KR20070093421A - Compositions curable with actinic energy ray - Google Patents

Abstract

[PROBLEMS] To provide an actinic-energy-ray-curable composition which, when used as a composition for pattern formation, has high sensitivity to exposure light and satisfactory developability and can form a fine precise pattern and which after curing is excellent in various properties including film strength, heat resistance, and chemical resistance; a composition for pattern formation which, when used in color filter formation in liquid-crystal panel production, not only has those performances but, after curing, has high elasticity and an elastic behavior which makes the cured composition suitable for use as columnar spacers and a protective film; and a coloring composition which, when used, e.g., for forming pixels of a color filter, gives a colored layer reduced in color unevenness and contrast unevenness. [MEANS FOR SOLVING PROBLEMS] The actinic-energy-ray-curable compositions contain as an essential ingredient a compound (a) having two or more ethylenically unsaturated groups, a tertiary amine group, and an acid group.

Description

Active energy ray curable composition {COMPOSITIONS CURABLE WITH ACTINIC ENERGY RAY}

TECHNICAL FIELD The present invention relates to an active energy ray-curable composition, and the composition of the present invention can be used for various uses, such as compositions for forming patterns such as inks, paints, and resists, and in particular, the pattern is formed because of its excellent alkali developability. It can use suitably as a composition for, and belongs to these technical fields. The composition of the present invention can be particularly preferably used for liquid crystal panel production, and specifically, it can be suitably used for applications such as columnar spacer production, color filter protective film production, and color layer formation for color filters. It also belongs to the field.

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

In this case, since polyfunctional (meth) acrylate is alkali insoluble, the film remainder of the unhardened part coating film generate | occur | produced at the time of image development, and there existed a problem that sufficient resolution was not obtained, but a hydroxyl group and a (meth) acryloyl group Examination of the carboxyl group-containing polyfunctional (meth) acrylate obtained by adding the compound which has the thing with bivalent carboxylic anhydride has been made | formed.

However, depending on the use used, hardness and developability may be insufficient even in the said carboxyl group-containing polyfunctional (meth) acrylate.

Therefore, in order to further improve hardness and developability, a carboxyl group-containing polyfunctional obtained by addition reaction of a compound having at least one hydroxyl group and at least two (meth) acryloyl groups with a dianhydride of a tetravalent carboxylic acid ( Examination of meth) acrylate is also made (patent document 1).

However, also when using the carboxyl group-containing polyfunctional (meth) acrylate of patent document 1, since there existed a shortage of crosslinking density, it had a problem that cured film strength, heat resistance, and chemical-resistance were inferior.

On the other hand, in the composition for active energy ray hardening pattern formation for color filters used in manufacture of a liquid crystal panel, the crosslinking density of hardened | cured material and alkali solubility are many requested | required.

As a composition for active energy ray hardening pattern formation for color filters, the composition containing the polyfunctional (meth) acrylate compound which does not have a carboxyl group, alkali-soluble resin, a photoinitiator, and the organic solvent is known (patent document 2).

In order to improve the crosslinking density and alkali solubility of hardened | cured material, this invention increased the introduction ratio of the photocurable group and acidic functional group of alkali-soluble resin, but there is a limit to the quantity of the photocurable group and acidic functional group which can be introduced, The problem that the viscosity of a composition rises and coating applicability is impaired also arises.

In order to solve this problem, the composition for pattern formation using the polyfunctional (meth) acrylate which has a carboxyl group is proposed (patent document 3). However, according to this composition, since the compound which has one carboxyl group is used in 1 molecule, alkali solubility improves, but especially when content of alkali-soluble resin is small, developability was insufficient and sensitivity was not enough.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-089416 (claims)

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-105456 (claims)

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-91954 (claims)

The first object of the present invention is that when used as a composition for forming an active energy ray-curable pattern, the exposure sensitivity is high, developability is good, precise and accurate patterns can be formed, and the cured film strength after curing, It is to provide an active energy ray-curable composition having excellent physical properties such as heat resistance and chemical resistance.

The second object of the present invention is, when used for the production of color filters in liquid crystal panel production, in addition to the above-described performance, it is highly elastic after curing and for pattern formation having an elastic behavior suitable for columnar spacers and protective films. In providing a composition, and when forming the pixel of a color filter, etc., a colored layer provides the active energy ray hardening type coloring composition with few color unevenness or contrast unevenness.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. In addition, in this specification, (meth) acryl means an acryl and / or methacryl, (meth) acrylate means an acrylate and / or methacrylate, and (meth) acryloyl means acryloyl And / or methacryloyl.

The present invention relates to an active energy ray-curable composition containing a compound (a) (hereinafter referred to as "(a) component") having two or more ethylenically unsaturated groups, tertiary amino groups and acidic groups.

Hereinafter, the component (a) and the other components will be described.

1. (a) Component

As (a) component used in this invention, if it is a compound which has two or more ethylenically unsaturated groups, tertiary amino groups, and an acidic group, various compounds can be used. As (a) component, the compound which has three or more ethylenically unsaturated groups is preferable in the reason that it is excellent in sclerosis | hardenability, and the hardened | cured material is high hardness.

As an ethylenically unsaturated group in (a) component, a (meth) acryloyl group, a (meth) allyl group, a vinyl group, etc. are mentioned, A (meth) acryloyl group is preferable at the point which is easy to obtain and manufacture. Do.

As an acidic group in (a) component, a carboxyl group, a sulfonyl group, a phosphoric acid group, etc. are mentioned, A carboxyl group is preferable at the point which is easy to acquire and manufacture.

As an acid value which shows the ratio of the acidic group in 1 molecule of (a) component, 10-150 mgKOH / g is preferable from a reason for being excellent in developability and a pattern shape when a composition is used for pattern formation, More preferably, Is 20 to 100 mgKOH / g.

As molecular weight of (a) component, the thing of 400-3,000 is preferable.

As (a) component, you may consist of multiple types of the compound mentioned later.

As (a) component, at least 1 sort (s) chosen from the compound of following (a-1)-(a-3) is preferable because it can manufacture easily.

(a-1): The compound which has three or more (meth) acryloyl groups (henceforth "a polyfunctional (meth) acrylate"), and the primary or secondary amine which has an acidic group (henceforth "acidic amine" Michael addition reaction product (henceforth "(a-1)").

(a-2): Michael addition reaction product of the compound which has three or more (meth) acryloyl groups and an acidic group (henceforth "acidic polyfunctional (meth) acrylate"), and an acidic amine [Hereafter, "(a-2 )].

(a-3): Michael addition reaction product of the acidic polyfunctional (meth) acrylate, the primary or secondary amine (hereinafter referred to as "amine") having no hydroxyl group and acidic group [hereinafter "(a-3) Is called.

Hereinafter, these (a-1)-(a-3) are demonstrated.

1-1. (a-1)

As the polyfunctional (meth) acrylate in (a-1), various compounds can be used as long as it is a compound having three or more (meth) acryloyl groups.

