TWI390346B - Active line hardening composition - Google Patents

Description

Active energy line hardening composition

[0001] The present invention relates to an active energy ray-curable composition, and the composition of the present invention can be used for patterning in inks, paints, and resist films. The various uses of the composition of the present invention are particularly useful as a composition for forming a pattern because of excellent alkali developability, and the present invention belongs to such a technical field. The composition of the present invention can be preferably used particularly in the production of a liquid crystal panel, specifically, in the production of a columnar spacer, the production of a color filter protective film, and the formation of a colored layer for a color filter. Ideally applicable, the invention also falls within the field of such technology.

[0002] Previously, as a resist film ( ), solder resist film ( And a resist film used for a colored resist film or the like which is a colored layer of a color filter is often used as a (partial) acrylate (( ) In this case, in order to achieve an increase in the sensitivity of the composition and an increase in the hardness of the cured product, a compound having a plurality of (meta) acrylate groups (hereinafter referred to as "polyfunctional (partial) acrylate) has been used. ").

In this case, since the polyfunctional (bias) acrylate is insoluble in alkali, and the uncured portion of the coating film remains during development, and sufficient resolution cannot be obtained, the hydroxyl group is contained. Base and (partial) propylene sulfhydryl ( ) Carboxyl group obtained by addition reaction of a compound of a group with a divalent carboxylic acid anhydride ( The polyfunctional (partial) acrylates of the group have been discussed for a long time.

However, depending on the use thereof, even the above-mentioned carboxyl group-containing polyfunctional (meta) acrylate has insufficient hardness and developability.

Here, in order to further improve hardness and developability, one or more hydroxyl groups and two or more (partially) acryl groups are contained (( ) The carboxyl group-containing polyfunctional (meta) acrylate obtained by the addition reaction of a compound of the group with a tetravalent carboxylic acid dianhydride has also been discussed (Patent Reference 1).

[0005] However, even in the case of using a carboxyl group-containing polyfunctional (bias) acrylate as described in Patent Reference 1, since the crosslinking density is insufficient, there is a cured film strength, heat resistance, and chemical resistance. Good question.

On the other hand, regarding the composition for forming an active energy ray-hardening dies for a color filter used in the production of a liquid crystal panel, there are many requirements for the crosslinking density and alkali solubility of the cured product.

As a composition for forming an active energy ray-hardening pattern for a color filter, a composition containing a carboxyl group-free polyfunctional (meta) acrylate compound, an alkali-soluble resin, a photopolymerization initiator, and an organic solvent has been a human Know (Patent Reference 2).

In the present invention, in order to increase the crosslinking density and alkali solubility of the cured product, although the ratio of the photocurable functional group to the acidic functional group of the alkali-soluble resin is increased, the number of photocurable functional groups and acidic functional groups which can be cited is increased. Above the limit, there has also been a problem that the viscosity of the composition increases and the appropriateness of the coating is impaired.

In order to solve this problem, a composition for pattern formation containing a carboxyl group-containing polyfunctional (meta) acrylate has been proposed (Patent Reference 3). However, according to this composition, since alkali solubility is improved by using a compound having one carboxyl group in a molecule, particularly in the case where the content of the alkali-soluble resin is small, the developability is incomplete, and the sensitivity is not complete. .

[0007] [Patent Reference 1] Patent Publication No. 2001-089416 (Patent Application Scope) [Patent Reference 2] Patent Publication No. 2000-105456 (Patent Application Scope) [Patent Reference 3] Patent Announcement 2001-91954 Bulletin (Scope of Patent Application)

When the first object of the present invention is used as a composition for forming an active energy ray-curable pattern, it has excellent developability due to high exposure sensitivity, and can form a precise and correct pattern, and after hardening, the cured film A variety of articles such as strength, heat resistance, and chemical resistance are excellent in properties, and a composition for forming an active energy ray hardening pattern can be provided.

A second object of the present invention relates to the manufacture of a liquid crystal panel, which is used for the production of a color filter, and which has the above-mentioned properties and has high elasticity after hardening, and is suitable for a columnar separator ( And a composition for forming a pattern of elasticity of the protective film; and an active energy line hardening mold coloring composition which provides a colored layer stain or a contrasting stain when the color filter plate is formed.

The invention will be described in detail below, and, in accordance with the present description, (partial) acrylic acid (( ) ) means acrylic acid ( And/or methacrylic acid ( (meaning) acrylates and acrylates and / or methacrylates have the same meaning, (partial) acrylonitrile ( ) ) means acrylonitrile ( And/or methacrylic acid ( ).

【way of solving the problem】

The present invention relates to an active energy ray-curable composition containing two or more ethylene ( Sexually unsaturated group, 3-stage amino group ( A compound based on an acidic group (hereinafter referred to as "(a) component"). The components (a) and other components are described below.

1. (a) component

When the component (a) used in the present invention is a compound having two or more ethylenically unsaturated groups, a tertiary amino group, and an acidic group, various compounds can be used. In the component (a), a compound having three or more ethylenically unsaturated groups is remarkably excellent in curability, and the formed cured product has high hardness, and therefore is desirable. As the ethylenically unsaturated group related to the component (a), (partially) acryloyl group, (partial) allyl group (( ) Base) and ethylene ( The base can be used, and the (pre) acrylonitrile group is preferable from the viewpoint of easy availability and manufacture.

(a) The acid group related to the component, a carboxyl group or a sulfuryl group can be used ( Base and phosphorus The acid group or the like is preferably a carboxyl group from the viewpoint of easy availability and production.

The ratio of the acidic group in the (a) component is represented by the acid value, and when the composition is used for pattern formation, the acidity is 10 to 150 mg for the reason that the developability and the pattern shape are excellent. KOH/per gram is ideal, and more desirably, 20 to 100 mg KOH/g.

The molecular weight of the component (a) is preferably from 400 to 3,000.

The component (a) may be composed of several kinds of compounds described later.

[0012] In order to easily produce the component (a), it is desirable to select one or more of the following compounds (a-1) to (a-3).

[0013] (a-1): a compound having three or more (partially) acrylonitrile groups (hereinafter referred to as "polyfunctional (partial) acrylate") and a primary or secondary amine having an acidic group ( ) (hereinafter referred to as "acid amine") by Michael ( The product obtained by the addition reaction (hereinafter referred to as "(a-1)").

(a-2): a product obtained by a Michael addition reaction of a compound having three or more (partially) acrylonitrile groups and an acidic group (hereinafter referred to as "acidic polyfunctional (bias) acrylate") and an acid amine (hereinafter referred to as "(a-2)").

(a-3): a product obtained by a Michael addition reaction of an acidic polyfunctional (meta) acrylate with a hydroxyl group and a primary or secondary amine having no acid group (hereinafter referred to as "amine") (hereinafter referred to as " (a-3)").

The following is explained in relation to (a-1)~(a-3).

[0014] 1-1. (a-1) A polyfunctional (meta) acrylate which is related to (a-1) is to be produced. When a compound having three or more acryloyl groups is used, various compounds can be used.

As the polyfunctional (meta) acrylate, specifically, trimethylolpropane tri (meta) acrylate ( ( ) ), pentaerythritol tri (partial) acrylate ( ( ) ), pentaerythritol tetra (meta) acrylate, ditrimethylolpropane tetra (meta) acrylate, dipentaerythritol penta (meta) acrylate, and dipentaerythritol hexa(di) acrylate a poly(meta) acrylate; an alkylene oxide of the above polyol ( ) a poly(meta) acrylate of the additive; and an isocyanoic acid ( Acid oxidized alkylene The addition of the third (partial) acrylate and the like are employed. The above oxidized alkylene may be exemplified by ethylene oxide ( ), propylene oxide, and the like.

Among these examples, compounds having 4 or more (partially) acryl groups are preferred, specifically, dipentaerythritol tetra(p) acrylate, dipentaerythritol penta(penta) acrylate, and hexa The cured product obtained from the acrylate is particularly desirable because of its high elastic deformation rate.

[0015] As the acid amine, it is preferred to have a carboxyl group or a secondary amine.

As a suitable amine, an amino acid, specifically, a monoamine such as aminocaproic acid, a secondary amine such as valine, a diamine having a primary amino group or a secondary amino group such as glycosaminoglycine can be used. use.

[0016] A specific embodiment of (a-1) is represented by the following chemical formula. The chemical reaction formula (1) uses 1 mol of dipentaerythritol hexaacrylate [(A)] as a polyfunctional (meta) acrylate, and 1 mol of a carboxyl group-containing secondary amine [(B) As an example of an acid amine.

In the chemical formula (A), A is represented by an acrylonitrile oxide group, and A' is represented by -OCOCH ₂ CH ₂ -.

[0017]

[0018] 1-2. (a-2) An acidic polyfunctional (meta) acrylate according to (a-2), which is a compound having three or more (partially) acryloyl groups and one hydroxyl group (hereinafter referred to as "hydroxy polyfunctional group" (Partially) acrylate") is synthesized by reacting a compound having one or two acid anhydride groups (hereinafter referred to as "anhydride") in the same molecule.

