JP2019026800A - Curable composition - Google Patents

Abstract

To provide a curable composition, wherein, although it is a solvent-free curable composition, it has low viscosity and excellent alkali developability, and has low metal ion concentration.SOLUTION: A curable composition contains a mixture (A) containing a compound with an acid anhydride added to a mixture (a) containing a compound having a hydroxyl group and two or more (meth) acryloyl groups, the (A) component having an acid value of 20-70 mgKOH/g and a 25°C viscosity of 50-9,500 mPa s.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, and preferably to an active energy ray curable composition. The composition of the present invention can be used for various uses such as pattern forming agents such as photosensitive lithographic printing plates and color resists, coating agents such as hard coats, printing inks and adhesives. It can be preferably used and belongs to these technical fields.
In the present specification, an acryloyl group and / or a methacryloyl group is represented as a (meth) acryloyl group, an acrylate and / or methacrylate is represented as a (meth) acrylate, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. It expresses.

  Conventionally, a composition containing a (meth) acrylate compound is often used as a resist used in an etching resist, a solder resist, and a color resist that forms a colored layer of a color filter. In that case, the polyfunctional (meth) acrylate which has two or more (meth) acryloyl groups is used for the purpose of the improvement of the sensitivity of a composition, the improvement of the hardness of hardened | cured material, etc.

  Many of the polyfunctional (meth) acrylates used in conventional resists are insoluble in alkali, and as a result, a film residue of an uncured part (unexposed part) occurs during development, and sufficient resolution cannot be obtained. There was a point.

As an active energy ray-curable pattern forming composition for a color filter, a composition containing a polyfunctional (meth) acrylate having no carboxyl group, an alkali-soluble resin, a photopolymerization initiator and an organic solvent is known. (Patent Document 1).
In this invention, in order to improve the crosslink density and alkali solubility of the cured product, the introduction ratio of the photocurable group and acidic functional group of the alkali-soluble resin is increased. There is a limit to the amount of the functional group, and the viscosity of the composition increases, resulting in a problem that coating suitability is impaired.

  Therefore, a carboxyl group-containing polyfunctional (soluble in alkali) obtained by reacting a hydroxyl group-containing polyfunctional (meth) acrylate having a hydroxyl group and a plurality of (meth) acryloyl groups with an acid anhydride such as a carboxylic anhydride. Photosensitive compositions containing a (meth) acrylate have been proposed (Patent Documents 2, 3 and 4).

JP 2000-105456 A JP 2001-089416 A Japanese Patent Laid-Open No. 2001-091954 JP 2014-215515 A

However, the conventional photosensitive composition containing the carboxyl group-containing polyfunctional (meth) acrylate compound described in Patent Documents 2 to 4 is photosensitive containing a polyfunctional (meth) acrylate having no carboxyl group. Although the alkali developability is improved as compared with the composition, the solubility in an alkaline aqueous solution is not yet sufficient, an uncured residue is generated during development, and a further improvement in alkali developability is required.
In addition, when the compositions of Patent Documents 2 to 4 are solvent-free curable compositions that do not contain an organic solvent, since the viscosity is insufficient, handling properties and coating properties are improved. There was a problem.
In addition, the conventional photosensitive composition may be contained in the metal ion in the composition due to the carboxyl group-containing polyfunctional (meth) acrylate of the blending component, and the electrical characteristics of the ion elution from the cured film Decrease sometimes became a problem. In particular, when the carboxyl group-containing polyfunctional (meth) acrylate raw material (meth) acrylate is produced by a dehydration esterification reaction, it contains an alkali metal due to the alkali metal hydroxide used in the neutralization step. In this case, there is a need for a purification step for removing the alkali metal, and even if the purification is performed, the reduction of the alkali metal may be insufficient.
The present invention has been made in view of the above circumstances, and its purpose is to provide a curable composition having excellent low viscosity and alkali developability, and having a low metal ion concentration, even if it is a solventless curable composition. Is to provide.

In order to solve the above problems, the inventors of the present invention have a curable composition containing an acidic group-containing polyfunctional (meth) acrylate having a specific acid value and a specific viscosity, which is excellent in low viscosity and alkali developability. The present inventors have found that the metal ion concentration is low and completed the present invention.
The present invention relates to a mixture (A) comprising a compound obtained by adding an acid anhydride to a mixture (a) [hereinafter referred to as “mixture (a)”] comprising a compound having a hydroxyl group and two or more (meth) acryloyl groups. Hereinafter, it is referred to as “component (A)”, the acid value of the component (A) is 20 to 70 mg KOH / g, and the viscosity at 25 ° C. is 50 to 9,500 mPa · s.

  Even when the composition of the present invention is a solvent-free composition, it has a low viscosity, is excellent in alkali developability, and has a low metal ion concentration.

The present invention relates to a curable composition containing the component (A), wherein the acid value of the component (A) is 20 to 70 mgKOH / g and the viscosity at 25 ° C. is 50 to 9,500 mPa · s.
Hereinafter, the component (A), other components, and applications will be described.

1. Component (A) Component (A) is a mixture containing a compound (a) [a mixture containing a compound having a hydroxyl group and two or more (meth) acryloyl groups] and an acid anhydride added thereto.
The component (A) needs to have an acid value of 20 to 70 mgKOH / g and a viscosity at 25 ° C. of 50 to 9,500 mPa · s.
The component (A) needs to have an acid value of 20 to 70 mgKOH / g, preferably 20 to 65 mgKOH / g.
When the acid value of the component (A) is less than 20 mgKOH / g, the alkali developability becomes insufficient. On the other hand, when it exceeds 70 mgKOH / g, the viscosity of the composition becomes high.
In addition, the acid value in this invention means the milligram number of potassium hydroxide required in order to neutralize the acid contained in 1g of samples.
The component (A) needs to have a viscosity at 25 ° C. of 100 to 9,500 mPa · s, and preferably 500 to 9,500 mPa · s.
When the viscosity of the component (A) is less than 50 mPa · s, the suitability for coating with a thick film becomes insufficient. On the other hand, when the viscosity exceeds 9,500 mPa · s, the suitability for coating with a thin film is insufficient. End up.
The viscosity in the present invention means a value measured at 25 ° C. using an E-type viscometer.

  Next, the mixture (a) and the acid anhydride, which are raw material compounds of the component (A), and the method for producing the component (A) will be described.

1-1. Mixture (a)
The mixture (a) is a mixture containing a compound having a hydroxyl group and two or more (meth) acryloyl groups, and a mixture containing a compound having a hydroxyl group and three or more (meth) acryloyl groups is preferred.
Specific examples of the compound having two or more (meth) acryloyl groups and hydroxyl groups include trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, ditrimethylolpropane di (meth) acrylate and trimethylolpropane. (Meth) acrylate, di (meth) acrylate and tri (meth) acrylate of pentaerythritol, di (meth) acrylate and tri (meth) acrylate of diglycerin, di (meth) acrylate of dipentaerythritol, tri (meth) acrylate , Tetra (meth) acrylate and penta (meth) acrylate, and polyglycerin poly (di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate and penta (meth) acrylate) Meth) acrylate.

The mixture (a) in the present invention includes a compound having a hydroxyl group and one (meth) acryloyl group by-produced in the production process and a compound having three or more (meth) acryloyl groups not having a hydroxyl group. You can leave.
Examples of the compound having a hydroxyl group and one (meth) acryloyl group include, based on preferred compounds, mono (meth) acrylate of ditrimethylolpropane, mono (meth) acrylate of pentaerythritol, and mono (meth) acrylate of dipentaerythritol ( And (meth) acrylate.
Examples of the compound having three or more (meth) acryloyl groups not having a hydroxyl group include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth). ) Acrylate and the like.
The compound having a hydroxyl group and one (meth) acryloyl group and the compound having three or more (meth) acryloyl groups not having a hydroxyl group are contained in the mixture (a) at a ratio of 20 to 80% by weight. It may be included.

The mixture (a) is preferably a mixture of compounds having a high hydroxyl value, preferably a mixture having a hydroxyl value of 10 to 100 mgKOH / g, more preferably 10 to 90 mgKOH / g, and 10 to 80 mgKOH / g. It is particularly preferred.
By making the hydroxyl value of the mixture (a) 10 mgKOH / g or more, the acid value of the component (A) can be made desired, and by making the hydroxyl value 100 mgKOH / g or less, The viscosity can be as desired.
In the present invention, the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of a sample.

The mixture (a) is a mixture of various polyfunctional (meth) acrylates as described above, but it is preferable to use a mixture having a small proportion of high molecular weight substances as side reactions.
The high molecular weight substance in the mixture (a) is a value obtained by gel permeation chromatography (hereinafter referred to as “GPC”) measurement, and is an area% of the high molecular weight substance defined by the following formula (1). Is preferably less than 25%.
High molecular weight area% = [(R−IL) / R] × 100 (1)
The symbols and terms in formula (1) mean the following.
R: total area of detection peaks in mixture (a) I: area of detection peaks containing ideal structure (meth) acrylate L: weight average molecular weight (hereinafter referred to as detection peak containing ideal structure (meth) acrylate) Total area of detection peak with small (Mw) and ideal structure (meth) acrylate: The number of hydroxyl groups contained per molecule of raw alcohol and the same number of (meth) acryloyl groups per molecule, and Michael addition A polyfunctional (meth) acrylate having no mold structure is meant.
As a specific example of the ideal structure (meth) acrylate, for example, a preferable polyhydric alcohol is pentaerythritol tetra (meth) acrylate in the case of pentaerythritol, and dipentaerythritol hexa (meth) in the case of dipentaerythritol. Acrylate.
In the present invention, Mw means a value obtained by converting a molecular weight measured by GPC using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent based on the molecular weight of polystyrene.