Specifically as a polyfunctional (meth) acrylate, a trimethol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, and a ditrimethol propane tetra (meth) Polyol poly (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Poly (meth) acrylates of alkylene oxide adducts of the polyols; And tri (meth) acrylates of isocyanuric acid alkylene oxide adducts. Ethylene oxide, a propylene oxide, etc. are mentioned as said alkylene oxide.

Among these, the compound which has four or more (meth) acryloyl groups is preferable. It is especially preferable because the elastic strain rate of the hardened | cured material from which dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and hexa (meth) acrylate are obtained is higher.

As acidic amine, the primary or secondary amine which has a carboxyl group is preferable.

Examples of the amines include amino acids, and specific examples include primary amines such as aminocaproic acid, secondary amines such as proline, and diamines having primary amino groups such as glycylglycine and secondary amino groups.

The specific example of (a-1) is shown to following formula (1). Formula (1) uses 1 mol of dipentaerythritol hexaacrylate [(A)] as polyfunctional (meth) acrylate, and uses 1 mol of secondary amines [(B)] which have a carboxyl group as acidic amine. This is an example.

In the formula (A), A represents an acryloyloxy group of acrylic, A 'is -OCOCH ₂ CH ₂ - shows a.

1-2. (a-2)

The acidic polyfunctional (meth) acrylate in (a-2) is referred to as a compound (hereinafter referred to as "hydroxy polyfunctional (meth) acrylate") having three or more (meth) acryloyl groups and one hydroxyl group. ) And a compound having one or two acid anhydride groups in the same molecule (hereinafter referred to as "acid anhydride").

Specific examples of the hydroxy polyfunctional (meth) acrylate include pentaerythritol triacrylate, dipentaerythritol penta (meth) acrylate, and the like.

As hydroxy polyfunctional (meth) acrylate, the compound which has four or more (meth) acryloyl groups in the same molecule is preferable.

As hydroxy polyfunctional (meth) acrylate in this invention, you may contain the compound which has three or more (meth) acryloyl groups by-produced in a manufacturing process. For example, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. These usually contain pentaerythritol tri (meth) acrylate in pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate in dipentaerythritol hexa (meth) acrylate.

The compound which has these three or more (meth) acryloyl groups may be contained in the ratio of 20-80 mass% in the hydroxy polyfunctional (meth) acrylate component.

As the acid anhydride, succinic anhydride, 1-dodecenyl succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, tetramethylene anhydride, tetrahydro phthalic anhydride, methyl Compound which has one acid anhydride group in the same molecule, such as tetrahydro phthalic anhydride, endo methylene tetrahydro phthalic anhydride, methylendo methylene tetrahydro phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, or anhydrous Pyromellitic acid, phthalic anhydride dimer, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfontetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and 1,2,3,4-butane tetracarboxylic Acid dianhydride, diphenyl ether tetracarboxylic anhydride, trimellitic acid ethylene glycol anhydride Switch and the like can be given hotel (as commercial products, for example, there are, trade name: LA kasit FIG TMEG-100 Nippon Chemical Co., Ltd.).

As a manufacturing method of an acidic polyfunctional (meth) acrylate, it should follow a conventional method.

For example, the method of making hydroxy polyfunctional (meth) acrylate and an acid anhydride react at 60-110 degreeC for 1 to 20 hours in presence of a catalyst is mentioned.

Examples of the catalyst in this case include N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide and zinc oxide. Can be mentioned.

Examples of acidic amines include those mentioned above.

The specific example of (a-2) is shown to following formula (2). Formula (2) uses the secondary amine [(B) which has a carboxyl group as acidic amine, using 1 mol of acid anhydride adducts ((C)] of dipentaerythritol pentaacrylate as acidic polyfunctional (meth) acrylate. ] Is an example of using 1 mole of].

In Formula (C), A and A 'represent the same group as Formula (A).

1-3. (a-3)

Examples of the acidic polyfunctional (meth) acrylate in (a-3) include those mentioned above.

Specific examples of the amine include primary amines such as n-propylamine, n-butylamine, n-hexylamine and benzylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine and cyclo And secondary amines such as hexylamine and morpholine.

The specific example of (a-3) is shown to following formula (3). Formula (3) is an example in which 1 mol of amine [(D)] reacts with 2 mol of the acid anhydride adduct [(C)] of dipentaerythritol pentaacrylate as acidic polyfunctional (meth) acrylate.

However, in an actual reaction, when 1 mol of (D) is used with respect to 2 mol of (C), it may gelatinize, and less than 1 mol of (D) with respect to 2 mol of (C), Preferably, the reaction is carried out at a ratio of 0.8 mol or less.

1-4. Manufacturing method of (a-1)-(a-3)

(a-1)-(a-3) show that a polyfunctional (meth) acrylate and an acidic amine, an acidic polyfunctional (meth) acrylate and an acidic amine, and an acidic polyfunctional (meth) acrylate and an amine, respectively, It is obtained by addition reaction.

As a preferable ratio of a raw material component, what is necessary is just to set suitably according to the objective, Preferably it is as follows.

(a-1): 0.2-0.4 mol is preferable in the case of acidic primary amine with respect to 1 mol of total amounts of the (meth) acryloyl group in polyfunctional (meth) acrylate, and 0.4-0.8 mol is preferable in acidic secondary amine. desirable.

(a-2): 0.2-0.4 mol is preferable in the case of acidic primary amine with respect to 1 mol of total amounts of the (meth) acryloyl group of acidic polyfunctional (meth) acrylate, and 0.4-0.8 in the case of acidic secondary amine. Moles are preferred.

(a-3): 0.2-0.4 mol is preferable with respect to 1 mol of total amounts of the (meth) acryloyl group of an acidic polyfunctional (meth) acrylate, and 0.4-0.8 mol is preferable with a secondary amine. Do.

As a method of Michael addition reaction, it should follow a conventional method. Specifically, the method etc. which make these compounds react at normal temperature-about 50 degreeC for 1 hour or more are mentioned.

The polyfunctional unsaturated compound which is a raw material of (a-1)-(a-3) component, acidic amine, acidic polyfunctional (meth) acrylate, acidic amine, and acidic polyfunctional (meth) acrylate and amine are respectively independent. It can also be used in combination of 2 or more types.

1-5. (A) component having a hydroxyl group

As the component (a), a compound having a hydroxyl group (hereinafter referred to as "(a2)") is excellent in affinity with an aqueous solution which is a developing solution and excellent in developability when the composition is used for pattern formation. It is preferable for the reason.

As a specific example of (a2) component, the compound etc. which are shown below are mentioned.

1) As a polyfunctional (meth) acrylate in (a-1), three or more (meth) acryls, such as ditrimethyrol propane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate, Compound prepared using the compound having a diary and a hydroxyl group.

2) A hydroxyl group obtained by reacting an acid anhydride in a proportion less than the total amount of hydroxyl groups in the hydroxy polyfunctional (meth) acrylate as the acidic polyfunctional (meth) acrylate in (a-2) and (a-3). Compound prepared using an acidic polyfunctional (meth) acrylate having.

3) Michael addition reaction product of an acidic polyfunctional unsaturated compound and a primary or secondary amine (henceforth "hydroxylamine") which has a hydroxyl group (henceforth "(a2-1)").