[0019] As the hydroxypolyfunctional (meta) acrylate, specifically, pentaerythritol tri (meta) acrylate and dipentaerythritol penta (meta) acrylate can be used. As the hydroxypolyfunctional (meta) acrylate, a compound containing four or more (partially) acryl oxime groups in the same molecule is more preferable.

[0020] The hydroxy polyfunctional (meta) acrylate of the present invention may be contained, even if it contains a compound having three or more (partially) acrylonitrile groups which are produced by the production process, and examples thereof include pentaerythritol IV (for example). Partial) acrylate and dipentaerythritol hexa(meth) acrylate, etc., usually, pentaerythritol tetra (meta) acrylate contains pentaerythritol tri (meta) acrylate, dipentaerythritol hexa(di) acrylate It contains pentaerythritol penta (meta) acrylate.

Among these compounds having three or more (partially) acrylonitrile groups, the hydroxypolyfunctional (meta) acrylate component is preferably contained in a ratio of 20 to 80% by mass.

[0021] As the acid anhydride, for example, succinic anhydride can be used (anhydrous Acid), 1-dodecene anhydride (anhydrous 1- Acid), maleic anhydride (anhydrous Acid), glutaric anhydride (anhydrous Acid), itaconic anhydride (methylene succinic anhydride), phthalic anhydride (phthalic anhydride), hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrofurfuric anhydride, Methyltetrahydrofurfuric anhydride, benzylidene tetrahydrofuran anhydride, methyl bridgedmethylenetetrahydrofuran anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, benzene trimellitic anhydride, etc., having one in the same molecule An acid anhydride group compound; or a pyromellitic anhydride (anhydrous Acid), phthalic anhydride dimer, bisphenyl ether tetracarboxylic dianhydride, bisphenyl sulfonic acid dianhydride, benzophenone sulfonic acid dianhydride, and 1,2,3,4-butane tetracarboxylic acid Dihydride, bisphenyl ether tetracarboxylic anhydride, benzene trimellitic anhydride. Ethylene glycol ester (for example, a commercially available product, such as a new Japanese physicochemical company, trade name TMEG-100).

[0022] A method for producing an acidic polyfunctional (bias) acrylate can be carried out in accordance with a general industry method.

For example, a hydroxypolyfunctional (meta) acrylate and an acid anhydride are reacted at 60 to 110 ° C for 1 to 20 hours in the presence of a catalyst, and the like can be employed.

As a catalyst for this case, N,N-dimethylbenzylamine (N,N- can be used). ), triethylamine ( ), tributylamine, triethylenediamine, benzyltrimethylammonium chloride ( ), benzyl triethyl ammonium bromide ( ), tetramethylammonium bromide, cetyltrimethylammonium bromide, and lead oxide.

[0023] As the acid amine, the same as described above can be used.

[0024] A specific example of (a-2) is represented by the following chemical reaction formula (2) using an acid anhydride [(C)] of 1 mol of dipentaerythritol pentaacrylate as an acidic polyfunctional group ( Partial) acrylates, and examples in which 1 mole of a secondary amine having a carboxyl group is used as the acid amine.

In the chemical formula (C), A and A' are represented by the same functional group as the chemical formula (A).

[0025]

[0026] 1-3. (a-3) The acid polyfunctional (meta) acrylate of the above (a-3) is produced, and the same as described above can be used.

[0027] As the amine, specifically, a monoamine such as n-propylamine, n-butylamine, n-hexylamine or benzylamine; dimethylamine, diethylamine, bispropylamine, diisopropyl Amines such as amines, dibutylamine, cyclohexylamine and morpholine.

[0028] A specific example of (a-3) is represented by the following chemical reaction formula (3) using an acid anhydride addition of [2C] of pentaerythritol pentaacrylate [(C)] as an acid polyfunctional The base (partial) acrylate is compared to the embodiment in which 1 mole of amine [(D)] is used.

However, in the actual reaction, when 1 mol (D) is used for 2 mol (C), gelation occurs ( In the case of 2 mol (C), the reaction is carried out using (D) at a ratio of 1 mol or less, more preferably at a ratio of 0.8 mol or less.

[0029]

[0030] 1-4. The manufacturing methods (a-1) to (a-3) of (a-1) to (a-3) are respectively a polyfunctional (meta) acrylate and an acidic amine, and an acidic polyfunctional (meta) acrylate. With acidic amines, and acidic polyfunctional (meta) acrylates and amines, via Michael ( The substance obtained by the addition reaction.

The desired ratio of the raw material component is preferably set as appropriate according to the purpose, and is preferably as shown below.

(a-1): when the total amount of (partially) acrylonitrile groups in the polyfunctional (meta) acrylate is 1 mole, and in the case of an acidic primary amine, it is preferably 0.2 to 0.4 moles; In the case of acidic secondary amines, it is desirable to use 0.4 to 0.8 moles.

(a-2): when the total amount of (partially) acrylonitrile groups of the acidic polyfunctional (meta) acrylate is 1 mole, and in the case of an acidic primary amine, it is preferably 0.2 to 0.4 moles; In the case of acidic secondary amines, it is desirable to use 0.4 to 0.8 moles.

(a-3): When the total amount of (partially) acrylonitrile groups of the acidic polyfunctional (meta) acrylate is 1 mol, in the case of a primary amine, it is desirable to use 0.2 to 0.4 mol; In the case of secondary amines, it is desirable to use 0.4 to 0.8 moles.

The method of the Michael addition reaction may be carried out by following a general method. Specifically, for example, these compounds may be subjected to a reaction at a temperature of from ordinary temperature to 50 ° C for one hour or more, and such a method may be used.

Polyfunctional (partial) acrylates and acid amines, acidic polyfunctional (meta) acrylates and acid amines, and acidic polyfunctional (meta) acrylic acids of the raw materials of the components (a-1) to (a-3) The salt and the amine may be used singly or in combination of two or more.

[0031] 1-5. A compound having a hydroxyl group (a) as a component (a) and having a hydroxyl group (hereinafter referred to as "(a2)") is used as a composition for forming a pattern because of an aqueous solution containing a developing solution. It is ideal for reasons such as superior affinity and superior imaging.

[0032] As a specific example of the component (a2), the compounds listed below can be used.

1) As the polyfunctional (meta) acrylate related to (a-1), three or more of ditrimethylolpropane tri(penta) acrylate and dipentaerythritol penta(penta) acrylate are used. A compound produced by a compound of (acrylic) hydrazino group and a hydroxyl group.

2) as the acidic polyfunctional (meta) acrylate associated with (a-2) and (a-3), based on a small proportion of the total amount of hydroxyl groups in the hydroxypolyfunctional (meta) acrylate, A compound produced by reacting an acid anhydride-derived acidic polyfunctional (meta) acrylate with an acid anhydride.

3) A product obtained by a Michael addition reaction of an acidic polyfunctional unsaturated compound with a primary or secondary amine having a hydroxyl group (hereinafter referred to as "hydroxylamine") (hereinafter referred to as "(a2-1)").

Among these compounds, (a2-1) is preferable because the amount of introduction of the acidic group and the hydroxyl group can be easily adjusted according to the user's intention.

As the acidic polyfunctional (meta) acrylate related to (a2-1), the same as described above can be used.

In the case of hydroxylamine, specifically, a primary amine such as monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol or p-aminophenol; or N-methyl group can be used. A secondary amine such as ethanolamine, N-ethylethanolamine, N-ethylethanolamine, diethanolamine, 3-anilinophenol or 4-anilinophenol.

The acidic polyfunctional unsaturated compound and hydroxylamine may be used alone or in combination of two or more.

[0034] A specific example of (a2-1) is represented by the following chemical reaction formula (4). In the chemical reaction formula (4), as the acid polyfunctional (meta) acrylate, the acid anhydride "(C)" of 2 mol of dipentaerythritol pentaacrylate is used, and 1 mol of hydroxylamine is used. )" An example of a reaction.

However, in the actual reaction, for 1 mole of (C), if 1 mole of (E) is used, since there is gelation, 1 mole is used for 2 moles (C). In the following (E), a more desirable ratio is to use a reaction of 0.8 mol or less.

[0035]

[0036] Regarding the manufacturing method of (a2-1), the same method as described above may be followed.

[0037] 1-6. In the other examples, as the component (a) and the component (a2), in addition to the above, a polyfunctional (meta) acrylate or a hydroxypolyfunctional (meta) acrylate may be used in a Michael addition reaction with hydroxylamine. A compound obtained by an addition reaction of an acid anhydride with an acid anhydride (hereinafter referred to as "(a3-1)").