By setting the area% of the high molecular weight material within this range, the composition can have a low viscosity.
In addition, the molecular weight measured by GPC in the present invention means a value measured under the following conditions.
・ Detector: Differential refractometer (RI detector)
-Column type: Cross-linked polystyrene column-Column temperature: within 25-50 ° C-Eluent: THF

The mixture (a) comprises a compound obtained by a dehydration esterification reaction of a polyhydric alcohol having three or more alcoholic hydroxyl groups (hereinafter simply referred to as “polyhydric alcohol”) and (meth) acrylic acid, and a polyhydric alcohol. Any compound obtained by transesterifying a compound having one (meth) acryloyl group (hereinafter referred to as monofunctional (meth) acrylate) can be used.
As the mixture (a), a compound obtained by subjecting a polyhydric alcohol and a monofunctional (meth) acrylate to an ester exchange reaction can produce the mixture (a) having the specific hydroxyl value described above in a high yield. Since there are few high molecular weight bodies in a mixture (a), it is low viscosity and it is preferable at the point which is excellent in the coating property and leveling property of a composition. Further, the mixture (a) obtained by the transesterification reaction can reduce the concentration of alkali metal ions in the component (A) finally obtained as compared with the dehydration esterification reaction, specifically, It can be made less than 0.5 ppm, and is preferable in that there is no concern about a decrease in electrical characteristics due to ion elution from the cured film.

1-1-1. The dehydration esterification reaction mixture (a) can be produced by subjecting a polyhydric alcohol and (meth) acrylic acid to a dehydration esterification reaction.

The polyhydric alcohol is a polyhydric alcohol having 3 or more alcoholic hydroxyl groups, and various compounds can be used.
Specific examples of the polyhydric alcohol include trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, diglycerin, dipentaerythritol, and polyglycerin.
The polyglycerin is preferably a compound having a hydroxyl value of 700 to 1,200 mg KOH / g, more preferably 800 to 1,150 mg KOH / g, and preferably 850 to 1,100 mg KOH / g. g.

(Meth) acrylic acid used in the dehydration esterification reaction may be either acrylic acid or methacrylic acid, or both acrylic acid and methacrylic acid, but only acrylic acid is used. It is preferable to do.
Further, in the production of the mixture (a), instead of (meth) acrylic acid, (meth) acrylic acid equivalent, (meth) acrylic acid halide, (meth) acrylic anhydride, etc. may be used. Good.

When the mixture (a) is produced by a dehydration esterification reaction between a polyhydric alcohol and (meth) acrylic acid, the proportion of (meth) acrylic acid used is such that the hydroxyl value of the resulting (meth) acrylic acid ester is 10 There is no particular limitation as long as it is an amount of ˜100 mg KOH / g.
The molar amount of (meth) acrylic acid used is preferably less than the molar amount of the hydroxyl group of the polyhydric alcohol used, and is 0.75 to 1.25 molar equivalents relative to the total number of hydroxyl groups of the polyhydric alcohol. Preferably, it is 0.85-1.15 molar equivalent.

There is no restriction | limiting in particular as a manufacturing method of a mixture (a), Although well-known dehydration esterification reaction can be used, It is preferable to use a catalyst and a stabilizer.
As the catalyst, an acid catalyst can be preferably exemplified.
Moreover, as a stabilizer, well-known polymerization inhibitors, such as hydroquinone monomethyl ether, can be mentioned suitably. It is also preferable to use oxygen as a stabilizer, particularly a polymerization inhibitor. For example, unnecessary polymerization of (meth) acrylic acid or (meth) acrylate can be prevented by producing the mixture (a) in an oxygen-containing atmosphere. Moreover, it is preferable that it is 1-20 volume%, and, as for the content rate of oxygen in atmosphere, it is more preferable that it is 1-10 volume%.
Moreover, it is preferable that the manufacturing method of a mixture (a) includes the method of performing at least liquid-liquid extraction (separation) and refine | purifying. In the above embodiment, a compound having a hydroxyl value of 10 to 100 mgKOH / g can be easily produced.

1-1-2. The transesterification reaction mixture (a) can also be produced by transesterification of a polyhydric alcohol and a monofunctional (meth) acrylate in the presence of a transesterification catalyst.
According to the transesterification reaction between the polyhydric alcohol and the monofunctional (meth) acrylate used in combination with the catalysts X and Y, the polyhydric alcohol and (meth) acrylic acid in the mixture (a) are compared with the dehydration esterification reaction. Therefore, it is possible to produce a polyfunctional (meth) acrylate mixture having low viscosity and few impurities, and thus excellent physical properties.
Hereafter, the manufacturing method of a polyhydric alcohol, monofunctional (meth) acrylate, the catalyst X, the catalyst Y, and a mixture (a) is demonstrated.

1-1-2-1. As the polyhydric alcohol polyhydric alcohol, the same compounds as described above can be used, and pentaerythritol, ditrimethylolpropane, diglycerin, dipentaerythritol and polyglycerin are preferable.

1-1-2-2. The monofunctional (meth) acrylate used as a raw material of the monofunctional (meth) acrylate mixture (a) is a compound having one (meth) acryloyl group in the molecule, and is represented by the following formula (1), for example. Compounds.

In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic group having 1 to 50 carbon atoms.

Preferable specific examples of R ² in the general formula (1) include carbon such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group. Alkyl groups of formulas 1-8, alkoxyalkyl groups such as 2-methoxyethyl group, 2-ethoxyethyl group and 2-methoxybutyl group, and N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N , N-dimethylaminopropyl groups, and N, N-diethylaminopropyl groups and the like.
Specific examples of R ² in the general formula (1) include compounds described in JP 2017-39916 A, JP 2017-39917 A, and International Publication No. 2017/033732 in addition to the above. It is done.

In the present invention, these monofunctional (meth) acrylates can be used alone or in combination of two or more.
Among these monofunctional (meth) acrylates, carbon such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Preferred examples include alkyl (meth) acrylates having an alkyl group of 1 to 8; alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate; and N, N-dimethylaminoethyl (meth) acrylate, particularly polyhydric alcohols. More preferable examples are (meth) acrylates having an alkyl group having 1 to 4 carbon atoms, and alkoxyalkyl (meth) acrylates having an alkyl group having 1 to 2 carbon atoms, which exhibit good reactivity with respect to It is done.
Furthermore, the alkoxyalkyl (meth) acrylate which has a C1-C2 alkyl group which promotes melt | dissolution of a polyhydric alcohol and shows very favorable reactivity is still more preferable, and 2-methoxyethyl (meth) acrylate is especially preferable.
Furthermore, as monofunctional (meth) acrylate, monofunctional acrylate is particularly preferable because of its excellent reactivity.

  The ratio of the polyhydric alcohol and the monofunctional (meth) acrylate used in the method for producing the mixture (a) is not particularly limited, but the monofunctional (meth) acrylate is 0.4 per mol of the total hydroxyl group in the polyhydric alcohol. -10.0 mol is preferable, More preferably, it is 0.6-5.0 mol. By making the monofunctional (meth) acrylate 0.4 mol or more, side reactions can be suppressed. Moreover, the production amount of the mixture (a) can be increased and the productivity can be improved by adjusting the amount to 10.0 mol or less.

1-1-2-3. As the transesterification reaction catalyst in the method for producing the catalyst mixture (a), conventionally known ones such as a tin-based catalyst, a titanium-based catalyst, and sulfuric acid can be used.
In the present invention, it is preferable to use the following catalysts X and Y in combination as a catalyst in that the mixture (a) can be efficiently produced in high yield.
Catalyst X: a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as “azabicyclo compound”), an amidine or a salt or complex thereof (hereinafter referred to as “amidine compound”), a compound having a pyridine ring, or One or more compound catalysts selected from the group consisting of salts or complexes thereof (hereinafter referred to as “pyridine compounds”) and phosphines or salts or complexes thereof (hereinafter referred to as “phosphine compounds”): a compound containing zinc.
Hereinafter, the catalyst X and the catalyst Y will be described.