Among these, since (a2-1) is easy to adjust the introduction amount of an acidic group and a hydroxyl group arbitrarily, it is preferable.

In (a2-1), the above-mentioned thing is mentioned as acidic polyfunctional (meth) acrylate.

Specific examples of the hydroxyamine include primary amines such as monoethanolamine, 2- (2-aminoethoxy) ethanol, o-aminophenol, m-aminophenol, and p-aminophenol, N-methylethanolamine, and N. And secondary amines such as acetylethanolamine, diethanolamine, 3-anilinophenol, and 4-anilinophenol.

The acidic polyfunctional unsaturated compound and the hydroxy amine may be used alone, or two or more kinds thereof may be used in combination.

The specific example of (a2-1) is shown to following formula (4). Formula (4) is an example in which 1 mol of hydroxyamine [(E)] is reacted with 2 mol of the acid anhydride adduct [(C)] of dipentaerythritol pentaacrylate as an acidic polyfunctional (meth) acrylate. .

However, in actual reaction, when 1 mol of (E) is used with respect to 2 mol of (C), it may gelatinize, and less than 1 mol of (D) is preferable with respect to 2 mol of (C). Preferably, the reaction is conducted at a rate of 0.8 mol or less.

As a manufacturing method of (a2-1), it is good to follow the above methods.

1-6. Other example

As (a) component and (a2), the compound obtained by addition-reacting the Michael addition reaction product of polyfunctional (meth) acrylate or hydroxy polyfunctional (meth) acrylate, and hydroxylamine other than the above with an acid anhydride [follows] "(A3-1)"] is mentioned.

In the Michael addition reaction product of polyfunctional (meth) acrylate or hydroxy polyfunctional (meth) acrylate with hydroxylamine, when the equivalent ratio of hydroxyl group and acid anhydride group is 1, it becomes (a) component, Similarly, when the equivalent ratio of hydroxyl group and acid anhydride group is less than 1, it becomes (a2) component.

The specific example of (a3-1) is shown to following formula (5). Formula (5) uses 2 mol of dipentaerythritol hexaacrylate [(A)] as polyfunctional (meth) acrylate, and it is an acid anhydride [(F) with respect to 1 mol of hydroxyamine [(E)]. ] Is an example of 1 mol reaction.

However, in actual reaction, when 1 mol of (E) is used with respect to 2 mol of (A), it may gelatinize, and less than 1 mol of (E) with respect to 2 mol of (A), Preferably, the reaction is carried out at a ratio of 0.8 mol or less.

As a manufacturing method of (a3-1), any of the addition reaction of Michael and the addition reaction of an acid anhydride should follow the above method.

2. Other Ingredients

Although the composition of this invention is essential to the above-mentioned component (a), other components can be mix | blended as needed.

Specifically, a photoinitiator, an organic solvent, an unsaturated group containing compound, a pigment, dye, an antifoamer, a leveling agent, an inorganic filler, an organic filler, etc. can also be mix | blended. Moreover, you may add a small amount of antioxidant, a light stabilizer, a ultraviolet absorber, a polymerization inhibitor, etc. as needed.

Hereinafter, a photoinitiator, an organic solvent, and an unsaturated group containing compound are explained in full detail.

2-1. Photopolymerization initiator

Although the composition of this invention hardens | cures by irradiation of an active energy ray, as an active energy ray in this case, an electron beam, a visible ray, an ultraviolet-ray, etc. are mentioned. Among these, visible light or ultraviolet light is preferable because it does not require a special device and is simple.

In the case of the visible or ultraviolet curable composition, a photopolymerization initiator is blended into the composition. In addition, when setting it as an electron beam curable composition, it is not necessary to mix | blend a photoinitiator.

Examples of the photopolymerization initiator (hereinafter referred to as "(b) component") include a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, a polynuclear quinone compound, and a xane. Ton compounds, thioxanthone compounds, triazine compounds, ketal compounds, and the like.

Specific examples of the biimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-ratio. Imidazole, 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'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-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-tribro Mophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

When using a biimidazole type compound as (b) component, using a hydrogen donor together is preferable at the point which can improve a sensitivity further. The "hydrogen donor" as used here means the compound which can supply a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure.

As the hydrogen donor, mercaptan-based hydrogen donors, amine-based hydrogen donors and the like are preferable.

The mercaptan-based hydrogen donor is composed of a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, preferably one to three, more preferably one to two mercapto groups directly bonded to the mother nucleus. . Specific examples of the mercaptan-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, and 2,5-dimercapto-1,3,4-thiadiazole. And 2-mercapto-2,5-dimethylaminopyridine. Among 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 heterocycle as a mother nucleus and having at least one, preferably one to three, more preferably one to two amino groups directly bonded to the mother nucleus. Specific examples of the amine hydrogen donor include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiophenone. And ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, and 4-dimethylaminobenzonitrile.

The hydrogen donors may be used alone or in combination of two or more thereof. However, the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors may cause the formed spacers or pixels to fall off the substrate during development. It is difficult to do this, and the intensity and sensitivity of the spacer or the pixel are also preferable. Moreover, the hydrogen donor which has a mercapto group and an amino group simultaneously can also be used suitably.

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

Specific examples of the acetophenone-based compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2-hydroxy-2-methyl-1- Phenylpropane-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methyl-2-morpholi Nopropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-2-hydroxy propan-1-one, 1- (4-morpholinophenyl) -2- Benzyl-2-dimethylaminobutan-1-one, 1-hydroxy cyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one and the like.

Specific examples of the benzophenone compound 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, methylbenzoyl formate and the like.

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

As a specific example of a xanthone type compound, xanthone, a thioxanthone, 2-chloro thioxanthone, etc. are mentioned.

Specific examples of the triazine-based compound include 1,3,5-tris (trichloromethyl) -s-triazine and 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, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, and the like.

Among these, 1-hydroxycyclohexyl phenyl ketone and 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropane-1-one are polymerized by irradiation of an active energy ray even in a small amount. Since it is disclosed and promoted, it is preferably used in the invention.

(b) A component can be used individually or in combination of 2 or more types.

As a compounding ratio of (b) component, 0.5-20 mass parts is preferable with respect to 100 mass parts of solid content other than the photoinitiator in a composition. If it is less than 0.5 weight part, photocurability may become inadequate, and when it exceeds 20 mass parts, an exposure part may become easy to be broken at the time of alkali image development. Moreover, as a ratio of (b) component, 2-10 weight% is more preferable at the point which can obtain a high precision pattern.

2-2. Organic solvent

In this invention, an organic solvent can be mix | blended for the purpose of improving the coating property of a composition.

What is necessary is just an organic solvent (henceforth "(c) component") to not react with each component of a composition. The organic solvent which has the boiling point of 80-200 degreeC is preferable at the point which is excellent in applicability | paintability, and the drying speed of the coating film obtained is suitable, and the organic solvent which has a boiling point of 100-170 degreeC is especially more preferable.

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; Alkylene glycol ethers such as propylene glycol monomethyl ether; Alcohols such as ethanol, 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; lactams such as γ-butyrolactam and N-methyl-2-pyrrolidone; And lactones, such as (gamma)-butyrolactone, etc. are mentioned.