Regarding the product obtained by a Michael addition reaction of a polyfunctional (meta) acrylate or a hydroxyl group with a hydroxylamine, when the equivalent ratio of the hydroxyl group to the acid anhydride group is 1, the component (a) is formed; similarly, the equivalent ratio of the hydroxyl group to the acid anhydride group When it is less than 1, the component (a2) is formed.

[0038] A specific example of (a3-1) is represented by the following chemical reaction formula (5). Chemical reaction formula (5), using 2 mol of dipentaerythritol hexapolyacrylate [(A)] as a functional (bias) acrylate, and using 1 mol hydroxylamine [(E)], relative use 1 An example of the reaction by carrying out a molar anhydride [(F)].

However, in the actual reaction, if 1 mole of (E) is used for 2 moles (A), gelation may occur, so for 2 moles (A), use 1 mole or less. (E), a more desirable ratio is to use 0.8 moles or less to carry out the reaction.

[0039]

[0040] The production method of (a3-1), such as the Michael addition reaction and the addition reaction of an acid anhydride, may be carried out in the same manner as described above.

[0041] 2. Other components The composition of the present invention may be blended with other components as needed in addition to the above-mentioned component (a).

Specifically, such as a photopolymerization initiator, an organic solvent, an unsaturated group-containing compound, a pigment, a dye, a defoaming agent, a leveling agent ( 剤), inorganic filler (inorganic ) and organic fillers can also be used in combination. Further, it is also possible to add a small amount of an antioxidant, a light stabilizer, a UV absorber, and a polymerization preventing agent as needed.

Hereinafter, the contents of the photopolymerization initiator, the organic solvent, and the unsaturated group-containing compound will be described in detail.

[0042] 2-1. Photopolymerization initiator The composition of the present invention is a product which is hardened by irradiation with an energy source. Therefore, as the active energy source in this case, microwave, visible light, ultraviolet light or the like can be used. Among these, no special device is required, and visible light or ultraviolet light is preferable in order to be simple.

As a visible light or ultraviolet curing mold composition, a photopolymerization initiator is added to the composition. When it is used as a microwave hardening mold composition, it is not necessary to add a photopolymerization initiator.

[0043] As a photopolymerization initiator (hereinafter referred to as "(b) component"), for example, a biimidazole ( a compound, a benzoin ( a compound, acetophenone ( ) compounds, benzophenone ( ) compounds, α-dimethylketone (α- Compounds, multinuclear ruthenium ) compounds, xanthone ( ) compounds, thioxanthone ( a compound, triazotoluene ) compounds, and ketals Classes, etc. are all usable.

[0044] As a specific example of a biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylbenzene)-1,2 '-Diimidazole (2,2'- (2- )-4,4',5,5'- (4- )-1,2'- , 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylbenzene)-1,2'-bisimidazole (2,2'- (2- )-4,4',5,5'- (4- )-1,2'- ), 2,2'-bis(2-chlorophenyl-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4-dichlorobenzene) -4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichlorobenzene)-4,4',5,5'- Tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'- Bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, and 2,2'-bis(2,4,6-tribromobenzene) -4,4',5,5'-tetraphenyl-1,2'-bisimidazole (2,2'- (2,4,6- )-4,4',5,5'- -1,2'- ) can be used.

When a biimidazole compound is used as the component (b), since the hydrogen donor is used in combination, the sensitivity can be further improved, and it is desirable. The term "hydrogen donor" as used herein refers to a compound capable of providing a hydrogen atom to a group (atomic group) derived from a bisimidazole compound by exposure.

As a hydrogen donor, thiol ( Hydrogen supply systems such as amines and amines are preferred.

[0046] A thiol-based hydrogen donor having a benzene ring or a complex ring as a basic nucleus and directly bonded to the thiol group of the basic nucleus ( There are one or more, more preferably one to three, and more preferably one or two compounds. Specific examples of the mercaptan hydrogen donor are 2-hydrothiobenzothiazole and 2-hydrothiobenzoxazole (2- , 2-hydrothiobenzimidazole, 2,5-dihydrothio-1,3,4-thiathiazole and 2-hydrothio-2,5-dimethylaminopyridine can be used, Among these thiol-based hydrogen donors, 2-hydrothiobenzothiazole and 2-hydrothiobenzoxazole are preferred, and 2-hydrothiobenzothiazole is particularly preferred.

[0047] The amine hydrogen donor has a benzene ring or a complex ring as a basic nucleus, and one or more amino groups directly bonded to the basic nucleus, more preferably 1 to 3, and a compound having 1 to 2 For the more ideal. As a specific example of the amine hydrogen donor, 4,4'-bis(dimethylamine)benzophenone, 4,4'-bis(diethylamine)benzophenone, 4-diethylamine benzene can be used. Ethyl ketone, 4-dimethylaminopropiophenone, ethyl-4-dimethylamine benzoate, 4-dimethylamine benzoic acid, 4-dimethylamine benzyl cyanide, and the like.

[0048] The hydrogen donor may be used singly or in combination of two or more kinds, and one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors may be used in combination, and the formed separator may be a pixel during development. It is not easy to fall off from the substrate, and the strength and sensitivity of the separator or the pixel are also high, which is preferable. Further, a hydrogen donor having both a thiol group and an amine group is also a very suitable use component.

[0049] Specific examples of benzoin (benzophenone) compounds can be listed, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether and 2 - benzoquinone benzoin methyl and the like.

[0050] As a specific example of an acetophenone compound, 2,2-dimethoxyacetophenone (2,2- ), 2,2-diethoxyacetophenone (2,2- ), 2,2-dimethoxy-2-phenylacetophenone (2,2- -2- ), 2-hydroxy-2-methyl-1-phenylpropan-1-one (2- -2- -1- -1- ), 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one (1-(4-i-) )-2- -2- -1- ), 1-(4-methylphenylthio)-2-methyl-2-morpholinepropan-1-one (1-(4-) )-2- -2- -1- , 1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-hydroxypropan-1-one (1-[4-(2-) ) 〕-2- -2- -1- , 1-(4-morpholinylphenyl)-2-benzyl-2-dimethylaminobutan-1-one (1-(4-) )-2- -2- -1- ), 1-hydroxycyclohexylphenylacetone (1- And 2,2-dimethoxy-1,2-diphenylethan-1-one (2- -1- ) can be listed for use.

[0051] Specific examples of the benzophenone compound may, for example, be benzyl dimethyl ketone ( ),Benzophenone( ), 4,4'-bis(dimethylbenzophenone) (4,4'- ( )) and 4,4'-bis(diethylbenzophenone) (4,4'- ( ))Wait.

[0052] α-dimethylketone (α- Specific examples of the class of compounds, such as diethyl hydrazine ), benzophenone ( ), methyl benzoic acid ester ( ).

[0053] Multi-core 醌 (multi-core Specific examples of the class of compounds, such as green onion ( ), 2-ethyl onion, 2-t-butyl onion, and 1,4-naphthoquinone (1,4- )Wait.

[0054] xanthones ( Specific examples of the class of compounds, such as xanthones (for example) ), thioxanthone ( ), 2-chlorothioxanthone, and the like.

[0055] Trinitrotoluene ( Specific examples of the compound can be enumerated, for example, 1,3,5-tris(trichloromethyl)-s-triazine (1,3,5- ( )-s- ), 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine (1,3- ( )-5-(2'- )-s- ), 1,3-bis(trichloromethyl)-5-(4'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-methoxy Phenyl)-s-triazine (1,3- ( )-5-(2'- )-s- ), 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s- Triazine (2- -4,6- ( )-s- ), 2-(4'-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 6-bis(trichloromethyl)-s-triazine, 2-(4) -ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine (2-(4- )-4,6- ( )-s- And 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine (2-(4-n-) )-4,6- ( )-s- )Wait.

[0056] Among these examples, 1-hydroxycyclohexyl benzophenone (1- And 1-(4-methylphenylthio)-2-methyl-2-morpholinepropan-1-one, which promotes the initiation of polymerization even if it is irradiated with a small amount of active energy rays, so In the invention, it can be used ideally.

The component (b) may be used singly or in combination of two or more.

When the mass ratio of the solid portion other than the photopolymerization initiator in the composition is 100 as the mixing ratio of the component (b), the component (b) is preferably a mass of 0.5 to 20. If the mass of the component (b) is less than 0.5, the photocurability is incomplete. On the other hand, if the mass exceeds 20, the exposed portion is liable to fail when the alkali is developed. Further, as the ratio of the component (b), a pattern having a high accuracy can be obtained at a mass ratio of 2 to 10%, which is an advantage.

[0058] 2-2. Organic solvent In the present invention, in order to improve the paintability of the composition, an organic solvent may be added.

The organic solvent (hereinafter referred to as "(c) component") is excellent in that it does not react with each component of the composition. The coating property is excellent, and since the obtained coating film has a proper drying speed, an organic solvent having a boiling point of 80 to 200 ° C is preferable, and among them, an organic solvent having a boiling point of 100 to 170 ° C is more preferable. .