1-1-2-4. Catalyst X
The catalyst X is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds and phosphine compounds.
The catalyst X is preferably one or more compounds selected from the group consisting of an azabicyclo compound, an amidine compound, and a pyridine compound, among the compound groups described above. These compounds are excellent in catalytic activity and can preferably produce the mixture (a), and also form a complex with catalyst Y described later after completion of the reaction, and the complex can be easily obtained from the reaction solution after completion of the reaction by a simple method such as adsorption. Can be removed. In particular, since the complex with the catalyst Y becomes hardly soluble in the reaction solution, the azacyclo compound can be more easily removed by filtration and adsorption.
On the other hand, although the phosphine compound is excellent in catalytic activity, it is difficult to form a complex with the catalyst Y, or when the complex is formed, it is easily soluble in the reaction solution, and the phosphine compound in the reaction solution after the completion of the reaction. Since most of the compound remains dissolved, it is difficult to remove from the reaction solution by a simple method such as filtration and adsorption. For this reason, the phosphine-based catalyst remains in the final product, thereby causing turbidity and catalyst precipitation during storage of the product, and increasing the viscosity or gelation over time. May cause problems.

Specific examples of the azabicyclo compound include various compounds as long as the compound satisfies the cyclic tertiary amine having an azabicyclo structure, a salt of the amine, or a complex of the amine. 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. DABCO ”).
Specific examples of the azabicyclo compounds include compounds described in JP 2017-39916 A, JP 2017-39917 A, and International Publication No. 2017/033732.

  Specific examples of the amidine compound 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 Examples include phthalimide DBU.

Principal examples of pyridine-based 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”) and the like.
Specific examples of the pyridine-based compound include compounds described in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732.

  Examples of the phosphine compound include compounds having a structure represented by the following formula (2).

[In Formula (2), R < ³ >, R < ⁴ > and R < ⁵ > are a C1-C20 linear or branched alkyl group, a C1-C20 linear or branched alkenyl group, carbon number 6 Means an aryl group of ˜24 or a cycloalkyl group of 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different. ]
Represent. )

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.
Specific examples of the phosphine compound include compounds described in JP 2017-39916 A, JP 2017-39917 A, and International Publication No. 2017/033732.

  In this invention, these catalysts X can be used individually or in combination of 2 or more types. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferable, and particularly have good reactivity with polyhydric alcohols. At least one compound selected from the group consisting of readily available 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP is more preferable.

  The ratio of the catalyst X used in the method for producing the mixture (a) is not particularly limited, but 0.0001 to 0.5 mol of the catalyst X is preferably used with respect to 1 mol of the total hydroxyl groups in the polyhydric alcohol. More preferably, it is 0.0005-0.2 mol. By using 0.0001 mol or more of the catalyst X, the amount of the target mixture (a) produced can be increased, and by setting it to 0.5 mol or less, the production of by-products and coloring of the reaction liquid can be achieved. It can suppress and the purification process after completion | finish of reaction can be simplified.

1-1-2-5. Catalyst Y
The catalyst Y is a compound containing zinc.
As the catalyst Y, various compounds can be used as long as they contain zinc, but organic acids zinc and zinc diketone enolate are preferable because of excellent reactivity.
Examples of the organic acid zinc include dibasic acid zinc such as zinc oxalate and a compound represented by the following formula (3).

[In Formula (3), R < ⁶ > and R < ⁷ > are C1-C20 linear or branched alkyl groups, C1-C20 linear or branched alkenyl groups, C6-C24 An aryl group or a C5-C20 cycloalkyl group is meant. R ⁶ and R ⁷ may be the same or different. ]
As the compound of the formula (3), a compound in which R ⁶ and R ⁷ are linear or branched alkyl groups having 1 to 20 carbon atoms is preferable. In R ⁶ and R ⁷ , the linear or branched alkyl group having 1 to 20 carbon atoms is a functional group having no halogen atom such as fluorine and chlorine, and the catalyst Y having the functional group has a high yield. Is preferable because the mixture (a) can be produced.

  Examples of the zinc diketone enolate include compounds represented by the following formula (4).

[In Formula (4), R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R <^11> , R < ¹² > and R < ¹³ > are a hydrogen atom, a C1-C20 linear or branched alkyl group, C1-C20 A linear or branched alkenyl group, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms is meant. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different. ]

Specific examples of the compound containing zinc represented by the above formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, stearin. Examples include zinc oxide, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
In addition, about these compounds containing zinc, when the complex with the hydrate or solvate, or the catalyst X exists, this complex with the hydrate, the solvate, and the catalyst X is also a mixture (a). It can be used as the catalyst Y in the production method.

  Specific examples of the compound containing zinc represented by the above formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis (2,6-dimethyl-3,5-heptanedionato) zinc, bis ( 2,2,6,6-tetramethyl-3,5-heptanedionato) zinc, bis (5,5-dimethyl-2,4-hexanedionato) zinc and the like. In addition, about these compounds containing zinc, when the complex with the hydrate or solvate, or the catalyst X exists, this complex with the hydrate, the solvate, and the catalyst X is also a mixture (a). It can be used as the catalyst Y in the production method.

As the organic acid zinc and zinc diketone enolate in the catalyst Y, the aforementioned compounds can be used directly, but these compounds can also be generated and used in the reaction system.
For example, zinc compounds such as metal zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate (hereinafter referred to as “raw zinc compounds”) are used as raw materials. In the case of organic acid zinc, raw zinc compounds and organic acids are used. In the case of zinc diketone enolate, a method of reacting a raw material zinc compound with 1,3-diketone and the like can be mentioned.

  In this invention, these catalysts Y can be used individually or in combination of 2 or more types. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferable, and particularly acetic acid that exhibits good reactivity with polyhydric alcohol and is easily available. Zinc, zinc acrylate, and zinc acetylacetonate are preferred.

  The ratio of the catalyst Y used in the method for producing the mixture (a) is not particularly limited, but 0.0001 to 0.5 mol of the catalyst Y is preferably used with respect to 1 mol of the total hydroxyl groups in the polyhydric alcohol. More preferably, it is 0.0005-0.2 mol. By using 0.0001 mol or more of catalyst Y, the amount of the target mixture (a) produced can be increased, and by setting it to 0.5 mol or less, by-product formation and reaction liquid coloring can be achieved. It can suppress and the purification process after completion | finish of reaction can be simplified.

1-1-2-6. Transesterification As described above, the production method by the ester exchange reaction of the mixture (a) is preferably a production method in which the catalysts X and Y are used in combination as a catalyst. The production method will be described below.

  The use ratio of the catalyst X and the catalyst Y in the production method of the mixture (a) is not particularly limited, but 0.005 to 10.0 mol of the catalyst X is preferably used with respect to 1 mol of the catalyst Y, more Preferably it is 0.05-5.0 mol. By using 0.005 mol or more, the production amount of the target mixture (a) can be increased, and by making it 10.0 mol or less, production of by-products and coloring of the reaction solution are suppressed, The purification process after completion of the reaction can be simplified.

As a combination of the catalyst X and the catalyst Y used in the present invention, the catalyst X is an azabicyclo compound, the catalyst Y is preferably a compound represented by the formula (3), and the azabicyclo compound is DABCO. A combination in which the compound represented by the formula (3) is at least one compound selected from the group consisting of zinc acetate and zinc acrylate is most preferable.
In addition to being able to obtain the mixture (a) with good yield, this combination is excellent in the color tone after the completion of the reaction, and thus can be suitably used for various industrial applications in which the color tone is regarded as important. Furthermore, since the catalyst is available at a relatively low cost, it is an economically advantageous production method.

  The catalyst X and catalyst Y used in the present invention may be added from the beginning of the above reaction or may be added midway. Moreover, a desired use amount may be added all at once, or may be added in divided portions.

  It is preferable that the reaction temperature in the manufacturing method of a mixture (a) is 40-180 degreeC, More preferably, it is 60-160 degreeC. By setting the reaction temperature to 40 ° C. or higher, the reaction rate can be increased, and by setting it to 180 ° C. or lower, thermal polymerization of (meth) acryloyl groups in raw materials and products is suppressed, and coloring of the reaction liquid is performed. And the purification process after completion of the reaction can be simplified.

  The reaction pressure in the method for producing the mixture (a) is not particularly limited as long as the predetermined reaction temperature can be maintained, and the reaction may be performed in a reduced pressure state or in a pressurized state. Preferably it is 0.000001-10MPa (absolute pressure).

  In the method for producing the mixture (a), monohydric alcohol derived from monofunctional (meth) acrylate is by-produced as the transesterification proceeds. Although the monohydric alcohol may be allowed to coexist in the reaction system, the transesterification reaction can be further promoted by discharging the monohydric alcohol out of the reaction system.

In the method for producing the mixture (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 n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamyl. Hydrocarbons such as benzene, 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 tellurium, dimethylcellosolve, diglyme, triglyme and tetraglyme; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone And ketones such as 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 Ionic liquids such as phosphine oxides such as tributylphosphine oxide, imidazolium salts, piperidinium salts and pyridinium salts; silicon oil; and water Is mentioned.
Of these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred.
These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.

  In the method for producing the mixture (a), an inert gas such as argon, helium, nitrogen and carbon dioxide gas may be introduced into the system for the purpose of maintaining the color tone of the reaction solution satisfactorily, but the (meth) acryloyl group For the purpose of preventing polymerization of oxygen, an oxygen-containing gas may be introduced into the system. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like. As a method for introducing the oxygen-containing gas, there is a method in which the oxygen-containing gas is dissolved in the reaction solution or blown into the reaction solution (so-called bubbling).