(c) A component can be used individually or in combination of 2 or more types.

As a compounding ratio of (c) component, the ratio which becomes 10-50 mass% of solid content concentration of a composition is preferable.

2-3. Unsaturated group-containing compound

The composition of this invention can mix | blend unsaturated group containing compound (henceforth "(d) component") other than (a) component as needed.

As the (d) component, for example, phenoxyethyl (meth) acrylate, carbitol (meth) acrylate, N-vinylcaprolactone, acryloyl morpholine, glycidyl (meth) acrylate, 2-hydrate Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, nonanediol diacrylate, Polyethylene glycol di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, tribromophenyl (meth) acrylate, 2,2-bis (4- (meth) acryloyloxy Ethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl)- Propane, ethylene glycol di (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, trimetholpropane tri (meth) acrylate And pentaerythritol tetra (meth) acrylate, di (meth) acrylate of bisphenol A epoxy resin, various polyurethane poly (meth) acrylates, polyester poly (meth) acrylates, and the like.

(d) A component can be used individually or in combination of 2 or more types.

The preferable compounding ratio of (d) component is 0-50 mass% in a composition.

3. Active Energy Ray Curing Composition

The composition of this invention makes said (a) component essential.

The composition of this invention can be obtained by stirring and mixing (b) component-(e) component and other components as needed other than (a) component which is the said essential component as needed.

As a preferable combination of the composition of this invention, the composition containing (a) component and (b) component, the composition containing (a) component, (b) component and / or (c) component, (a) component, ( The composition containing b) component, (c) component, and / or (d) component is mentioned. What is necessary is just to mix | blend as these compounding ratios according to the above-mentioned preferable compounding ratio.

4. Uses

The composition of the present invention can be used for various uses. For example, coating materials, such as compositions for pattern formation, such as a resist, ink, and a coating material, etc. are mentioned.

As a composition of this invention, since it is excellent in alkali developability among these, it can be used suitably as a composition for pattern formation.

When using the composition of this invention as a composition for pattern formation, it is preferable to contain alkali-soluble resin. Hereinafter, alkali-soluble resin is demonstrated.

4-1. Alkali soluble resin

As alkali-soluble resin (henceforth "(e) component") in this invention, it acts as a binder with respect to (a) component, and is especially soluble with respect to the developing solution used in a developing process, Especially preferably an alkaline developing solution. It does not specifically limit if it has.

Examples of the component (e) include an addition polymer, polyester, epoxy resin, polyether, and the like, and an addition polymer obtained by polymerizing an ethylenically unsaturated monomer is preferable.

As (e) component, alkali-soluble resin which has a carboxyl group is preferable, Especially ethylenically unsaturated monomer which has 1 or more carboxyl groups (henceforth "carboxyl group-containing unsaturated monomer"), and ethylenically unsaturated monomer copolymerizable with this (hereinafter " Copolymer (hereinafter referred to as "carboxyl group-containing copolymer") is preferred.

As an example of a carboxyl group-containing unsaturated monomer, Unsaturated monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, (alpha)-chloroacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof; Mono [(meth) acryloyloxyalkyl] of bivalent or more polyvalent carboxylic acids, such as succinic acid mono (2- (meth) acryloyloxyethyl) and phthalic acid mono (2- (meth) acryloyloxyethyl) Esters; And mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -Carboxypolycaprolactone mono (meth) acrylate. Among these carboxyl group-containing unsaturated monomers, ω-carboxypolycaprolactone monoacrylate and phthalic acid mono (2-acryloyloxyethyl) are the trade names of Aronix M-5300 and M-5400 (Doagosei Co., Ltd.), respectively. It is commercially available.

A carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Moreover, what is necessary is just to copolymerize with a carboxyl group-containing unsaturated monomer as a copolymerizable unsaturated monomer, Aromatic vinyl compound, unsaturated carboxylic ester, unsaturated imides, macromonomer which has a mono (meth) acryloyl group at the terminal, etc. are preferable. Do.

As an aromatic vinyl compound, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, 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, and the like. Can be.

As unsaturated carboxylic acid ester, 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-hydroxy Propyl (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) acrylic Latex, methoxytriethylene glycol (meth) acrylate, Methoxy propylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ² , 6] decane-8-yl (meth) acrylic Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, and the like.

Examples of the unsaturated imides include maleimide, N-phenylmaleimide, N-cyclohexyl maleimide, and the like.

Examples of the macromonomers having a mono (meth) acryloyl group at the terminal include polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane, and the like. have.

As a copolymerizable unsaturated monomer, 2- (3,4,5,6- tetrahydrophthalimide) ethyl (meth) acrylate, 2- (2, 3- dimethyl maleimide) ethyl (meth) acrylate, etc. are also mentioned above. Imide (meth) acrylates; 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate and 3 Unsaturated carboxylic acid aminoalkyl esters such as -dimethylaminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Indenes such as indene and 1-methylindene; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; And aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.

As the carboxyl group-containing copolymer, (meth) acrylic acid is an essential component, and optionally selected from the group of succinic acid mono (2- (meth) acryloyloxyethyl) and ω-carboxypolycaprolactone mono (meth) acrylate. A carboxyl group-containing unsaturated monomer component which further contains at least 1 sort (s) compound, and styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , At least one copolymer selected from the group consisting of glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate 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, and (meth) acrylic acid / 2-hydroxyethyl ( Meta) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate / styrene copolymer, (meth ) Acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / Polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl ( (2) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethylmethacrylate 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 aerial Copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / benzyl (meth) Acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) Acrylate / N-phenylmaleic And the like can be de-copolymer.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, when the said copolymerization ratio is less than 5 mass%, the solubility with respect to the alkaline developing solution of the composition obtained tends to fall, while when it exceeds 50 mass%, the solubility with respect to an alkaline developing solution will become excessive, and when developing with alkaline developing solution, It tends to be easy to cause the spacer layer or the pixel to fall off from the substrate and to cause film roughness on the surface of the spacer.

As (e) component in this invention, since alkali-soluble resin which has an ethylenically unsaturated group in a side chain becomes excellent in the point that the crosslinking density of the cured film obtained improves, coating film strength, heat resistance, and chemical resistance improve. Do.

As alkali-soluble resin which has an ethylenically unsaturated group in a side chain, alkali-soluble resin which has a carboxyl group is preferable. As said resin, what added the unsaturated compound which has an epoxy group (henceforth "epoxy unsaturated compound") to the said carboxyl group-containing copolymer is mentioned.

As an epoxy-type unsaturated compound, epoxy group containing (meth) acrylates, such as glycidyl (meth) acrylate and cyclohexene oxide containing (meth) acrylate, etc. are mentioned.

The addition reaction can be carried out according to a conventional method, and can be produced by adding an epoxy unsaturated compound to a carboxyl group-containing copolymer in an organic solvent or in a solvent-free solvent. As conditions for addition reaction, reaction temperature, reaction time, and a catalyst may be selected suitably 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. Moreover, a number average molecular weight (henceforth "Mn") is 3,000-60,000 normally, Preferably it is 5,000-25,000.