Specifically, for example, toluene ( And xylene ( An aromatic compound; butyl acetate (tannic acid) ), benzyl acetate, propylene glycol methyl ether acetate ( And ethoxyethyl propionate ( Fatty acid esters; ethyl cellosolve ( And cellosolve such as butyl cellosolve (ethylene glycol-diethyl ether); alkenyl glycol ether such as propylene glycol methyl ether; alcohols such as ethanol, ethylene glycol and diethylene glycol; Methyl ether ) ethers; methyl. Isobutyl ketone ( And cyclohexanone ( Ketones; N,N-dimethylformamide (N,N- And other methotrexate; γ-butyl decylamine (γ- And N-methyl-2-pyrrolidone (N- -2- And other phthalamides; and γ-butyl lactone (γ-) And other lactones can be used.

The component (c) may be used alone or in combination of two or more.

The proportion of the component (c) is preferably 10 to 50% by mass of the solid content of the composition.

[0059] 2-3. Compound Containing Unsaturated Group The composition of the present invention may contain, in addition to the component (a), a compound containing an unsaturated group (hereinafter referred to as "(d) component").

As the component (d), for example, phenoxyethyl (meta) acrylate ( ( ) ), carbitol (partial) acrylate ( ( ) ), N-vinyl caprolactone (N- ), propylene morpholine ( ), epoxy propyl (partial) acrylate ( ( ) ), 2-hydroxy (partial) acrylate (2- ( ) ), 2-hydroxypropyl (meta) acrylate, 1,4-butanediol mono (meta) acrylate (1,4- ( ) ), 1,6-hexanediol di(meta) acrylate (1,6- ( ) ), decanediol di(pre) acrylate ( ), polyethylene glycol di(pre) acrylate ( ( ) ), 2-hydroxy-3-phenyloxopropyl (partial) acrylate (2- -3- ( ) ), tribromophenyl (partial) acrylate ( ( ) , 2,2-bis(4-(partial) propylene oxiranyloxyphenyl)-propane (2,2- (4-( ) )- , 2,2-bis(4-(partial) propylene oxiranodiethoxyphenyl)-propane, 2,2-bis(4-(partial) propylene oxiranoxytriethoxyphenyl)- Propane, ethylene glycol di(meta) acrylate ( ) ), tribromophenyl oxyethyl (meta) acrylate ( ( ) ), trimethylolpropane tri (partial) acrylate ( ( ) ), pentaerythritol tetra (meta) acrylate, bisphenol A type epoxy resin bis (meta) acrylate ( Type A Resin ( ) ), various polyurethane poly(meta) acrylates and Polyester poly(meta) acrylate or the like can be used.

The component (d) may be used singly or in combination of two or more.

The ideal blending ratio of the component (d) is a range of 0 to 50% by mass in the composition.

[0060] 3. Active Energy Line Hardening Composition The composition of the present invention must have the aforementioned component (a).

The composition of the present invention may be obtained by mixing and mixing the component (b) to the component (e) or other components in accordance with a method commonly used in the art, in addition to the component (a) of the above-mentioned essential component.

The preferred combination of the composition of the present invention means a composition comprising the component (a) and the component (b); a composition comprising the component (a), the component (b) and/or the component (c); a component, a component of the component (b), a component (c), and/or a component (d). The blending ratio of these compositions is blended and blended in accordance with the above-mentioned ideal blending ratio, and a good composition can be obtained.

[0061] 4. Use The composition of the present invention can be used for various applications, for example, a composition for pattern formation such as a resist, a coating material for inks and paints, and the like.

The composition of the present invention is excellent in alkali developability, and can be used as a composition for pattern formation.

When the composition of the present invention is used as a composition for pattern formation, a substance containing an alkali-soluble resin is preferable. Hereinafter, the alkali-soluble resin will be described.

[0062] 4-1. Alkali-soluble resin is used as the alkali-soluble resin (hereinafter referred to as "(e) component)) of the present invention, and as a binder for (a) component ( The function of the image developing liquid used in the related development processing is particularly preferably a substance which is soluble in the alkali developing solution, but is not particularly limited.

As the component (e), an addition polymer, a polyester, an epoxy resin, a polyether or the like can be used, and an addition polymer obtained by polymerizing an ethylenically unsaturated monomer is preferable.

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-containing unsaturated monomer") may be used. A copolymer of a monomer-copolymerized ethylenically unsaturated monomer (hereinafter referred to as "co-polymerizable unsaturated monomer") (hereinafter referred to as "carboxyl group-containing copolymer") is most preferable.

[0063] Examples of carboxyl group-containing unsaturated monomers are (partial) acrylic acid, crotonic acid ( Acid), α-chlorocrotonic acid (α- Unsaturated monocarboxylic acids such as acid) and bark acid; maleic acid ( Acid), maleic anhydride, fumaric acid Acid), isoconic acid Acid), isaconic anhydride, citraconic acid ( Acid), citraconic anhydride and mesaconic acid ( An acid or the like unsaturated dicarboxylic acid or an anhydride thereof; a trivalent or higher unsaturated polycarboxylic acid or an anhydride thereof; succinic acid mono(2-(meta)propene oxirane ( acid [2-( ) ]) and a single [(partial) propylene sulfonyl] ester of a divalent or higher polyvalent carboxylic acid such as 2-(meta)propenyl ethoxide or the like; and, for example, ω-carboxypoly Endoamine (ω- A single (partial) acrylate or the like having a carboxyl group and a hydroxyl group at both ends thereof is a single (partial) acrylate. Among these carboxyl group-containing unsaturated monomers, ω-carboxy polycaprolactam monoacrylate and phthalic acid mono(2-propene oxime) are respectively The trade names of M-5300 and M-5400 [East Asian Synthetic Co., Ltd.] are sold in the market.

The carboxyl group-containing unsaturated monomer may be used singly or in combination of two or more.

Further, as the copolymerizable unsaturated monomer, those which are copolymerized with the carboxyl group-containing unsaturated monomer are preferable, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and an unsaturated iminium ( Classes and macromonomers containing a single (partially) acrylonitrile group at the end are desirable.

[0065] As the aromatic vinyl compound, there may be mentioned styrene ( ), α-methylstyrene, o-vinyltoluene (o- ), m-vinyl toluene, p-vinyl toluene, p-chloroethylene (p- ), o-methoxystyrene (o- ), m-methoxystyrene, p-methoxystyrene, 2-vinylbenzyl methyl ether (2- ), 3-vinylbenzyl methyl ether, 4-vinylbenzyl methyl ether, 2-vinylbenzyl glycidyl ether (2- ), 3-vinylbenzyl glycidyl ether, and 4-vinylbenzyl glycidyl ether.

[0066] Examples of the unsaturated carboxylic acid esters include methyl (meta) acrylate, ethyl (meta) acrylate, n-propyl (meta) acrylate, and isopropyl (meta) acrylate. , n-butyl (meta) acrylate, isobutyl (meta) acrylate, butyl (meta) acrylate, t-butyl (meta) acrylate, 2-hydroxyethyl (meta) acrylate, 2-hydroxypropyl (meta) acrylate, 3-hydroxypropyl (meta) acrylate, 2-hydroxybutyl (meta) acrylate, 3-hydroxybutyl (meta) acrylate, 4-hydroxybutyrate Base (partial) acrylate, allyl ( (Partial) acrylate, benzyl (meta) acrylate, cyclohexyl (meta) acrylate, phenyl (meta) acrylate, 2-methoxyethyl (meta) acrylate, 2-phenoxy Base (partial) acrylate, methoxybisethylene glycol ( (Partial) acrylate, methoxytriethylene glycol (meta) acrylate, methoxypropylene glycol ( (Partial) acrylate, methoxydipropylene glycol (meta) acrylate, isobornyl ( ) (Partial) acrylate, tricyclo[5,2,1,0 ^{2 , 6} ]癸-8-醯 ( [5.2.1.0 ^{2 , 6} ] -8- (Partial) acrylate, 2-hydroxy-3-phenoxypropyl (meta) acrylate, and glycerol mono (meta) acrylate.

[0067] As the unsaturated imines, there may be mentioned, there is maleimine ( ), N-phenylmaleimine, and N-cyclohexylmaleimide.

[0068] Examples of the macromonomers having a mono(p-)acrylonitrile group at the terminal include polystyrene, polymethyl (meta) acrylate, and poly-n-butyl (meta) acrylate. And polysiloxane ( ) A substance that has a molecular chain lock.