In the method for producing the mixture (a), it is preferable to add a polymerization inhibitor to the reaction solution for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butyl hydroquinone, 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, 4-hydroxy-2,2,6,6-tetramethylpiperidine Organic polymerization inhibitors such as -1-oxyl, inorganic polymerization inhibitors such as copper chloride, copper sulfate and iron sulfate, and organic salt systems such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt A polymerization inhibitor is mentioned.
A polymerization inhibitor may be added individually by 1 type, or may be added in combination of 2 or more types, may be added from the beginning of this invention, and may be added from the middle. Moreover, a desired use amount may be added all at once, or may be added in divided portions. Moreover, you may add continuously via a rectification column.
The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm in the reaction solution, and more preferably 25 to 10,000 wtppm. By setting this ratio to 5 wtppm or more, the polymerization inhibition effect can be exerted, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification step after completion of the reaction can be simplified. Moreover, the fall of the cure rate of the mixture (a) obtained can be prevented.

  Although the reaction time in the manufacturing method of a mixture (a) changes with the kind and usage-amount of a catalyst, reaction temperature, reaction pressure, etc., Preferably it is 0.1 to 150 hours, More preferably, it is 0.5 to 80 hours.

  The method for producing the mixture (a) can be carried out by any of batch, semi-batch and continuous methods. As an example of a batch system, a polyhydric alcohol, a monofunctional (meth) acrylate, a catalyst, and a polymerization inhibitor are charged into a reactor, and stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction solution. Then, it can implement by the method of producing | generating the target mixture (a) by extracting the monohydric alcohol byproduced with progress of transesterification from a reactor by predetermined | prescribed pressure.

For the reaction product obtained by the method for producing the mixture (a), it is preferable to carry out a separation / purification operation because the desired mixture (a) can be obtained with high purity.
Examples of the separation / purification operation include a crystallization operation, a filtration operation, a distillation operation, and an extraction operation, and these are preferably combined. 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, and molecular distillation. And steam distillation, and the extraction operation includes solid-liquid extraction and liquid-liquid extraction.
A solvent may be used in the separation and purification operation.
Further, a neutralizing agent for neutralizing either or both of the catalyst and polymerization inhibitor used in the present invention, an adsorbing agent for removing by adsorption, and an acid or alkali for decomposing or removing by-products Further, activated carbon for improving the color tone, diatomaceous earth for improving the filtration efficiency and filtration speed, and the like may be used.

1-2. An acid anhydride (A) component is synthesize | combined by reaction of a mixture (a) and an acid anhydride.
Examples of the acid anhydride include succinic anhydride, 1-dodecenyl succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, One in the same molecule such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride A compound having an acid anhydride group, or pyromellitic anhydride, phthalic anhydride dimer, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 1, 2 , 3,4-Butane Tracarboxylic dianhydride, diphenyl ether tetracarboxylic anhydride, trimellitic anhydride / ethylene glycol ester (commercially available products include, for example, Shin Nippon Rika Co., Ltd., trade name Ricacid TMEG-100), etc. Can be mentioned.
Among these compounds, succinic anhydride and 1,2,3,4-butanetetracarboxylic dianhydride are preferable as the acid anhydride in terms of excellent reactivity.

1-3. (A) Manufacturing method of component (A) What is necessary is just to follow a conventional method as a manufacturing method of a component.
For example, a method of reacting the mixture (a) with an acid anhydride at 60 to 110 ° C. for 1 to 20 hours in the presence of a catalyst can be mentioned.
The catalyst in this case is triethylamine, tripropylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, triisooctylamine, tridodecylamine, methyldibutylamine, N, N-dimethylbenzylamine, N , N-dimethylcyclohexylamine, tricyclohexylamine, triphenylamine, tritolylamine, trixylamine, tertiary amines such as tribiphenylamine, trinaphthylamine and tribenzylamine; and benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetra Quaternary ammonium salts such as methylammonium bromide, tetrabutylammonium bromide and cetyltrimethylammonium bromide And it can be given zinc oxide.
These can use 1 type (s) or 2 or more types.

  The proportion of the component (A) in the composition may be appropriately selected according to the purpose and application, but is preferably 10 to 90% by weight in the composition.

2. Curable composition TECHNICAL FIELD This invention relates to the curable composition containing the said (A) component.
As a method for producing the composition, a step of producing a mixture (a) by subjecting a polyhydric alcohol and a monofunctional (meth) acrylate to an ester exchange reaction in the presence of the catalysts X and Y;
A production method including a step of producing the component (A) by adding an acid anhydride to the component (a) is preferable.
According to the production method, the component (A) having a specific acid value and viscosity can be produced in a high yield, and the resulting composition has a low viscosity because there are few high molecular weight compounds in the component (A) to be obtained. The product can be made excellent in coating property and leveling property, and the alkali metal ion contained in the component (A) becomes a very small amount, which is preferable in that there is no concern about a decrease in electrical characteristics due to ion elution from the cured film.
What is necessary is just to follow the manufacturing method of above-described (A) component as the said process.

What is necessary is just to set suitably as a viscosity of a composition according to the objective.
When the composition is used for a preferred application such as a coating agent, an ink and a pattern forming agent, the viscosity of the composition may be appropriately set according to the purpose, preferably 1 to 10,000 mPa · s, more preferably. 1 to 8,000 mPa · s. By setting it as the said viscosity range, it is excellent in the leveling property at the time of the coating of a composition, and shall be excellent in the external appearance of hardened | cured material.

Although the composition of this invention can be used for both an active energy ray hardening-type composition and a thermosetting type composition, an active energy ray hardening-type composition is preferable.
The composition of the present invention contains (A) as an essential component, but various components can be blended depending on the purpose.
As other components, preferable examples include photopolymerization initiators (hereinafter referred to as “component (B)”), thermal polymerization initiators (hereinafter referred to as “component (C)”), and ethylenic components other than the component (A). Examples thereof include compounds having an unsaturated group (hereinafter referred to as “component (D)”), alkali-soluble resins (hereinafter referred to as “component (E)”), organic solvents (hereinafter referred to as “component (F)”), and the like. .
As examples other than the above, pigments, dyes, antifoaming agents, leveling agents, inorganic fillers, organic fillers and light stabilizers, antioxidants, ultraviolet absorbers, and the like can also be blended. If necessary, a small amount of an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, and the like may be added.
Hereinafter, components (B) to (F), which are preferable other components, will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

2-1. (B) Component When the composition of the present invention is used as an active energy ray curable composition and further used as an electron beam curable composition, it does not contain the component (B) (photopolymerization initiator) and is an electron. It can also be cured by a wire.
In the case where the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible rays are used as active energy rays, the component (B) is further added from the viewpoint of ease of curing and cost. It is preferable to contain.
When an electron beam is used as the active energy ray, it is not always necessary to add it, but a small amount can be added as necessary in order to improve curability.

  Examples of the component (B) include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, thioxanthone compounds, triazine compounds, and ketals. And the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1 2,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2-bromophenyl) -4,4 ′, , 5′-Tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole And 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like.

When a biimidazole compound is used as the component (B), it is preferable to use a hydrogen donor in view of further improving the sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor, mercaptan hydrogen donors and amine hydrogen donors are preferable.

  The mercaptan-based hydrogen donor is composed of a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus. Specific examples of mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-2,5. -Dimethylaminopyridine etc. can be mentioned. Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

  The amine-based hydrogen donor is composed of a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus. Specific examples of amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and ethyl-4. -Dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, etc. can be mentioned.

  The hydrogen donors can be used alone or in admixture of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors can be used in combination. The formed spacer or pixel is preferable because it is difficult to drop off from the substrate during development, and the strength and sensitivity of the spacer or pixel are high. Also, a hydrogen donor having a mercapto group and an amino group at the same time can be preferably used.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether, and methyl 2-benzoylbenzoate.

  Specific examples of acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropan-1-one, -[4- (2-hydroxyethoxy) phenyl] -2-methyl-2-hydroxypropan-1-one, 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, Examples include 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1,2-diphenylethane-1-one. You can.

  Specific examples of the benzophenone compounds include benzyl dimethyl ketone, benzophenone, 4,4'-bis (dimethylbenzophenone), 4,4'-bis (diethylbenzophenone), and the like.

  Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.

  Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1,4-naphthoquinone.

  Specific examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone and the like.

  Specific examples of the triazine compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-methoxyphenyl) -s-triazine, 1,3-bis (Trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4′-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyv) Yl) -4,6-bis (trichloromethyl) -s-triazine and the like.

  Among these, 1-hydroxycyclohexyl phenyl ketone and 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropan-1-one initiate and accelerate the polymerization reaction by irradiation with active energy rays even in a small amount. Therefore, it is preferably used in the invention.

  (B) As a content rate of a component, 0.5-20 weight part is preferable with respect to 100 weight part of solid content other than (B) in a composition. If it is less than 0.5 part by weight, the photocurability may be insufficient. On the other hand, if it exceeds 20 parts by weight, the exposed part may be easily broken during alkali development. Furthermore, the ratio of the component (B) is more preferably 2 to 10% by weight because a highly accurate pattern can be obtained.