In addition, in this invention, Mw and Mn mean the value which carried out polystyrene conversion of the molecular weight measured by the gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran).

In the present invention, by using the (e) component having such specific Mw and Mn, a photosensitive resin composition excellent in developability is obtained, whereby a pattern having a sharp pattern edge can be formed, and at the time of development Residues, ground contamination, film residues, etc. are less likely to occur on the substrate and the light shielding layer of the unexposed part. Moreover, 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 ratio of (a) component and (e) component, 10-100 mass% of (a) component and 0-90 mass% of (e) component are preferable based on these total amounts, More preferably, (a) 30-100 mass% of components, and 0-70 mass% of (e) components. If the proportion of the component (a) is less than 10% by mass, the crosslinking density decreases, so that the coating film strength, heat resistance and chemical resistance tend to decrease.

As a ratio in the composition of (a) component and (e) component, 10-50 mass% is preferable in a composition as a total amount of (a) component and (e) component. If this ratio is less than 10 mass%, the film thickness after prebaking will become too thin. On the other hand, if it exceeds 50 mass%, the viscosity of a composition will become high too much, and applicability | paintability will become bad, or the film thickness after prebaking will become too thick.

4-2. Pattern Formation Composition

Since the composition of this invention has high exposure sensitivity, is very excellent in developability, and can form a precise and accurate pattern, it can be used suitably as a composition for pattern formation.

When using the composition of this invention as a composition for pattern formation, the composition which consists of (a), (b), (c) and (e) component is preferable.

As a pattern formation method using the said composition, it is following a conventional method, and after apply | coating a composition to a board | substrate and drying to form a coating film, it irradiates and hardens an active energy ray through the mask which has a specific pattern shape on this, The method of developing an unhardened part with a developing solution, etc. are mentioned.

Glass and plastics etc. are mentioned as a board | substrate. As a developing solution, an alkaline developing solution is preferable and it is as showing later in a specific example.

As a composition for pattern formation, resist, such as an etching resist and a soldering resist, a columnar spacer in liquid crystal panel manufacture, the coloring composition for forming pixels, a black matrix, etc. in a color filter, a color filter protective film, etc. are mentioned. have.

The composition of this invention can be used suitably by the use of the columnar spacer in a liquid crystal panel manufacture, the coloring composition for color filters, and the protective film for color filters among these uses.

When using for a columnar spacer and a color filter protective film use, in order to improve applicability | paintability and developability, you may add nonionic surfactant, such as polyoxyethylene lauryl ether, and fluorine-type surfactant. Moreover, you may add an adhesion | attachment adjuvant, a storage stabilizer, an antifoamer, etc. suitably as needed.

Hereinafter, the use of a columnar spacer (hereinafter only referred to as "spacer") and a coloring composition is demonstrated.

4-2-1. Spacer

The spacer is formed into a photocurable coating film of the composition by a photolithography method. Although the said spacer can be formed in arbitrary locations of a liquid crystal panel board | substrate, it is generally formed in the black matrix area | region which is a light shielding part of a color filter, or a TFT electrode. More specifically, it forms in the above-mentioned area | region on the pixel formed on the board | substrate, such as glass, on transparent electrodes, such as ITO, formed through the protective film as needed.

As a method of forming a spacer, it should follow a conventional method, for example, after apply | coating the composition of this invention to the film thickness necessary for forming a cell gap on a board | substrate, heating (it abbreviates as "prebaking" hereafter.) Then, the method of drying a coating film, forming through a process of exposure, image development, post-heating (it abbreviates as "post-baking" hereafter), etc. are mentioned.

When apply | coating a composition on a board | substrate, it apply | coats a little thick with respect to the design value of a cell gap in consideration of film | membrane reduction and deformation by image development, post-baking, etc. Specifically, it is preferable to make the film thickness after prebaking become 5-10 micrometers, and to be 6-7 micrometers.

As the coating method, for example, 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 coat method), etc. may be mentioned. The die coat method is used.

Prebaking is performed after apply | coating a composition on a board | substrate. As temperature and time in this case, about 5 to 15 minutes are mentioned at 50-150 degreeC.

Light is irradiated to the coating film surface after prebaking through the mask which has a predetermined pattern shape for forming a spacer.

Ultraviolet light or visible light is preferable, and the light to be used uses wavelength light of 240 nm to 410 nm obtained from a high pressure mercury lamp, a metal halide lamp, or the like.

Although light irradiation conditions are based on the kind of light source, the absorption wavelength of the photoinitiator to be used, the film thickness of a coating film, etc., it is preferable to make it the approximate amount of light irradiation 50-600mJ / cm <2>. If the amount of light irradiation is less than 50 mJ / cm 2, it becomes poor in curing and the exposed portion tends to fall off during development. On the other hand, if the amount of light irradiation is larger than 600 mJ / cm 2, a precise spacer pattern tends to be difficult to be obtained.

After irradiating the coating film surface, the unexposed part is removed with a developer.

As a developing solution, the aqueous solution of an alkali compound can be used. As an alkaline compound, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, ammonia, tetramethylammonium hydroxide, etc. are mentioned, for example. In addition, in order to promote the development speed, an appropriate amount of water-soluble organic solvents such as methanol, ethanol, isopropanol and benzyl alcohol and various surfactants may be added to the developing solution.

The developing method may be any of a liquid coating method, a dipping method and a spray method. After the development, the pattern portion is washed with water for 0.5 to 1.5 minutes and dried by compressed air or the like to obtain a spacer pattern.

The obtained spacer pattern is post-baked in the temperature range of 150-350 degreeC with heating apparatuses, such as a hotplate and oven, and the liquid crystal panel spacer of this invention is obtained.

By post-baking, the residual solvent and the water absorbed at the time of image development can volatilize, and the heat resistance of a spacer can be improved. Although the film thickness of a spacer changes with the cell gap setting value of a liquid crystal panel, it is designed so that it may become 3-5 micrometers after a rough postbaking.

When the composition of the present invention is used for spacer production, compression of a planar indenter (indenter having a flat surface of 100 µm x 100 µm) is performed at room temperature using an ultra-small hardness tester (manufactured by Fischer Instruments Co., Ltd., H-100C). It is preferable that the elastic strain ([elastic strain / total strain measurement) × 100] measured at the condition that the load becomes 0.2 GPa is 60% or more.

By using such a composition, it has sufficient hardness that it is hard to plastically deform with respect to a compression load at room temperature, and has the flexibility to track liquid crystal shrinkage and expansion in the use environment temperature range of a liquid crystal display device. Therefore, the liquid crystal panel substrate obtained by the present invention can form an accurate and uniform cell gap without causing plastic deformation when bonding by the room temperature cell crimping method, and particularly in the ODF method. Also when crimping | bonding is used, it can use suitably.

4-2-2. Coloring composition

When using the composition of this invention as a coloring composition, a pigment and a pigment dispersant are further mix | blended. Hereinafter, these components are demonstrated.

