or / and a zinc diketone enolate.

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