2-2. (C) component When using the composition of this invention as a thermosetting type composition, a thermal-polymerization initiator can be mix | blended.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid , T-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl 2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2, 5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t- Butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide Id, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.
Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, and azodi-t-butane.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

The amount of these thermal polymerization initiators used is 100 parts by weight of the total amount of the component (A). When the component (D) described later is blended, the total amount of the total amount of the components (A) and (D) is 100 parts by weight The amount is preferably 10 parts by weight or less.
When the thermal polymerization initiator is used alone, it may be carried out in accordance with conventional means of normal radical thermal polymerization. In some cases, it is used in combination with the component (B) (photopolymerization initiator). For the purpose of improving the temperature, thermosetting can also be performed.
Hereinafter, the component (A) or the components (A) and (D) are referred to as “curable components”.

2-3. (D) Component In the composition of this invention, the compound which has ethylenically unsaturated groups other than (A) component which is (D) component can be mix | blended with the composition of this invention as needed.
Examples of the ethylenically unsaturated group in component (D) include a (meth) acryloyl group, a vinyl group, and a (meth) allyl group.
Preferable specific examples of the component (D) include a compound having one vinyl, a monofunctional (meth) acrylate, and a compound having two or more (meth) acryloyl groups.
Examples of the compound having one vinyl include N-vinylcaprolactone.
Examples of the monofunctional (meth) acrylate include the compounds described above, and preferable examples include phenoxyethyl (meth) acrylate, carbitol (meth) acrylate, (meth) acryloylmorpholine, glycidyl (meth) acrylate, and 2-hydroxy. Examples include ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 1,4-butanediol mono (meth) acrylate.
Examples of the compound having two or more (meth) acryloyl groups include 1,6-hexanediol di (meth) acrylate, nonanediol diacrylate, polyethylene glycol di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meta ) Acrylate, tribromophenyl (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) -propane, ethylene glycol di (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythri Rutetora (meth) acrylate, bisphenol A type epoxy resin di (meth) acrylate, various types of polyurethane (meth) acrylates and polyester poly (meth) acrylate.
(D) The preferable mixture ratio of a component is the range of 0 to 50 weight% in a composition.

2-4. Component (E) The alkali-soluble resin as component (E) in the present invention acts as a binder for component (A) and is preferably soluble in a developer used in the development processing step, particularly preferably an alkali developer. If it has, it will not specifically limit.
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 the component (E), an alkali-soluble resin having a carboxyl group is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group-containing unsaturated monomer”) and this A copolymer (hereinafter referred to as “carboxyl group-containing copolymer”) with an ethylenically unsaturated monomer copolymerizable with (hereinafter referred to as “copolymerizable unsaturated monomer”) is preferred.

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; maleic acid, maleic anhydride, fumaric acid, itacon Unsaturated dicarboxylic acids such as acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2- ( Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as (meth) acryloyloxyethyl) and phthalic acid mono (2- (meth) acryloyloxyethyl); and ω-carboxy Examples include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as polycaprolactone mono (meth) acrylate. Can. Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are Aronix M-5300 and M-5400 [Toagosei Co., Ltd., respectively. It is commercially available under the trade name of “Co., Ltd.”.
The carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.

  The copolymerizable unsaturated monomer may be any copolymerizable with a carboxyl group-containing unsaturated monomer, such as an aromatic vinyl compound, an unsaturated carboxylic acid ester, an unsaturated imide, and a terminal. Macromonomers having a mono (meth) acryloyl group are preferred.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 2 -Vinyl benzyl methyl ether, 3-vinyl benzyl methyl ether, 4-vinyl benzyl methyl ether, 2-vinyl benzyl glycidyl ether, 3-vinyl benzyl glycidyl ether, 4-vinyl benzyl glycidyl ether, etc. are mentioned.

As unsaturated carboxylic acid esters, 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-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, methoxydi Propylene 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 Examples include glycerol mono (meth) acrylate.

  Examples of unsaturated imides include maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  Examples of the macromonomer having a mono (meth) acryloyl group at the terminal include those having a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane. it can.

As the copolymerizable unsaturated monomer, in addition to the above, 2- (3,4,5,6-tetrahydrophthalimido) ethyl (meth) acrylate, 2- (2,3-dimethylmaleimido) ethyl (meth) Imide (meth) acrylates such as acrylate; 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl ( Unsaturated carboxylic acid aminoalkyl esters such as meth) acrylate and 3-dimethylaminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Indens such as indene and 1-methylindene; Vinyl acetate, vinyl propionate, butyric acid Carboxylic acid vinyl esters such as nyl 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 admixture of two or more.

  As the carboxyl group-containing copolymer, (meth) acrylic acid is an essential component, and in some cases, from the group of succinic acid mono (2- (meth) acryloyloxyethyl), ω-carboxypolycaprolactone mono (meth) acrylate. Carboxyl group-containing unsaturated monomer component further containing at least one selected compound, styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , A copolymer with at least one selected from the group consisting of glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer (hereinafter referred to as “carboxyl group-containing copolymer (α)”). ) Is preferred.

  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 (meta ) Acrylate / polystyrene macromonomer copolymer, (meta Acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic Acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxy Ethyl] / still / Allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Ω-carboxypolycacrolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio is 5% by weight or more, the resulting composition can be excellent in solubility in an alkali developer, while when it is 50% by weight or less, the alkali developer In this case, it is possible to prevent the spacer layer and pixels from falling off the substrate and the spacer surface from becoming rough when developing with an alkali developer.

  As a method for producing the carboxyl group-containing copolymer, known methods such as ordinary suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization can be used. However, since it is preferable that the obtained vinyl polymer is substantially solvent-free, in the case of solution polymerization, the step of volatilizing the solvent after the polymerization is performed when an aqueous dispersion of the polymer is obtained. Preferably there is a step of separating or drying the water.

As these polymerization methods, a solution polymerization method is preferable, and since the molecular weight distribution of the obtained component (E) becomes small, a part of a mixed solution composed of a monomer mixture, a polymerization solvent and a thermal polymerization initiator is heated and stirred. Then, after starting the reaction, a production method in which the remainder of the mixture is sequentially dropped into the reaction solution is preferable.
Furthermore, a method of polymerizing a vinyl monomer in the presence of a chain transfer agent having a carboxyl group by solution polymerization is preferable in that the resulting polymer has a low viscosity.

(E) As a manufacturing method of component, the manufacturing method which superposes | polymerizes a monomer at high temperature is especially preferable.
According to this high temperature continuous polymerization method, the component (E) having a low molecular weight and a low viscosity can be produced. Further, the polymerization method does not require the use of a thermal polymerization initiator, or even when a thermal polymerization initiator is used, a copolymer having a desired molecular weight can be obtained with a small amount of use. It has high purity and contains almost no impurities that generate radical species, and stable physical properties can be obtained. Also, a copolymer having a lower molecular weight distribution than that obtained by conventional solution polymerization can be obtained.
Furthermore, the component (E) obtained by high-temperature continuous polymerization is excellent in the following points as compared with the copolymer obtained by solution polymerization. That is, since the component (E) obtained by continuous polymerization at high temperature has a terminal double bond, it reacts with the component (A) when the composition is cured by irradiation with active energy rays, and the unreacted (E) It can suppress that a component bleeds out. Further, in high-temperature continuous polymerization, a low molecular weight copolymer can be obtained without using a chain transfer agent, so that the cured film has excellent weather resistance.
As a more specific method of high temperature continuous polymerization, the method described in JP-A-2014-081487 may be followed.

As the component (E) in the present invention, the alkali-soluble resin having an ethylenically unsaturated group in the side chain improves the crosslinking density of the resulting cured film, and improves the coating strength, heat resistance, and chemical resistance. Since it becomes the thing excellent in the point, it is preferable.
The alkali-soluble resin having an ethylenically unsaturated group in the side chain is preferably an alkali-soluble resin having a carboxyl group. Examples of the resin include those obtained by adding an unsaturated compound having an epoxy group (hereinafter referred to as “epoxy unsaturated compound”) to the carboxyl group-containing copolymer.
Examples of the epoxy unsaturated compound include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and cyclohexene oxide-containing (meth) acrylate.
As a method for the addition reaction, a conventional method may be followed, and it can be produced by adding an epoxy unsaturated compound to a carboxyl group-containing copolymer in an organic solvent or without a solvent. As conditions for the addition reaction, the reaction temperature, reaction time, and catalyst may be appropriately selected according to each reaction.

The weight average molecular weight (hereinafter referred to as “Mw”) of the component (E) is usually 3,000 to 300,000, preferably 5,000 to 100,000. The number average molecular weight (hereinafter referred to as “Mn”) is usually 3,000 to 60,000, preferably 5,000 to 25,000.
In addition, in this invention, Mw and Mn mean the value which converted the molecular weight measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in polystyrene conversion.
In the present invention, by using such a component (E) having specific Mw and Mn, a photosensitive resin composition excellent in developability can be obtained, whereby a pattern having sharp pattern edges can be obtained. In addition to being able to be formed, residues, background stains, film residues, and the like are less likely to occur on the unexposed portion of the substrate and the light shielding layer during development. Moreover, the ratio (Mw / Mn) of Mw and Mn of (E) component is 1-5 normally, Preferably it is 1-4.
(E) A component can be used individually or in combination of 2 or more types.