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

As a specific example of an organic pigment, the compound classified as pigment in the color index (Issue of The Society of Dyers and Colourists), ie, the thing assigned the following color index (CI) number is mentioned. Can be. C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Yellow-based pigments such as Pigment Yellow 185; C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 177, C.I. Red pigments such as Pigment Red 254; And C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Blue pigments such as Pigment Blue 15: 6; C.I. Pigment Green 7, C.I. Green pigments such as pigment green 36; C.I. Pigment Violet 23, C.I. Pigment violet 23:19 et al.

In addition, phthalocyanine having a high bromination ratio, which is difficult to disperse conventionally, for example, high brightness G pigment of Monastral Green 6YC and 9YC (manufactured by Abyssia Co., Ltd.), and the central metal is a metal other than copper, for example, Mg, Al, Si High color purity G pigments composed of dissimilar metal phthalocyanine pigments such as, Ti, V, Mn, Fe, Co, Ni, Zn, Ge and Sn can be used.

Specific examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zincated, lead sulfate, lead yellow, zinc sulfur, bengal (red iron oxide (III)), cadmium red, ultramarine blue, chromium oxide green, cobalt green, Umber, titanium black, synthetic iron black, carbon black, etc. are mentioned. In this invention, a pigment can be used individually or in mixture of 2 or more types.

Among these pigments, the pigment dispersion liquid can impart excellent dispersibility to various pigments that are commonly used in color filters for liquid crystal display devices, and specifically, C.I. Pigment Yellow 150, C.I. Pigment Green 36, C.I. Pigment Green 7, C.I. Pigment Yellow 138, C.I. Pigment Yellow 83, C.I. Pigment Blue 15: 6, C.I. Pigment Violet 23, C.I. Pigment Red 177, C.I. Pigment Red 254 and C.I. Pigment yellow 139, the said phthalocyanine pigment with a high bromination rate, and the pigment dispersion containing at least 1 sort (s) chosen from the group which consists of the said dissimilar metal phthalocyanine pigment can be used suitably.

The pigment dispersant is not particularly limited, and various pigment dispersants may be used.

Specific examples of pigment dispersants that can be used include nonanoamide, decanamide, dodecaneamide, N-dodecylhexaamide, N-octadecylpropioamide, N, N-dimethyldodecaneamide and N, N-dihexyl. Amide compounds such as acetamide, amines such as diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N ', N'-tetramethylmethaneamine, triethylamine, tributylamine and trioctylamine Compound, 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-diamino ethane, 1,4-bis (2-hydroxyethyl) Amine etc. which have hydroxyl groups, such as a piperazine and 1- (2-hydroxyethyl) piperazine, etc. can be illustrated, In addition, compounds, such as nipopetamide, isonipecotamide, and nicotinic acid amide, are mentioned. have.

Moreover, (co) polymers of unsaturated carboxylic ester, such as polyacrylic acid ester; (Partial) amine salts, (partial) ammonium salts and (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid; (Co) polymers and modified substances of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters; Polyurethanes; Unsaturated polyamides; Polysiloxanes; Long-chain polyaminoamide phosphates; Amides and salts thereof obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyesters may be mentioned.

Moreover, as a commercial item of a dispersing agent, Shigenox-105 (brand name, the product made by Hot Call Chemical Co., Ltd.), Disperbyk-101, copper-130, copper-140, copper-170, copper-171, copper-182, copper-2001 [more than, Big Chemie Japan Co., Ltd.], EFKA-49, copper -4010, copper-9009 (more than, made in EFKA CHEMICALS company), sole spas 12000, copper 13240, copper 13940, copper 17000, copper 20000, copper 24000GR, copper 24000SC, 27000, 28000, 33500 (above, made by Geneka Co., Ltd.), PB821, 822 (above, made by Ajinomoto Co., Ltd.), etc. are mentioned.

A pigment dispersant is 10-90 mass parts normally with respect to 100 mass parts of pigments, Preferably it uses in the ratio of 20-80 mass parts.

You may mix | blend a sunscreen, a ultraviolet absorber, a surface conditioner (leveling agent), and other components with a coloring composition as needed.

Although the coloring composition may be manufactured by mixing (a) component, a pigment, a pigment dispersing agent, and other components directly to (c) component as needed, and disperse | distributing using a well-known dispersing machine, pigment dispersion becomes inadequate Since this exists, the method of preparing a pigment dispersion liquid previously is preferable.

According to this method, the photosensitive coloring composition excellent in the pigment dispersibility can be obtained easily. In this method, especially when mix | blending (e) component, a pigment is mixed and disperse | distributed to the pigment, a pigment dispersing agent, and the solvent for disperse | distributing some (e) component as needed (henceforth a "dispersion solvent"). The dispersion is prepared in advance. On the other hand, a clear resist liquid is prepared by mixing and dissolving or disperse | distributing (a) component and the solvent for diluting (e) component and another component (henceforth "dilution solvent") separately as needed. And the coloring composition excellent in pigment dispersibility is obtained easily by mixing the obtained pigment dispersion liquid and clear resist liquid, and performing a dispersion process as needed. According to this method, since a dispersion solvent and a dilution solvent can be selected, a wide range of solvent selection is also possible.

In the case of not preliminarily preparing a pigment dispersion, first, a pigment, a pigment dispersant, and an alkali-soluble resin are added to the organic solvent, if necessary, sufficiently mixed and stirred to disperse the pigment, and then the remainder of the carboxyl group-containing polyfunctional acrylate and the like. By adding and mixing the components of, the pigment dispersibility is completed without being inhibited by other compounding components in the pigment dispersion step, and also excellent in stability.

What is necessary is just to follow a conventional method as a formation method of the colored layer using the obtained coloring composition. Specifically, after the composition is applied to a substrate to form a coating film and dried, a part of the coating film is selectively cured by irradiating the coating film with light rays in a predetermined pattern, followed by post-baking after development with an alkaline liquid, In addition, a colored coating film having a predetermined pattern is obtained by thermosetting.

Ultraviolet light or visible light is preferable, and the light to be used uses wavelength light of 240 nm to 410 nm obtained from a high pressure mercury lamp, a metal halide lamp, or the like. Irradiation energy required for hardening is about 10-500 mJ / cm <2> normally. In an exposure process, the predetermined position of a coating film can be selectively exposed and hardened by irradiating a laser beam to the surface of a coating film, or irradiating a light ray through a mask.

In addition, thermosetting is generally dried at 50-200 degreeC using a vacuum dryer, oven, a hotplate, or other apparatus which can give heat, and it hardens by heating at the temperature of about 120-250 degreeC after that.

The hardened part in the coating film has a structure in which the pigment is uniformly dispersed in the matrix formed by the crosslinking network formed by the photocuring reaction and the thermosetting reaction according to the present invention.

Since this coloring composition is excellent in sclerosis | hardenability, and crosslinking density rises and it hardens uniformly to the inside, it is hard to become an inverse taper at the time of image development, and a pattern which is a forward taper shape, a sharp edge, and a favorable surface smoothness is formed.

Moreover, since the impurity is trapped in the matrix of the high crosslinking density hardened to the inside at the time of hardening, and it is hard to elute to a liquid crystal layer, the coloring composition of this invention obtains a highly cured colored cured film. In particular, when producing the colored layer of a liquid crystal panel using this coloring composition, it is possible to keep the voltage of a display part stably, and high electrical reliability.