[0069] As a copolymerizable unsaturated monomer, in addition to the foregoing, there may be 2-(3,4,5,6,-tetrahydrophthalene imino) (2-(3,4, 5,6- )) an imide (partial) acrylate such as ethyl (meta) acrylate or 2-(2,3-dimethylmaleimide)ethyl (meta) acrylate; 2-aminoethyl Acrylate, 2-dimethylaminoethyl (meta) acrylate, 2-aminopropyl (meta) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meta) acrylate And amino carboxylic acid esters of unsaturated carboxylic acids such as 3-dimethylaminopropyl (meta) acrylate; glycidyl acrylates of unsaturated carboxylic acid such as glycidyl (meta) acrylate; And hydrazines such as 1-methyl hydrazine; vinyl acetate (tannic acid) ), vinyl acrylates such as vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl methyl ether ( ), ethyl ether, and allyl ethers such as allyl glycidyl ether; (partial) acrylonitrile (( ) ), α-chloropropene nitrile, and cyanide vinyl fork ( Chemical And other vinyl cyanide compounds; (partial) decyl acrylate (( ) ), α-chloro(poly)acrylic acid decylamine, and unsaturated amides such as N-2-hydroxyethyl (meta) decyl acrylate; and, 1,3-butadiene (1,3- ), isoprene ( ), and chloroprene ( The aliphatic conjugated diene etc. are used, for example.

These copolymerizable unsaturated monomers may be used singly or in combination of two or more.

[0070] As a carboxyl group-containing copolymer, (partial) acrylic acid is an essential component, and may be, from the case of succinic acid, mono [2-(meta)propene oxime), ω-carboxypolycaprolactone ( a group of at least one selected from the group consisting of acrylates; and a component of a carboxyl group-containing unsaturated monomer, which may be derived from styrene, methyl (meta) acrylate, 2-hydroxyethyl (meta) acrylate, allyl (Partial) acrylate, benzyl (meta) acrylate, glycerol mono (meta) acrylate, N-phenyl maleimide, polystyrene macromonomer, and polymethyl methacrylate macromonomer ( A group such as at least one type of compound is selected, and a copolymer of the two (hereinafter referred to as "carboxyl-containing copolymer (α)") is desirable.

[0071] Specific examples of the carboxyl group-containing copolymer (α) include: (partial) acrylic acid/methyl (meta) acrylate copolymer, (partial) acrylic acid/benzyl (meta) acrylate copolymer, (bias) Acrylic acid/2-hydroxyethyl (meta) acrylate / benzyl (meta) acrylate copolymer, (partial) acrylic acid / glycidyl (partial) acrylate copolymer, (meta) acrylic / methyl (meta) acrylic acid Salt/polystyrene macromonomer copolymer, (partial) acrylic acid/methyl (meta) acrylate/polymethyl methacrylate copolymer, (partial) acrylic acid / benzyl (meta) acrylate / polystyrene Macromonomer copolymer, (partial) acrylic acid / benzyl (meta) acrylate / polymethyl methacrylate copolymer, (meta) acrylic acid / 2-hydroxyethyl (meta) acrylate / benzyl (bias Acrylate/polystyrene macromonomer copolymer, (partial) acrylic acid/2-hydroxyethyl (meta) acrylate / benzyl (meta) acrylate / polymethyl methacrylate copolymer, (bias Acrylic/styrene/benzyl (partial) acrylate/N-phenylmaleimide copolymer, (partial) acrylic acid/succinic acid mono [2-(partial) propylene oxime ester] / styrene / benzyl Base (partial) acrylate / N-phenylmaleimide copolymer, (partial) acrylic acid / succinic acid mono [2-(partial) propylene ethoxide] / styrene / allyl (partial) acrylate / N-phenyl Malay Imine copolymer, (meta) acrylic acid / styrene / benzyl (meta) acrylate / glycerol mono (meta) acrylate / N-phenyl maleimide copolymer, (partial) acrylic / ω-carboxy poly The indoleamine mono (polar) acrylate / styrene / benzyl (meta) acrylate / glycerin mono (partial) acrylate / N-phenyl maleimide copolymer, etc. can be used.

[0072] Regarding the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is usually from 5 to 50% by mass, and more desirably from 10 to 40% by mass. In this case, the copolymerization ratio is less than 5% by mass, and the obtained composition tends to have a reduced solubility in the alkali developing solution. On the other hand, the solubility in the alkali developing solution is more than 50% by mass. When it is developed with an alkali developing solution, it tends to gradually fall off from the separator layer or the pixel substrate or the surface of the separator layer is cracked.

[0073] As the component (e) according to the present invention, the crosslinking density of the cured film obtained by the alkali-soluble resin having an ethylenically unsaturated group in the branch is increased, and the film strength, heat resistance and chemical resistance are also improved. Due to this significant advantage, it is ideal.

An alkali-soluble resin having an ethylenically unsaturated group in the branched chain is preferably an alkali-soluble resin having a carboxyl group. As a related resin, a user may be mentioned, and in the above-mentioned carboxyl group-containing copolymer, an epoxy resin is added ( A product of a radical unsaturated compound (hereinafter referred to as "epoxy unsaturated compound").

Examples of the epoxy-based unsaturated compound include users such as glycidyl (trans) acrylate and cyclohexene oxalate ( An epoxy group-containing (partial) acrylate such as a (partial) acrylate. As a method of the addition reaction, it can be produced by adding a reaction of an epoxy group-containing unsaturated compound to a carboxyl group-containing copolymer in an organic solvent or in a solvent-free state according to a general method. . As a condition for the addition reaction, if the reaction temperature, reaction time, and catalyst required for each reaction can be properly selected, good results can be obtained.

The mass molecular weight (hereinafter referred to as "Mw") of the component (e) is usually 3,000 to 300,000; more preferably, it is 5,000 to 100,000. Further, the number average molecular weight (hereinafter referred to as "Mn") is usually 3,000 to 60,000; more preferably, it is 5,000 to 25,000.

Further, in the present invention, the meaning of Mw and Mn means a value obtained by gel permeation chromatography (GPC, solvent: tetrahydrofuran), and the molecular weight is converted to polystyrene.

According to the present invention, since such a component (e) having a specific Mw and Mn is used, a photosensitive resin composition having remarkable development properties can be obtained, and as a result, a pattern having a sharp pattern edge can be formed, and at the same time, Residues, contamination, film residue, and the like are less likely to occur on the substrate on the unexposed portion and on the light shielding layer during development. Further, the ratio (Mw/Mn) of Mw and Mn of the component (e) is usually from 1 to 5, preferably from 1 to 4.

The component (e) may be used singly or in combination of two or more.

[0075] The ratio of the component (a) to the component (e) is based on the total amount of the two components, and the mass ratio of the component (a) is 10 to 100% by mass and the mass ratio of the component (e) is 0 to 90%. More preferably, the component (a) has a mass ratio of 30 to 100% and the component (e) has a mass ratio of 0 to 70%; and when the ratio of the component (a) is less than 10% by mass, the coating is lowered due to a decrease in crosslinking density. Film strength, heat resistance, and chemical resistance tend to decrease.

The ratio in the composition of the component (a) and the component (e) is preferably 10 to 50% by mass based on the total amount of the two components; if the ratio is less than 10% The mass ratio is such that the film thickness after pre-baking becomes too thin; on the other hand, if the mass ratio exceeds 50%, the viscosity of the composition becomes too high to deteriorate the coating work, and the film thickness after pre-baking is Become too thick.

[0076] 4-2. Composition for pattern formation The composition of the present invention can be suitably used as a composition for pattern formation because the exposure sensitivity is high and the developability is remarkable and fine, and a correct pattern can be formed.

When the composition of the present invention is used as a composition for pattern formation, a composition comprising the components (a), (b), (c) and (e) is desirable.

[0077] As a composition for pattern formation, a resist such as a resist and a solder resist is etched, a liquid crystal panel is produced, a columnar spacer, a pixel for forming a color filter, or The color composition of the black matrix, and the color filter protective film.

In the use of the liquid crystal panel, the composition of the present invention can be preferably used in accordance with the use of a columnar separator, a coloring composition for a color filter, and a protective film for a color filter.

When the columnar separator and the protective film for a color filter are used for the purpose, in order to improve the paintability and developability, a nonionic surfactant such as polyoxyethylene dodecyl ether may be added, or Fluorinated surfactant. Further, an adhesive, a storage stabilizer, and a defoaming agent may be added in accordance with the needs thereof.

The use of the columnar separator (hereinafter simply referred to as "separator") and the coloring composition will be described below.

[0079] 4-2-1. Separator The separator is formed by a photo-hardening coating film of a composition according to a photoelectric lithography method. The spacer may be formed in any size at any position of the liquid crystal panel substrate, but is generally formed in a black matrix range or a thin film transistor (TFT) electrode of the light shielding portion of the color filter.

The method of forming the separator may be carried out according to a general method. For example, the composition of the present invention may be used, for example, on a substrate such as glass, after applying a thick film to the substrate, and then heating it (hereinafter referred to as " Pre-baked") A method in which the coating film is dried, exposed, imaged, and heated (hereinafter referred to as "post-bake").

[0080] When the composition is applied to the substrate, it is considered that the film is thinned or deformed due to development, post-baking, etc., and a certain thickness is applied to the set value of the slit of the hole. Specifically, it is desirable to have a film thickness of 5 to 10 μm or even 6 to 7 μm after prebaking.