As a content rate of (E) component, 10-90 weight% of (E) component is preferable on the basis of the total amount of a sclerosing | hardenable component and (E) component, More preferably, it is 30-80 weight%. (E) By making the ratio of a component into this range, the fall of a crosslinking density can be prevented and it can be excellent in coating film strength, heat resistance, and chemical resistance.
The proportion of the total amount of the curable component and the component (E) in the composition is preferably 10 to 50% by weight in the composition. When this ratio is 10% by weight or more, the film thickness after pre-baking is prevented from becoming too thin. On the other hand, when it is 50% by weight or less, the viscosity of the composition is prevented from being increased and the coating property is excellent. In addition, the film thickness after pre-baking is prevented from becoming too thick.

2-5. (F) Component Although the composition of the present invention has a low viscosity even without a solvent, an organic solvent as the (F) component can be blended for the purpose of further improving coating properties. .
(F) A component should just be a thing which does not react with each component of a composition. An organic solvent having a boiling point of 80 to 200 ° C. is preferable, and an organic solvent having a boiling point of 100 to 170 ° C. is more preferable because the coating property is excellent and the drying speed of the obtained coating film is moderate.
Specifically, for example, aromatic compounds such as toluene and xylene; fatty acid esters such as butyl acetate, benzyl acetate, propylene glycol monomethyl ether acetate and ethoxyethyl propionate; cellosolves such as ethyl cellosolve and butyl cellosolve; propylene glycol monomethyl ether Alcohol glycol ethers such as ethanol, alcohols such as ethylene glycol and diethylene glycol; ethers such as diethylene glycol dimethyl ether; ketones such as methyl isobutyl ketone and cyclohexanone; formamides such as N, N-dimethylformamide; γ-butyrolactam and N-methyl-2 -Lactams such as pyrrolidone; and lactones such as γ-butyrolactone.
(F) As a mixture ratio of a component, the ratio from which the solid content density | concentration of a composition will be 10 to 50 weight% is preferable.

3. Applications The curable composition of the present invention can be used in various applications, such as compositions for pattern formation such as photolithographic printing plates and color resists, coating agents such as hard coats, printing inks and adhesives. It can be used for various uses such as, and can be preferably used for a pattern forming composition.

  The composition of the present invention can be preferably used as an active energy ray-curable composition, and further has excellent alkali developability. Therefore, among the above applications, pattern formation that is required to have excellent alkali developability is required. It can be preferably used as a composition for use.

The active energy ray-curable composition of the present invention can be preferably used as a pattern-forming composition because it has high exposure sensitivity and is excellent in developability and can form a precise and accurate pattern.
When the active energy ray-curable composition of the present invention is used as a pattern forming composition, the pattern forming composition preferably contains a photopolymerization initiator and an organic solvent. What was mentioned above should just be used as a photoinitiator and an organic solvent.

The composition for pattern formation comprising the active energy ray-curable composition of the present invention is a resist for etching resist, solder resist, etc., columnar spacer in liquid crystal panel production, coloring for forming pixels, black matrix, etc. in color filters. It can be effectively used as a composition, a color filter protective film and the like.
Among the uses described above, the pattern forming composition comprising the active energy ray-curable composition of the present invention is more preferable for the use of columnar spacers, color filter coloring compositions, and color filter protective films in liquid crystal panel production. Can be used.

When the active energy ray-curable composition of the present invention is used for forming a columnar spacer, a color filter coloring composition, and a color filter protective film, the composition is coated with a polymer in order to improve coatability and developability. Surfactants such as nonionic surfactants such as oxyethylene lauryl ether and fluorosurfactants can also be added. Moreover, you may contain the adhesion | attachment adjuvant, the storage stabilizer, the antifoamer, etc. suitably as needed.
The case where the active energy ray-curable composition of the present invention is used for a columnar spacer (hereinafter sometimes simply referred to as “spacer”) and as a coloring composition will be described below.

3-1. The columnar spacer is formed of a cured coating film obtained by curing an active energy ray-curable composition with active energy rays by a photolithography method. The spacer can be formed at an arbitrary size and at an arbitrary position on the liquid crystal panel substrate. In general, the spacer is often formed on a black matrix region which is a light shielding portion of the color filter or on the TFT electrode.
As a method for forming the spacer, a conventional method may be followed. For example, after applying the active energy ray-curable composition of the present invention to a film thickness necessary to form a cell gap on a substrate such as glass. And a method of heating (hereinafter referred to as “pre-baking”) to dry the coating film, followed by exposure, development, and post-heating (hereinafter referred to as “post-baking”).

When the active energy ray-curable composition is applied on the substrate, it is applied slightly thicker than the design value of the cell gap in consideration of film reduction or deformation due to development, post-baking or the like. Specifically, it is applied so that the film thickness after pre-baking is preferably 4 to 7 μm, particularly 3 to 5 μm. Examples of the coating method include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, a die coating method (slit coating method), etc., and generally a spin coating method or a die coating method. The method is used.
After applying the active energy ray-curable composition on the substrate, pre-baking is performed. In this case, the temperature and time are preferably 50 to 150 ° C., particularly 80 to 120 ° C. and about 3 to 15 minutes.

The pre-baked coating film surface is irradiated with active energy rays through a mask having a predetermined pattern shape for forming a spacer. The active energy ray to be used is preferably ultraviolet rays and / or visible rays, and particularly preferably light having a wavelength of 240 nm to 410 nm obtained from a high pressure mercury lamp, a metal halide lamp or the like.
The irradiation conditions of active energy rays (especially light) depend on the type of active energy ray source (light source), the absorption wavelength of the photopolymerization initiator used, the film thickness of the coating film, etc. It is preferable to be 50 to 600 mJ / cm ² . If the amount of light irradiation is too small, the exposed portion tends to drop off during development due to poor curing, while if the amount of light irradiation is too large, it becomes difficult to obtain a fine spacer pattern.

After the above-described light irradiation, a developer is applied to the coating surface to remove an unexposed portion (uncured portion). In general, an aqueous solution of an alkaline compound is used as the developer. Examples of the alkaline compound include potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, tetramethylammonium hydroxide, etc. Among them, potassium hydroxide and sodium carbonate are preferably used.
An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropanol, or benzyl alcohol, or various surfactants may be added to the developer to accelerate the development rate.
The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. After development, the pattern portion is washed with water for 0.5 to 1.5 minutes and air-dried with compressed air or the like to obtain a spacer pattern.
The obtained spacer pattern is post-baked in a temperature range of 150 to 350 ° C. with a heating device such as a hot plate or oven to form a liquid crystal panel spacer.
By post-baking, the residual solvent and moisture absorbed during development can be volatilized, and the heat resistance of the spacer can be improved. The thickness of the spacer varies depending on the cell gap setting value of the liquid crystal panel, but is preferably designed to be 3 to 5 μm after post-baking.

  The liquid crystal panel substrate having the spacer formed as described above using the active energy ray-curable composition of the present invention can form an accurate and uniform cell gap when bonding is performed by the room temperature cell pressure bonding method. In particular, the present invention can also be suitably used when performing room-temperature cell pressure bonding in the ODF method (liquid crystal dropping method).

3-2. Coloring composition When the active energy ray-curable composition of the present invention is used as a coloring composition, a pigment and a pigment dispersant are further blended.
The kind of pigment is not particularly limited, and one or more of various organic pigments and inorganic pigments can be used.

Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (C.I. ) Can be listed. C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as C.I. Pigment Yellow 185; I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 177, C.I. I. Red pigments such as C.I. Pigment Red 254; I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. Blue pigments such as CI Pigment Blue 15: 6; I. Pigment green 7, C.I. I. Green pigments such as C.I. Pigment Green 36; I. Pigment violet 23, C.I. I. Pigment violet 23:19 and the like.
In addition, phthalocyanines with high bromination rates, such as Monastral Green 6YC and 9YC (manufactured by Avicia Co., Ltd.), which have been difficult to disperse in the past, high brightness G pigments, metals whose central metal is other than copper, such as Mg, Al, Si , Ti, V, Mn, Fe, Co, Ni, Zn, Ge, Sn, etc., high color purity G pigments made of different metal phthalocyanine pigments can be used.

Specific examples of inorganic pigments include carbon black, titanium black, synthetic iron black, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose [red iron oxide (III)] , Cadmium red, ultramarine blue, chromium oxide green, cobalt green, and amber.
The active energy ray-curable composition of the present invention can contain one or more of the above-described pigments.

  Further, by using a pigment dispersant together with the pigment, the pigment can be favorably dispersed in the active energy ray-curable composition. In particular, by using a pigment dispersant, various pigments that are widely used in color filters for liquid crystal display devices, specifically C.I. I. Pigment yellow 150, C.I. I. Pigment Green 36, C.I. I. Pigment green 7, C.I. I. Pigment yellow 138 C.I. I. Pigment yellow 83, C.I. I. Pigment blue 15: 6, C.I. I. Pigment violet 23, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. One or two or more pigments selected from the group consisting of CI Pigment Yellow 139, the phthalocyanine pigment having a high bromination rate, and the dissimilar metal phthalocyanine pigment can be well dispersed in the active energy ray-curable composition.