Moreover, since the said coloring composition can disperse | distribute a pigment of high concentration finely and uniformly, and since coloring property is high, it can form the coloring pattern with a large coloring density, even if it is thin, and a wide color reproduction area | region.

Although a coloring composition can be used for forming various colored coating films, it is especially suitable for forming the colored layer which comprises the detail of a color filter, ie, a pixel or a black matrix.

[Effects of the Invention]

Since the composition of this invention requires (a) component which is excellent in sclerosis | hardenability and alkali developability, when used as a composition for active-energy-ray-curable pattern formation, it has high exposure sensitivity, good developability, and a precise and accurate pattern. Can be formed, and after curing, excellent physical properties such as coating film strength, heat resistance and chemical resistance are obtained.

In addition, the composition of the present invention can be produced even without containing the alkali-soluble resin (e) component, and even when the component (e) is blended, the blending ratio can be reduced. The ratio of a) component can be mix | blended a lot.

Furthermore, since the composition of the present invention has high elasticity at room temperature after curing, it is excellent in that plastic deformation of the pattern is unlikely to occur, and is particularly suitable for forming columnar spacers and color filter protective films, and is excellent in alkali developability. Suitable for forming a layer.

This invention relates to the active-energy-ray-curable composition which makes the said (a) component essential.

As (a) component, 1 or more types chosen from the compound of said (a-1)-(a-3) is preferable.

Moreover, as (a) component, the compound of (a2) which has a hydroxyl group further is preferable. As (a2), the compound of (a2-1) is preferable.

Moreover, as (a) component and (a2), the compound of said (a3-1) is more preferable.

As the composition of the present invention, it is preferable to further contain the component (b) or / and the component (c).

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

As a composition for pattern formation, it can also use suitably as a composition for columnar spacers, the composition for color filter protection, or the coloring composition for color filters.

EXAMPLE

Hereinafter, an Example and a comparative example are given and this invention is demonstrated more concretely.

In addition, below, a "part" means a mass part and "%" means a mass%.

○ Production example 1 [production of (a-1)]

An acrylate mixture containing 110 g of ethanol, dipentaerythritol penta, and hexaacrylate in a 30:70 (mass ratio) in a 500 ml glass flask equipped with a stirring device, a thermometer and a water-cooled condenser; 100 g was added, and 10 g of proline was added at room temperature, followed by reaction for 4 hours. The reaction was carried out in an air atmosphere.

As a result, a solution containing 50% of (a-1) (hereinafter referred to as "a1") having an acid value of 45 mgKOH / g (solid content conversion) was obtained.

○ Production example 2 [production of (a2-1)]

16 g of succinic anhydride, 250 g of g1, and 0.13 g of metoquinone were put into the flask like the manufacture example 1, and it heated up at 85 degreeC. After adding 1.3 g of triethylamine as a catalyst therein, the reaction was carried out for 4 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen to obtain a compound having an acid value of 34 mg KOH / g (hereinafter referred to as "h1").

Subsequently, 103 g of DMDG (Nippon Yukazai Co., Ltd. make: brand name DMDG, hereinafter referred to as "DMDG") and 100 g of g1 were added thereto, and 2.6 g of ethanolamine was added at room temperature, followed by reaction for 4 hours in an air atmosphere. Was performed.

This obtained the solution which contains 50% of (a2-1) (henceforth "a2") of acid value 33 mgKOH / g (solid content conversion) and hydroxyl value (solid content conversion) 23 mgKOH / g as solid content.

H1 was also used in Comparative Examples 2, 5, 8 and 11.

○ Production example 3 [production of (a3-1)]

Into the same flask as in Production Example 1, 114 g of DMDG and 100 g of g1 were added, and 5.4 g of ethanolamine was added at room temperature, followed by reaction for 4 hours. The reaction was carried out in an air atmosphere.

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

As a result, a solution containing 50% of (a3-1) (hereinafter referred to as "a3") having an acid value of 70 mgKOH / g (solid content conversion) was obtained.

○ Production example 4 [production of (e) component]

In a detachable flask equipped with a stirrer, thermometer, reflux condenser, dropping lot and nitrogen introduction conduit, 52% benzyl methacrylate, 23% acrylic acid, 2 times DMDG, 2,2'-azo Bis (2-methylbutylonitrile) was added 10% with respect to the total amount of the monomers and dissolved uniformly. Thereafter, the mixture was stirred at 85 ° C for 2 hours under a nitrogen stream, and further reacted at 100 ° C for 1 hour. In the solution thus obtained, glycidyl methacrylate was 25%, triethylamine was 10% to glycidyl methacrylate, hydroquinone was 1% to glycidyl methacrylate, and the monomer and glycine added DMDG was added so that the combined weight of dimethyl methacrylate could be 35%, and it stirred at 100 degreeC for 5 hours, and obtained the target copolymer solution (solid content concentration 31.5%).

Mw of the obtained (e) component (henceforth "e1") was 14,200, the acid value was 84 mgKOH / g and the hydroxyl value was 96 mgKOH / g.

○ Comparative Production Example 1 [Production of (i1) Component]

DMDG 91g, 1,2,3,4-butanetetracarboxylic acid dianhydride [manufactured by Shin-Nippon Rika Co., Ltd .: product name: Rikashitdo T-100 in a 500 ml glass flask equipped with a stirring device, a thermometer, and a water-cooled condenser. 10 g, 150 g of g1, and 0.08 g of metoquinone were put, and it heated up at 95 degreeC. After 0.8 g of triethylamine was added thereto, the reaction was carried out for 8 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen.

As a result, a solution containing 65% of a compound having an acid value of 34 mg KOH / g (hereinafter referred to as [i1]) as a solid content was obtained.

○ Examples 1-6, Comparative Examples 1-6 (resin composition for spacer or protective film)

(A)-(c) component and (e) component were mixed according to the conventional method so that it might become the ratio shown in following Table 1 and 2, and the resin composition for spacers or protective films was adjusted.

Evaluation shown below was performed using the obtained composition. Their results are shown in Tables 1 and 2.

<Developing>

The composition shown in Table 1 and 2 was apply | coated by the spin coater on the 10-cm size chromium mask glass board | substrate, and this coating film was dried for 10 minutes with 80 degreeC ventilation dryer, and the coating film of 5 micrometers of dry film thicknesses was formed. The obtained coating film was spray-developed with 0.5 wt% sodium carbonate aqueous solution, the time until complete dissolution was measured, and the following reference | standard evaluated.

○: completely dissolved within 15 seconds.

Δ: completely dissolved within 60 seconds

X: It does not melt | dissolve completely within 60 second.

<Residue>

The presence or absence of the melt | dissolution residue on the surface of the board | substrate after developability evaluation was observed, and the following reference | standard evaluated.

○: There is no melting residue at all.

△: There are some dissolved residues.

X: The melting residue is very large.