As a method of painting, for example, a printing method, a spray method, a roller coating method, a curtain coating method, a spin coating method, a dye coating method (slit coating method), or the like can be used, and generally, a rotation is used. Coating or dye coating methods are commonly used.

[0081] After the composition is applied to the substrate, prebaking is performed. The temperature and time in this case can be used at 50 to 150 ° C for 5 to 15 minutes.

[0082] The surface of the pre-baked coating film is irradiated with light passing through a mask having a pattern shape set to form a spacer.

The light used, ultraviolet or visible light is ideal, using high-pressure mercury or halogen lamps to emit light from 240 nm to 410 nm.

The conditions of light irradiation are about 50 to 600 millijoules (mJ) per square centimeter (cm ² ) depending on the type of the light source, the absorption wavelength of the photopolymerization initiator used, or the thickness of the coating film. ideal. When the amount of light irradiation is less than 50 mJ/cm 2 , it becomes poorly hardened, and the exposed portion is easily dropped when developing; on the other hand, when the amount of light irradiation exceeds 600 mJ/cm 2 , it tends to be difficult to obtain a fine separator. Graphics.

[0083] In the foregoing, after the surface of the coating film is irradiated with light, the unexposed portion is removed with a developing solution.

An aqueous solution of an alkali compound can be used as a developing solution. As an alkali compound, for example, potassium hydroxide (water acidification) ), sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, ammonia, tetramethylammonium hydroxide ( )Wait. Further, in order to increase the development speed, it is also possible to add an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or the like to the developing solution.

The development method, such as a liquid pouring method, a dipping method, and a spraying method, may be used. After the image is developed, it is washed with water for about 0.5 to 1.5 minutes, and the pattern portion is washed, and then compressed air or the like is used to wind up, and a spacer pattern is obtained.

[0084] The obtained separator pattern is post-baked in a temperature range of 150 to 350 ° C by a heating device such as a hot plate or an oven to obtain a liquid crystal panel separator of the present invention.

Since there is a post-baking operation, the residual solvent or the water absorbed during development can be evaporated, and the heat resistance of the separator can be improved. The film thickness of the separator differs depending on the set value of the slit of the liquid crystal panel, and is roughly designed to be 3 to 5 μm after the intended baking.

[0085] The composition of the present invention is used in the case of manufacturing a separator, using an ultra-fine hardness tester [() , H-100C], at room temperature, when the compressive load of a flat indenter (100 μm × 100 μm plane is under pressure) is 0.2 GPa, the elastic deformation rate [(elastic deformation rate / total) The variable amount) × 100] is 60% or more, that is, it is ideal.

Due to the use of such a composition, at room temperature, there is sufficient hardness which is not easily plastically deformed for the compressive load, and flexibility in which the liquid crystal contracts and expands in the temperature range of the use environment of the liquid crystal display device. Therefore, in the case where the substrate for a liquid crystal panel obtained by the present invention is bonded by a room temperature perforation, the plastic deformation does not occur, and a correct and uniform aperture slit can be formed, particularly in accordance with the ODF method. The thermoporous eye is legally applied and can be properly utilized.

[0086] 4-2-2. Coloring composition In the case where the composition of the present invention is used as a coloring composition, a pigment and a pigment dispersing agent are further blended. The components related to this section are explained below.

[0087] The pigment is not particularly limited, and various organic or inorganic pigments can be used.

As a specific example of the organic pigment, according to the "Pigment Index" (CI; The Society of Dyers and Colourists, the compound of the classified pigment, in other words, the following pigment index (CI) number can be used: CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, etc. Yellow pigment; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 177, CI Pigment Red 254 and other red pigments; and, CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI pigment blue 15:6 and other blue pigments; CI pigment green 7, CI pigment green 36 and other green pigments; CI pigment violet 23, CI pigment violet 23:19 and so on.

Also, phthalocyanine with a high bromination rate that was previously difficult to disperse ( ), for example, single star green ( ) 6YC, 9YC ( High-brightness G pigment produced by the company, the center metal can use metals other than copper, such as magnesium, aluminum, barium, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, antimony, tin, etc. High color purity G pigment obtained from pigment.

[0088] Further, as a specific example of the above inorganic pigment, titanium oxide (acidification) can be used. ), barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc chromium, iron trioxide, cadmium red, buddha green, chromium oxide, cobalt green ( Green) ), titanium black, synthetic iron oxide black, carbon black, and the like. The pigments of the present invention may be used singly or in combination of two or more.

Among these pigments, it is possible to provide remarkable dispersibility for various pigments widely used in filters for liquid crystal display devices. Specifically, from CI Pigment Yellow 150, CI Pigment Green 36, CI Pigment Green 7, CI Pigment Yellow 138, CI Pigment Yellow 83, CI Pigment Blue 15: 6 C. I. Pigment Violet 23, CI Pigment Red 177, CI Pigment Red 254, and CI Pigment Yellow 139, the above-mentioned phthalocyanine pigment having a high bromination rate, or a group of the above-mentioned different kinds of metal phthalocyanine pigments, wherein at least one pigment is selected to prepare a pigment dispersion, and the pigment is dispersed. The liquid can be used properly.

[0090] The pigment dispersion liquid is not particularly limited, and various pigment dispersion liquids can be used.

As a specific example of a pigment dispersion which may be used, guanamine ( ), decylamine, dodecylamine, N-dodecylhexylamine, N-octadecylpropionamide, N,N-dimethyldodecanamine, and N,N-dihexyl Amidoxime compound such as acetamide; diethylamine , an amine compound such as diheptylamine, dibutylhexadecaneamine, N,N,N',N'-tetramethylmethylamine, triethylamine, tributylamine and trioctylamine; Ethanolamine ), diethanolamine, triethanolamine, N,N,N',N'-tetrakis(hydroxyethyl)-1,2-diaminoethane (N,N,N',N'-( )-1,2- ), N, N, N'-tris(hydroxyethyl)-1,2-diaminoethane, N,N,N',N'-tetrakis(hydroxyethylpolyoxyethylene)-1,2-di Aminoethane, 1,4-bis(2-hydroxyethyl)pyridazine (1,4- (2- ) And a hydroxyl group-containing amine such as 1-(2-hydroxyethyl)pyridazine, etc., may be exemplified herein, and other compounds such as piperidinamide, isopiperidinamide or nicotinic acid amide may also be used. .

Further, a copolymer of an unsaturated carboxylic acid ester such as polyacrylate or a (partial) ammonium salt of a copolymer of an unsaturated carboxylic acid ester such as polyacrylate or the like may be mentioned. Partially an ammonium salt or a (partial) alkylamine salt; a copolymer of a hydroxyl group-containing unsaturated carboxylic acid ester such as a hydroxyl group-containing polyacrylate; or a denature thereof; a polyurethane; an unsaturated polyamine Polysiloxanes; long-chain polyaminoguanamine phosphates; decylamines obtained by reacting poly(lower alkyleneimine) with polyesters containing free carboxyl groups or salts thereof.

[0092] In addition, as a commercial product of a dispersing agent, there may be mentioned, -105 (trade name, Made by the company); Disperbyk-101, Disperbyk-130, Disperbyk-140, Disperbyk-170, Disperbyk-171, Disperbyk-182, Disperbyk-2001 (above . Manufactured by the company; EFKA-49, EFKA-4010, EFKA-9009 (above EFKA CHEMICALS); 12000, 13240, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 33500 (above Made by the company); PB821, PB 822 (made by Ajinomoto Co., Ltd.).

When the amount of the pigment dispersant used is 100 or less, the pigment dispersant is usually 10 to 90% by mass, preferably 20 to 80% by mass.

[0094] The coloring composition is further blended with an ultraviolet blocking agent, a purple line absorbent, a surface conditioner (leveling agent), and other ingredients in accordance with the needs thereof.

[0095] The colored composition may be produced by directly mixing the component (a), the pigment, the pigment dispersant, and other components as needed, and the component (c), and dispersing it by using a disperser well known in the art. However, a method of pre-modulating the pigment dispersion is preferred because of the incomplete pigment dispersion.

According to this method, a photosensitive coloring composition excellent in pigment dispersibility can be easily obtained. In this case, in particular, in the case of formulating the component (e), it is mixed and dispersed in a solvent for dispersing a pigment, a pigment dispersant, and a component (e) which is required to be required (hereinafter referred to as "dispersion solvent"). Therefore, the pigment dispersion is prepared in advance. On the other hand, the component (a) other than the above and the component (e) or other component which is required to be used are mixed in a solvent (hereinafter referred to as "dilution solvent") for dilution purposes, and dissolved or dispersed according to the preparation. Pure liquid resist liquid). Then, the obtained pigment dispersion liquid and the pure resist liquid are mixed, and if necessary, dispersion treatment is carried out, whereby a coloring composition having remarkable pigment dispersibility is easily obtained. According to this method, since the dispersing solvent and the diluting solvent can be individually selected, the range of solvent selection becomes wide.