The kind of the pigment dispersant is not particularly limited, and any pigment dispersant can be used as long as it can disperse the pigment as described above in the active energy ray-curable composition.
Specific examples of usable pigment dispersants include amide compounds such as nonanoamide, decanamide, dodecanamide, N-dodecylhexamide, N-octadecylpropioamide, N, N-dimethyldodecanamide, N, N-dihexylacetamide and the like. , Amine compounds such as diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine, trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethylpolyoxyethylene) -1,2-di Examples include amines having a hydroxy group such as aminoethane, 1,4-bis (2-hydroxyethyl) piperazine, and 1- (2-hydroxyethyl) piperazine. In addition, compounds such as nipecotamide, isonipecotamide, and nicotinamide can be used.

  In addition to the above-mentioned compounds, as pigment dispersants, (co) polymers of unsaturated carboxylic esters such as polyacrylic acid esters, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid ( (Partial) amine salts, (partial) ammonium salts, (partial) alkylamine salts, (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters, modified products thereof, polyurethanes, saturated polyamides , Polysiloxanes, long-chain polyaminoamide phosphates, amides obtained by the reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters, salts thereof, and the like can be used.

  Further, as a pigment dispersant, “Shigenox-1055” manufactured by Hakkol Chemical Co., “Disperbyk-101”, “Same-130”, “Same-140”, “Same-170” manufactured by Big Chemie Japan Co., Ltd., "-171", "-182", "-2001", "EFKA-49", "-4010", "-9009" manufactured by EFKA CHEMICALS, "Solspurse 12000" manufactured by Zeneca Corporation ”,“ 13240 ”,“ 13940 ”,“ 17000 ”,“ 20000 ”,“ 24000GR ”,“ 24000SC ”,“ 27000 ”,“ 28000 ”,“ 28000 ”,“ 33500 ”, Ajinomoto Co., Inc. ) “PB821”, “PB822”, etc. can also be used.

  The pigment dispersant is preferably used in a proportion of generally 10 to 90 parts by weight, particularly 20 to 80 parts by weight, based on 100 parts by weight of the pigment.

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

The coloring composition is produced by directly mixing the component (A), the component (E), the pigment, the pigment dispersant, and other components as necessary, into an organic solvent and dispersing the mixture using a known disperser. However, since the dispersion of the pigment may be insufficient, a method of preparing a pigment dispersion in advance and mixing it with the component (A) and the component (E) is preferable. An active energy ray-curable composition for a colored composition in which the pigment is well dispersed in the composition can be easily obtained.
As a preferable production method, a pigment dispersion is prepared in advance by mixing a pigment and a pigment dispersant with an organic solvent. Separately, a component (A) and, if necessary, another component and an organic solvent are mixed (A ) Component-containing liquid is prepared, and at that time, (E) component is contained in one or both of the pigment dispersion liquid and (A) component-containing liquid, and the pigment dispersion liquid thus prepared and (A) The coloring composition excellent in pigment dispersibility can be obtained by mixing a component containing liquid and performing a dispersion process further as needed. According to this method, since the organic solvent for preparing the pigment dispersion and the organic solvent for preparing the component (A) -containing liquid can be selected separately, the range of solvent selection is widened.

  When producing a colored composition without preparing a pigment dispersion in advance, first add the pigment, the pigment dispersant and, if necessary, the component (E) to the organic solvent, and mix and agitate the pigment. After dispersing, by mixing the remaining components such as component (A), not only does the dispersibility of the pigment not be disturbed by the other compounding components in the pigment dispersion step, but also excellent stability It becomes.

  The colored composition obtained as described above is applied to a support to form a coating film, dried, and then applied by irradiating the coating film with active energy rays such as light rays in a predetermined pattern. A portion of the membrane is selectively cured. Subsequently, after developing with an alkali developer, post-baking is performed, and further heat curing is performed to obtain a colored coating film having a predetermined pattern.

The active energy ray used for curing the coloring composition is preferably ultraviolet rays and / or visible rays, and more preferably light having a wavelength of 240 nm to 410 nm emitted from a high-pressure mercury lamp or a metal halide lamp. The irradiation energy required for curing is generally about 10 to 500 mJ / cm ² . In the exposure step, a predetermined position of the coating film can be selectively exposed and cured by irradiating the surface of the coating film with laser light or irradiating light through a mask.

The obtained colored pattern is post-baked in a temperature range of 150 to 350 ° C. with a heating device such as a hot plate or oven to form a colored layer.
By post-baking, the residual solvent and moisture absorbed during development can be volatilized, and the heat resistance of the pixel can be improved. The thickness of the colored layer varies depending on the set value of the liquid crystal panel, but it is preferable to design it to be approximately 1 to 2 μm after post-baking.

The cured portion of the coating is uniformly dispersed in a matrix formed by a network of crosslinks in which the component (A), which is a polyfunctional (meth) acrylate, is formed by a photocuring reaction and a thermosetting reaction. Has a structured.
The coloring composition comprising the active energy ray-curable composition of the present invention is excellent in curability, has a high crosslinking density, and solidifies uniformly well to the inside, so that it is difficult to reverse taper during development, and has a forward taper shape and sharp edges. And a pattern with good surface smoothness is formed.
In addition, the colored composition comprising the active energy ray-curable composition of the present invention has high electrical reliability because impurities are confined in a matrix having a high crosslink density that has solidified well to the inside during curing and is not easily eluted into the liquid crystal layer. A highly colored cured film can be obtained. In particular, when a colored layer of a liquid crystal panel is produced using this colored composition, the voltage of the display portion can be stably maintained and electric reliability is high.
Furthermore, the coloring composition comprising the active energy ray-curable composition of the present invention can disperse a high-concentration pigment finely and uniformly, and has a high coloring property, so that even if it is thin, a coloring pattern having a high coloring concentration can be obtained. It can be formed and has a wide color reproduction range.
The colored composition comprising the active energy ray-curable composition of the present invention can be used to form various colored coatings, and in particular, forms a colored layer constituting the details of the color filter, that is, a pixel or a black matrix. Suitable for

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “parts” means parts by weight.

1. Production example
1) Production Example 1 [ Production of mixture (a) by transesterification]
In a 1 liter flask equipped with a stirrer, thermometer, gas introduction tube, rectification column and cooling tube, 86.33 parts (0.34 mol) of dipentaerythritol and 690.05 parts of 2-methoxyethyl acrylate (5.30 mol), 4.08 parts (0.04 mol) of DABCO as catalyst X, 6.52 parts (0.04 mol) of zinc acetate as catalyst Y, and 1.63 parts (0 of hydroquinone monomethyl ether) 0.013 mol) and 0.05 part (0.0003 mol) of phenothiazine were charged, and oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
2-methoxyethanol and 2-methoxyethyl acrylate by-produced as the transesterification progresses while adjusting the pressure in the reaction system in the range of 250-760 mmHg while heating and stirring the reaction liquid at a temperature of 120-145 ° C. Was extracted from the reaction system via a rectification column and a cooling tube. Further, 2-methoxyethyl acrylate in the same weight part as the extracted liquid was added to the reaction system as needed. After 24 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
After cooling the reaction solution to room temperature and separating the precipitate by filtration, 12.0 parts of aluminum silicate [KYOWARD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] is added to the filtrate to dry dry air. Then, distillation under reduced pressure was carried out for 8 hours at a temperature of 70 to 95 ° C. and a pressure of 0.001 to 100 mmHg to separate a distillate containing unreacted 2-methoxyethyl acrylate. 2.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the obtained filtrate was used as a purified product.
As a result of analyzing the composition of the purified product using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were contained as main components (hereinafter referred to as “( a1) "). The yield of the purified product was 80%.
The acid value, hydroxyl value, high molecular weight GPC area%, viscosity and sodium ion concentration of the purified product obtained were measured according to the following methods.
As a result, the acid value was 0.02 mgKOH / g, the hydroxyl value was 46 mgKOH / g, the high molecular weight GPC area% was 13.5 area%, the viscosity was 2,740 mPa · s, and the sodium ion concentration was 24 ppb.

(1) Method for measuring hydroxyl value An acetylating reagent is added to a sample and heat-treated in a warm bath at 92 ° C. for 1 hour. After standing to cool, a small amount of water is added and heat-treated in a warm bath at 92 ° C. for 10 minutes. After allowing to cool, the hydroxyl value was determined by titrating the acid with a potassium hydroxide ethanol solution using a phenolphthalein solution as an indicator.

(2) Method for measuring acid value Using a phenolphthalein solution as an indicator, the sample was neutralized with a potassium hydroxide ethanol solution to determine the acid value.

(3) High molecular weight GPC area%
About the obtained refinement | purification processed material, the area% of the high molecular weight body was computed by GPC measurement of the following conditions.

◆ GPC measurement conditions and equipment: GPC system name manufactured by Waters Co., Ltd. 1515 2414 717P RI
-Detector: RI detector-Column: Guard column Shodex KFG (8 μm 4.6 × 10 mm) manufactured by Showa Denko KK, two types of this column Watergel HR 4E THF (7.8 × 300 mm) + styragel HR 1THF (7.8 × 300 mm)
Column temperature: 40 ° C
-Eluent composition: THF (containing 0.03% sulfur as internal standard), flow rate 0.75 mL / min-Calculation method of high molecular weight area (%) From GPC measurement results, based on the following formula (1) Calculated.
High molecular weight area% = [(R−IL) / R] × 100 (1)
The symbols and terms in formula (1) are as described above.

(4) Viscosity The viscosity of the purified product obtained was measured with an E-type viscometer (25 ° C.).

(5) Concentration of sodium ion About the purified product obtained, an inductively coupled plasma (ICP) emission analyzer [SPECTRO CIROS-120 manufactured by Ametech Co., Ltd.] and an ICP mass spectrometer [Agilent Technology Co., Ltd. Agilent 7500cs] are used. Measured using.

2) Production Example 2 [Production of Component (A)]
A 500 ml glass flask equipped with a stirrer, a thermometer, and a water-cooled condenser was charged with 200 g of the acrylate mixture (a1) (hydroxyl value 46 mgKOH / g) obtained in Production Example 1, 8.2 g of succinic anhydride, and methoquinone 0. .10 g was added and the temperature was raised to 85 ° C. The catalyst was reacted for 3 hours after adding 1.0 g of triethylamine as a catalyst. The reaction was performed under a mixed atmosphere of air / nitrogen.
As a result, a compound (hereinafter referred to as “(A-1)”) having an acid value of 21.0 mg KOH / g, a viscosity of 5,260 mPa · s, and a sodium ion concentration of 26 ppb was obtained.

3) Production Example 3 [Production of Component (A)]
Except that the amount of raw material succinic anhydride was changed to 16.4 g, synthesis was carried out according to Production Example 1, and a compound having an acid value of 40.5 mg KOH / g, a viscosity of 7,950 mPa · s, and a sodium ion concentration of 27 ppb (hereinafter referred to as “a”) "(A-2)") was obtained.

4) Production Example 4 [ Production of acid anhydride adduct other than component (A)]
In place of the raw material (a1), the following DPHA was changed to 9.7 g of succinic anhydride, and all synthesis was performed according to Production Example 2, acid value 26.1 mgKOH / g, viscosity 11,470 mPa · s. And a compound having a sodium ion concentration of 4,100 ppb (hereinafter referred to as “(A-1) ′”).
DPHA: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture (ratio: about 30/70) (acid value 0.02 mg KOH / g, hydroxyl value 27.0 mg KOH / g, sodium ion concentration 4,300 ppb)

2. Examples 1 and 2, Comparative Examples 1 to 3
The components (A), (B), (D) and (E) were mixed according to a conventional method so as to have the ratio shown in Table 2 below, thereby preparing an ultraviolet curable composition.
Using the obtained composition, the viscosity and sodium ion concentration were measured according to the same method as described above. Further, alkali developability was evaluated according to the following method. The results are shown in Table 2.

<Developability>
A composition shown in Table 1 was coated on a 10 cm-drawn chromium mask glass substrate with a spin coater to form a coating film having a dry film thickness of 10 μm.
The obtained coating film was immersed in a 1.0 wt% aqueous sodium carbonate solution (23 ° C.), and the time until complete dissolution was measured and evaluated according to the following criteria.
○: Dissolves in less than 90 seconds.
Δ: Dissolves in 90 seconds or more and less than 180 seconds.
*: It dissolves in 180 seconds or more.

The numbers in the column of the composition in Table 1 mean the number of parts, and are shown as a solid content ratio.
In addition, the symbol in Table 1 means the following.
Component (A): (A-1): Succinic anhydride adduct of the mixture (a1) obtained in Production Example 2 (A-2): Succinic acid of the mixture (a1) obtained in Production Example 3 Anhydride adduct
(B) Ingredient SB-PI: 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropan-1-one, manufactured by Sojyo Industrial Co., Ltd., trade name SB-PI777
Component (D) : (a1): acrylate mixture obtained in Production Example 1 DPHA: dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture (ratio: about 30/70)
(A-1) ′: Succinic anhydride adduct of acrylate obtained in Production Example 4
Component (E) ARUFON: Solvent-free carboxyl group-containing acrylic polymer (Mw 2,000, acid value 70 mg KOH / g, viscosity 5,030 mPa · s (25 ° C.)), ARUFON UC-3510 manufactured by Toagosei Co., Ltd.

The compositions of Examples 1 and 2 had a low viscosity even without solvent, were excellent in alkali developability, and had a low concentration of sodium ions.
On the other hand, the compositions of Comparative Examples 1 and 2 having an acid value less than the lower limit of the present invention are poor in alkali developability although the viscosity is low, and the composition of Comparative Example 2 is sodium ion. Has become a high concentration.
Although the composition of Comparative Example 3 having a viscosity exceeding the upper limit of the present invention was excellent in alkali developability, the viscosity was high, and sodium ions were at a high concentration.

  The curable composition of the present invention is preferably used as an active energy ray curable composition, pattern forming agents such as photosensitive lithographic printing plates and color resists, coating agents such as hard coats, printing inks and adhesives, etc. It can be used for various applications, and can be particularly preferably used for a pattern forming agent.

Claims (17)

A mixture (A) containing a compound obtained by adding an acid anhydride to a mixture (a) containing a compound having a hydroxyl group and two or more (meth) acryloyl groups, and the acid value of the component (A) is 20 to A curable composition having 70 mg KOH / g and a viscosity at 25 ° C. of 50 to 9,500 mPa · s. The curable composition according to claim 1, wherein the mixture (a) is a mixture containing a compound having a hydroxyl group and three or more (meth) acryloyl groups. The curable composition according to claim 1 or 2, wherein the mixture (a) has a hydroxyl value of 10 to 100 mgKOH / g. The above-mentioned mixture (a) is a value obtained by gel permeation chromatography measurement, and is less than 25% as area% of the high molecular weight substance defined by the following formula (1). 4. The curable composition according to any one of 3 above.
High molecular weight area% = [(R−IL) / R] × 100 (1)
The symbols and terms in formula (1) mean the following.
-R: total area of detection peaks in component (A)-I: area of detection peaks including ideal structure (meth) acrylate-L: detection having a weight average molecular weight smaller than detection peaks including ideal structure (meth) acrylate Total peak area / ideal structure (meth) acrylate: 2 containing the same number of (meth) acryloyl groups per molecule as the number of hydroxyl groups per molecule of raw material alcohol, and no Michael addition structure It means a compound having the above (meth) acryloyl group. The curable composition according to any one of claims 1 to 4, wherein the mixture (a) is a mixture containing dipentaerythritol (meth) acrylate. The aforementioned mixture (a) is obtained by subjecting a polyhydric alcohol having 3 or more alcoholic hydroxyl groups and a compound having one (meth) acryloyl group to an ester exchange reaction in the presence of the following catalysts X and Y. The curable composition according to any one of claims 1 to 5, which is a mixture containing a compound having a hydroxyl group and two or more (meth) acryloyl groups.
Catalyst X: One or more compounds selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof, amidines or salts or complexes thereof, and compounds having a pyridine ring or salts or complexes thereof.
Catalyst Y: Compound containing zinc. The curable composition according to claim 6, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The curable composition according to claim 6 or 7, wherein the catalyst X is a cyclic tertiary amine having an azabicyclo structure, a salt or a complex thereof, and the catalyst Y is an organic acid zinc or / and a zinc diketone enolate. object. The active energy ray hardening-type composition containing the composition of any one of Claims 1-8. The active energy ray-curable composition according to claim 9, further comprising a photopolymerization initiator (B). The active energy ray-curable composition according to claim 9 or 10, further comprising an alkali-soluble resin (E). The active energy ray hardening-type composition for pattern formation containing the composition of Claim 10 or Claim 11. In the presence of the following catalysts X and Y, a polyhydric alcohol having three or more alcoholic hydroxyl groups and a compound having one (meth) acryloyl group are transesterified to produce a hydroxyl group and two or more (meth). A mixture comprising a compound having an acryloyl group, producing the mixture (a);
A curable composition comprising a step of adding an acid anhydride to the mixture (a) to produce a mixture (A) having an acid value of 20 to 70 mgKOH / g and a viscosity of 25 ° C. of 50 to 9,500 mPa · s. Manufacturing method.
Catalyst X: One or more compounds selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof, amidines or salts or complexes thereof, and compounds having a pyridine ring or salts or complexes thereof.
Catalyst Y: Compound containing zinc. The method for producing a curable composition according to claim 13, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The curable composition according to claim 13 or 14, wherein the catalyst X is a cyclic tertiary amine having an azabicyclo structure, a salt or a complex thereof, and the catalyst Y is an organic acid zinc or / and a zinc diketone enolate. Manufacturing method. (A) The manufacturing method of the curable composition of any one of Claims 13-15 including the process of mixing a photoinitiator (B), after manufacturing a component. The manufacturing method of the curable composition of any one of Claims 13-16 including the process of further mixing alkali-soluble resin (E).