[0097] When the pigment dispersion liquid is not prepared in advance, first, a pigment, a pigment dispersant, and an alkali-soluble resin as needed are added to an organic solvent, and the mixture is sufficiently mixed and stirred to disperse the pigment, and the carboxyl group is added. The residual components such as the polyfunctional acrylate are mixed, and in the dispersion work of the pigment, not only the pigment dispersibility is achieved, but also the stability is remarkable because of other mixed components.

[0098] The colored composition obtained in this manner is applied to a support to form a coating film, and after drying, a part of the coating film is selectively irradiated by irradiating the light onto the coating film according to a predetermined pattern. After hardening, it is developed with an alkali solution, post-baked, and then thermally cured to obtain a colored coating film having a predetermined pattern.

[0099] The light used, ultraviolet or visible light is ideal, and light from 240 nm to 410 nm can be used from a high-pressure mercury lamp or a halogen lamp. The energy required for hardening is usually 10 to 500 mJ/mm 2 . In the exposure operation, the surface of the coating film may be irradiated with laser light, or the light may be irradiated through the mask to selectively expose and harden the coating film at the set position.

[0100] Also, heat hardening, usually using a vacuum dryer, an oven, a heating plate, or other means for providing heat, drying at a temperature of 50 to 200 ° C, and then heating at a temperature of 120 to 250 ° C to make it hardening.

[0101] The portion of the coating film that has been hardened by the cross-linking and bonding network formed by the photohardening reaction and the thermosetting reaction according to the present invention described above has a structure in which the pigment is uniformly dispersed.

[0102] The coloring composition has excellent hardenability, and the crosslinking density is improved. Since the interior is uniformly and uniformly hardened, it is difficult to form a reverse taper during development (reverse ), in the forward taper state, a pattern with sharp edges and good surface smoothness can be formed.

Further, in the coloring composition of the present invention, the crosslinking density is hardened evenly inside the hardening, and the impurities are blocked inside in the high matrix, and high dielectric reliability can be obtained because the liquid crystal layer is not easily dissolved. The color hardened film. In particular, when the colored layer of the liquid crystal panel is produced by using the colored cured film, the voltage of the display panel can be stabilized, so that the power reliability is high.

Further, the coloring composition described above can finely and uniformly disperse a pigment having a high concentration, and since the coloring shape is high, even if it is thin, the coloring concentration is sufficient to form a large colored pattern, and the color reproduction range is large. Very wide.

[0105] The coloring composition can be suitably used for various colored coating films, in particular, a coloring layer constituting the details of the color filter, that is, a pixel or a black matrix.

[The effect of the present invention]

When the component (a) having excellent curability and alkali developability is required as the composition of the present invention, it can be used as a composition for forming an active energy ray-hardening dies pattern, and high exposure sensitivity can be formed. It has a good image, a fine and precise pattern, and, after hardening, becomes an excellent product of various properties such as film strength, heat resistance and chemical resistance.

Further, the composition of the present invention can be formed into a pattern even if the alkali-soluble resin (e) component is not contained, and the blending ratio may be reduced even in the case of blending the component (e), and relatively more The ratio of the component (a) of the crosslinkable component is formulated.

Further, since the composition of the present invention has high elasticity at room temperature after hardening, the pattern has an advantage that plastic deformation is less likely to occur, and in particular, it is suitable for forming a columnar separator and a color filter protective film, and is suitable for alkali Excellent imaging and suitable for forming colored layers.

[Best way to implement the invention]

[0107] The present invention relates to an active energy ray-curable composition in which the above component (a) is an essential component.

It is preferable that one or more of the compounds (a-1) to (a-3) are selected as the component (a).

Further, as the component (a), a compound containing a hydroxyl group (a2) may also be used, which is also desirable. As (a2), the compound of (a2-1) is desirable.

Further, as the component (a) and (a2), the compound of the above (a3-1) is desirable.

Further, as a component of the present invention, it is preferable to use a component containing the component (b) or/or the component (c).

The composition of the present invention can be preferably used for the formation of a pattern, and in this case, it is preferable to further contain the component (e).

Further, the composition for pattern formation can be preferably used as a composition for a columnar spacer, a composition for a color filter protective film, or a colored composition for a color filter protective film.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples.

In addition, as for the following description, the term "part" refers to the meaning of the mass part; the term "%" means the meaning of the percentage of the mass part.

[0109] ◎ Production Example 1 [manufacturing of (a-1)] In a 500 ml glass flask apparatus stirring apparatus, a thermometer, and a water-cooled condenser, 110 g of ethanol was contained, and the ratio of 30:70 (mass ratio) was contained. A mixture of pentaerythritol pentaacrylate and hexaacrylate acrylate (hydrogen oxyhydroxide price 36 mg potassium hydroxide / g, hereinafter referred to as "g1") 100 g, and valine was added at room temperature ( After that, the reaction was carried out for 4 hours. The reaction is carried out under the atmosphere.

As a result, a solution containing 50% of a solid portion of (a-1) (hereinafter referred to as "a1") having an acid value of 45 mg of potassium hydroxide per gram (converted from a solid portion) was obtained.

[0110] ◎ Production Example 2 [Production of (a2-1)] In the same flask as in Production Example 1, 16 g of succinic anhydride, 250 g of "g1", and methoxyquinone were placed. ) 0.13 grams, raising the temperature to 85 ° C. After 1.3 g of the catalyst triethylamine was added thereto, the reaction was carried out for 4 hours. The reaction was carried out in a mixed gas of air/nitrogen to obtain a compound having an acid value of 34 mg of potassium hydroxide per gram (hereinafter referred to as "h1").

Next, in a separate flask, 103 g of DMDG (trade name: DMDG, hereinafter referred to as DMDG), 100 g of "g1", and 2.6 g of ethanolamine were added at room temperature, and the reaction was carried out. It was placed in the atmosphere for 4 hours.

Thus, the acid value was 33 mg of potassium hydroxide per gram (converted from the solid portion), and the hydroxyl group (converted from the solid portion) was 23 mg of potassium hydroxide per gram (a2-1) (hereinafter referred to as " The solid portion of a2") is a 50% solution.

Also, "h1" is also used in Comparative Examples 2, 5, 8 and 11.

Manufacture Example 3 [Production of (a3-1)] In the same flask as in Production Example 1, 114 g of DMDG and 100 g of "g1" were placed, and after adding 5.4 g of ethanolamine at room temperature, the reaction was carried out. The reaction was placed in the atmosphere in an hour.

Then, 15 g of succinic anhydride, 0.6 g of triethylamine, and 0.06 g of methoxyindole were added, and the temperature was raised to 85 ° C, and the reaction was carried out for 8 hours, and the reaction was carried out in a mixed gas of air/nitrogen.

As a result, a solution containing 50% of a solid portion of (a3-1) (hereinafter referred to as "a3") having an acid value of 70 mg of potassium hydroxide per gram (calculated as a solid portion) was obtained.

◎Production Example 4 [Production of (e) component] A stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube were placed in a separable flask, 52% for phenyl methacrylate, 23% for acrylic acid, and DMDG. Two times the total amount of the monomers, a relative amount of 10% of 2,2'-azo-bis(2-methylbutyronitrile) monomer was added to uniformly dissolve. Then, nitrogen gas was poured, and the mixture was stirred at 85 ° C for 2 hours, and then, the reaction was carried out at 100 ° C for 1 hour. Subsequently, 25% of glycidyl methacrylate was added to the obtained solution, 10% of triethylamine relative to glycidyl methacrylate, and 1% of hydroquinone relative to glycidyl methacrylate. And DMDG as a monomer filled with a total mass of 35% with glycidyl methacrylate, and stirred at 100 ° C for 5 hours to obtain a desired copolymer solution (concentration of the solid portion was 31.5%).

The obtained component (e) (hereinafter referred to as "e1") had a molecular weight (Mw) of 14,200, an acid value of 84 mg of potassium hydroxide per gram, and a hydroxyl group of 96 mg of potassium hydroxide per gram.

[0113] ◎Comparative Production Example 1 [Production of component (i1)] A stirring device, a thermometer, and a water-cooled condenser were placed in a 500 ml glass flask, and 91 g of DMDG and 1,2,3,4-butane were placed. Tetracarboxylic dianhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., trade name BT-100, hereinafter referred to as "BT-100") 10 gram, "g1" 150 gram, methoxy oxime 0.08 gram, the temperature was raised to 95 °C. After 0.8 g of triethylamine was further added thereto, the reaction was carried out for 8 hours, and the reaction was carried out in a mixed gas of air/nitrogen.

As a result, a solution containing 65% of a solid portion of a compound having an acid value of 34 mg of potassium hydroxide per gram (hereinafter referred to as "i1") was obtained.

[0114] ◎ Examples 1 to 6 and Comparative Examples 1 to 6 (resin or resin composition for protective film) The ratios shown in the following Tables 1 and 2 are mixed according to the general method (a) to (c) The component and the component (e) are adjusted to a resin composition for a separator or a protective film.

Using the resulting composition, the evaluations shown below were carried out and the results are shown in Tables 1 and 2.

[0115] <Developing property> The composition described in the first and second paragraphs was coated on a chrome-plated glass substrate of 10 cm X 10 cm by a rotary coater, and the coating film was blown with an air dryer of 80 ° C. The air was blown for 10 minutes to dry, and a coating film having a dried film thickness of 5 nm was formed. The obtained coating film was subjected to spray development with a 0.5% by weight aqueous solution of sodium carbonate, and the time at which it was completely dissolved was measured, and evaluated according to the following criteria.

○: Completely dissolved in 15 seconds.

△: Completely dissolved in 60 seconds.

X: Not dissolved at all within 60 seconds.

[0116] <Residue> Observe the presence or absence of dissolved residue on the surface of the substrate after the imaging evaluation, and evaluate it according to the following criteria.

○: There was no dissolved residue at all.

△: Only a small amount of residue was dissolved.

X: There are many dissolved residues.

[0117] <Evaluation of Elastic Deformation Rate> The composition described in Tables 1 and 2 was applied on a chrome-plated glass substrate of 10 cm X 10 cm by a rotary coater, and the coating film was blown at 80 ° C. The dryer was blown for 10 minutes to dry, and a coating film having a dried film thickness of 6 nm was formed. The obtained coating film was irradiated at a distance of 100 μm with an ultrahigh pressure mercury lamp equipped with a near-middle line of a photomask, with an ultraviolet light of 300 mJ/cm 2 (in terms of 365 nm illuminance). Then, it was immersed in a 0.5% by weight aqueous solution of sodium carbonate at 23 ° C for 60 seconds to carry out alkali development, and only the unhardened portion of the coating film was removed. Thereafter, heat treatment was carried out in the same manner as in the environment of 200 ° C for 30 minutes to form a columnar separator having a height of 5 μm and a diameter of 15 μm.

The elastic deformation rate of the obtained columnar separator at room temperature was measured by an ultra-micro hardness tester equipped with a flat head (forming a 100 μm X 100 μm indenter) The company manufactures, H-100C), the compressive load is measured under the condition of 0.2 GPa, and is calculated according to [(elastic deformation amount / total deformation measurement) × 100].

【0118】

【0119】

[0120] The figures relating to the composition fields of Schedules 1 and 2 represent the weight (mass), and a1~a3, e1 and i1 are expressed in proportion to the solid portion.

Further, the abbreviations associated with Tables 1 and 2 have the following meanings: Irg907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane (2- -1-(4- )-2- -1- ),by Company manufacturing, trade name 907.

[0121] The compositions of Examples 1 to 6 exhibited very remarkable developability, and there was no residue at all on the substrate. More than this, the cured product of these compositions is a separator or a protective film and has a sufficient elastic deformation rate.

In view of the above, Comparative Examples 1 and 4 using "g1" of an alkali-insoluble polyfunctional acrylate, or a carboxyl group obtained by addition reaction of a compound having a hydroxyl group and a (meta)acrylic group with a divalent carboxylic acid anhydride The compositions of Comparative Examples 2 and 5 of "h1" of a functional group (bias) acrylate are incomplete in development and residue; and have one or more hydroxyl groups and two or more (partial) acrylic groups. The composition of Comparative Examples 3 and 6 of the "i1" of the carboxyl group-containing polyfunctional (meta) acrylate obtained by the addition reaction of a compound with a tetravalent carboxylic acid dianhydride, the development property of the residue-free substance is Not complete.

[0122] ◎ Examples 7 to 13 and Comparative Examples 7 to 13 (cyan coloring composition) The ratios shown in the following Schedules 3 and 4 are (a) to (c) and (e) The ingredients, pigments, and dispersing agents are mixed according to the general practice and formulated into a colored composition.

Using the obtained composition, the developability and the residue were evaluated in accordance with the following methods. The results are shown in Schedule 3 and Schedule 4.

<Development property> In the examples 1 to 6, the development was carried out in the same manner except that the dry film thickness was 2 μm. The obtained coating film was subjected to spray development with a 0.5% by weight aqueous solution of sodium carbonate, and the time at which it was completely dissolved was measured, and it was evaluated according to the following criteria.

○: Completely dissolved in 60 seconds.

△: Completely dissolved in 90 seconds.

X: Not dissolved at all within 90 seconds.

[0124] The surface of the substrate after the <residue> imaging evaluation was wiped 10 times with a cotton swab containing ethanol, and the cotton swab was examined for coloration, and evaluated according to the following criteria.

○: The cotton swab is completely uncolored.

△: The cotton swab is slightly colored.

X: There is coloring on the cotton swab.

[0125] [Schedule 3]

【0126】

[0127] In addition, the abbreviations in Schedules 3 and 4 are the same as those shown in Schedule 1.

PB: Pigment, C.I. Pigment Blue 15:6.

DIS: pigment dispersant, Disperbyk-2001, solid part 46% (main solvent: propyl methoxyacetate, methoxypropanol, butyl cellosolve)

[0128] The compositions of Examples 7 to 13 were excellent in developability, and there was no residue at all on the substrate.

On the other hand, in the compositions of Comparative Examples 8 and 11 using "g1", the development properties and the residue were completely failed, and the compositions of Comparative Examples 7, 9, and 12 using "h1" were used for development and residue. Failed completely; the composition of Comparative Examples 10 and 13 using "i1" had no residue and its imaging properties were incomplete.

[0129] ◎ Examples 14 to 16 and Comparative Examples 14 to 16 (red coloring composition) The ratios shown in the following Tables 5 and 6 are (a) to (e) components, pigments, and The pigment dispersant is mixed according to a general usual method to prepare a coloring composition.

Using the obtained composition, the relevant developability and residue were evaluated in the same manner as in Examples 7 to 13, and the results are shown in the attached Tables 5 and 6.

【0130】

【0131】

[0132] In addition, the abbreviations referred to in Schedules 5 and 6 are the same as those shown in Schedules 1 and 3, except as noted below.

PR: A pigment, C.I. Pigment Red 177.

[0133] The compositions of Examples 14 to 16 were excellent in developability, and there was no residue at all on the substrate.

On the other hand, in Comparative Example 14 using "g1" or the composition of Comparative Example 15 using "h1", the development property and the residue were completely failed, and the composition of Comparative Example 16 using "i1" was used for the development. Sex and residue are completely unsatisfactory.

[Possible use in industry]

The composition of the present invention can be used for various applications such as inks, paints, and resists, and can be used as a composition for pattern formation such as a resist.

Further, the composition of the present invention can be suitably used for the production of a liquid crystal panel, and a composition for a columnar spacer and a color filter protective film, a color filter, and a coloring composition by forming a pixel or a black matrix. .

Claims (8)

An active energy ray-curable composition comprising a compound (a) having two or more (partially) propylene fluorene, a tertiary amino group and an acidic group as an essential component active energy ray-curable composition, and the compound (a) One or more of the following compounds (a-1) to (a-3), (a2-1), and (a3-1) are used as the active energy line hardening type composition; (a- 1): a Michael addition reaction product of a compound having 3 or more (partially) propylene fluorenyl groups with a primary amine or a secondary amine having an acidic group; (a-2): having 3 or more (partially) acrylonitrile groups And a Michael addition reaction product of a compound having an acidic group and a primary or secondary amine having an acidic group; (a-3): a compound having 3 or more (partially) acrylonitrile groups and an acidic group and having no acidic group and a Michael addition reaction product of a hydroxyl group monoamine or a secondary amine; (a2-1): a compound having three or more (partially) propylene fluorenyl groups and an acidic group and a Michael plus a hydroxyl group primary or secondary amine a reaction product; (a3-1): a Michael addition reaction product having a compound of three or more (partially) propylene groups and a primary or secondary amine having a hydroxyl group, The compound obtained by addition reaction of acid anhydride. The active energy line hardening type composition of claim 1, further comprising a photopolymerization initiator. The active energy line hardening composition of claim 1 further includes an organic solvent. The active energy line hardening composition of claim 2, and further comprising an organic solvent. The active energy ray-curable composition of any one of the first to fourth aspects of the patent application is prepared as a composition for forming an active energy ray-curable pattern. The active energy line hardening type composition of claim 5, and further contains an alkali soluble resin. For example, the active energy ray-curable composition of the fifth aspect of the patent application is used as a composition for a columnar separator, a composition for a color filter protective film, or a coloring composition for a color filter. The composition of the columnar separator, the composition for a color filter protective film, or the coloring composition for a color filter is prepared as an active energy wire hardening type composition of the sixth aspect of the invention.