<Evaluation of Elastic Strain>

On the chrome mask glass substrate having a size of 10 cm, the compositions shown in Tables 1 and 2 were applied by a spin coater, and the coating film was dried for 10 minutes with a blow dryer at 80 ° C to form a coating film having a dry film thickness of 6 µm. . The photomask was arrange | positioned at the distance of 100 micrometers from this coating film, and the ultraviolet-ray was irradiated with the intensity | strength (365 nm roughness conversion) of 300 mJ / cm <2> with an ultrahigh pressure mercury lamp by the proximity aligner. Subsequently, it immersed in 0.5 wt% sodium carbonate aqueous solution of 23 degreeC of liquid temperature for 60 second, and developed alkali, and removed only the unhardened part of the coating film. Thereafter, the substrate was left to stand in an atmosphere of 200 ° C. for 30 minutes to conduct heat treatment to form columnar spacers having a height of 5 μm and a diameter of 15 μm.

The elastic strain at room temperature of the obtained columnar spacer was compressed using an ultra-small hardness tester (manufactured by Fischer Instruments Co., Ltd., H-100C) equipped with a planar indenter (a indenter having a plane of 100 µm x 100 µm). It calculated as [(elastic deformation amount / total deformation coefficient) x100] when measured on the conditions which become a load 0.2GPa.

The number of the column of the composition in Table 1 and 2 means the mass part, and a1-a3, e1, and i1 were shown as ratio of solid content.

In addition, the symbol in Table 1 and 2 means the following.

Irg907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, Chiba Specialty Chemicals, Inc.

The compositions of Examples 1 to 6 were extremely developable and had no residue on the substrate. Moreover, those hardened | cured materials were those which had sufficient elastic strain for a spacer or a protective film.

On the other hand, the carboxyl group-containing obtained by adding Comparative Example 1 and 4 which use g1 which is a conventional alkali-insoluble polyfunctional acrylate, and the compound which has a hydroxyl group and a (meth) acryloyl group with a bivalent carboxylic anhydride. The compositions of Comparative Examples 2 and 5 using h1, which is a polyfunctional (meth) acrylate, are insufficient in both developability and residue, and have 4 or more compounds having at least one hydroxyl group and at least two (meth) acryloyl groups. Although the composition of Comparative Examples 3 and 6 using i1 which is a carboxyl group-containing polyfunctional (meth) acrylate obtained by addition reaction with the dianhydride of carboxylic acid, there was no residue but the developability was insufficient.

○ Examples 7-13 and Comparative Examples 7-13 (blue coloring composition)

The coloring composition was adjusted by mixing (a)-(c) component and (e) component, a pigment, and a pigment dispersing agent in accordance with a conventional method so that it may become the ratio shown to following Tables 3 and 4.

Using the obtained composition, the developability and the residue were evaluated according to the following method. Their results are shown in Tables 3 and 4.

<Developing>

In the developability test in Examples 1-6, it tested by the same method except making a dry film thickness into 2 micrometers. The obtained coating film was spray-developed with 0.5 wt% sodium carbonate aqueous solution, the time until complete dissolution was measured, and the following reference | standard evaluated.

○: completely dissolved within 60 seconds.

Δ: completely dissolved within 90 seconds

X: It does not melt | dissolve completely within 90 second.

<Residue>

The board | substrate surface after developability evaluation was wiped 10 times with the cotton swab containing ethanol, and the presence or absence of coloring of the cotton swab was investigated and it evaluated on the following reference | standard.

○: The cotton bud is not colored at all.

?: The cotton swab is weakly colored.

X: The cotton swab is colored.

In addition, the symbol in Tables 3 and 4 shows the same meaning as Table 1 except the following.

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

DlS: pigment dispersant, Disperbyk-2001, solid content 46% (main solvent: methoxypropyl acetate, methoxypropanol, butyl cellosolve)

The compositions of Examples 7-13 were very developable and there was no residue on a board | substrate at all.

On the other hand, the compositions of Comparative Examples 8 and 11 using g1 are not sufficiently developable and residues at all, while the compositions of Comparative Examples 7, 9 and 12 using h1 are insufficient in both developability and residues. There were no residues in the compositions of Comparative Examples 10 and 13 used, but the developability was insufficient.

○ Examples 14-16, Comparative Examples 14-16 (red coloring composition)

The coloring composition was adjusted by mixing (a)-(c) component and (e) component, a pigment, and a pigment dispersing agent in accordance with a conventional method so that it may become the ratio shown in following Tables 5 and 6.

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

In addition, the symbol in Tables 5 and 6 shows the same meaning as Table 1 and Table 3 except the following.

PR: pigment, C.I. Pigment Red 177

The compositions of Examples 14-16 were very developable and had no residue on the substrate.

On the other hand, neither the developability nor the residue of the composition of the comparative example 14 using g1 and the comparative example 15 using h1 was sufficient at all, and the composition of the comparative example 16 using i1 was insufficient in both developability and a residue.

The composition of this invention can be used for various uses, such as an ink, a coating material, and a resist, and can be used suitably as a composition for pattern formation, such as a resist.

Moreover, the composition of this invention can be used suitably as a coloring composition for forming the columnar spacer in the liquid crystal panel manufacture, the composition for color filter protective films, and the pixel, black matrix, etc. in a color filter.

Claims (11)

An active energy ray curable composition comprising a compound (a) having two or more ethylenically unsaturated groups, tertiary amino groups and acidic groups as essential components. The active energy ray-curable composition according to claim 1, wherein the component (a) is a compound (a2) further having a hydroxyl group. The active energy ray-curable composition according to claim 1, wherein the component (a) is at least one selected from compounds of the following (a-1) to (a-3). (a-1): Michael addition reaction product of the compound which has three or more (meth) acryloyl groups, and the primary or secondary amine which has an acidic group. (a-2): Michael addition reaction product of the compound which has three or more (meth) acryloyl groups and an acidic group, and the primary or secondary amine which has an acidic group. (a-3): Michael addition reaction product of the compound which has three or more (meth) acryloyl groups and an acidic group, and the primary or secondary amine which does not have an acidic group and a hydroxyl group. The active energy ray-curable composition according to claim 2, wherein (a2) is a compound of the following (a2-1). (a2-1): Michael addition reaction product of the compound which has three or more (meth) acryloyl groups and an acidic group, and a primary or secondary amine which has a hydroxyl group. The active energy ray curable composition according to claim 1 or 2, wherein the component (a) or the component (a2) is a compound of the following (a3-1). (a3-1): A compound obtained by addition-reacting a Michael addition reaction product of a compound having three or more (meth) acryloyl groups with a primary or secondary amine having a hydroxyl group with an acid anhydride. The active energy ray-curable composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator. The active energy ray-curable composition according to any one of claims 1 to 6, further comprising an organic solvent. It consists of the composition in any one of Claims 1-7, The composition for active energy ray hardening pattern formation. The composition for forming an active energy ray-curable pattern according to claim 8, further comprising an alkali-soluble resin. After applying the composition of Claim 8 or 9 to a board | substrate, and forming a coating film, it is irradiated and hardened | cured by irradiating an active energy ray through the mask which has a specific pattern shape on this, and developing an uncured part with a developing solution. The pattern formation method characterized by the above-mentioned. The composition for columnar spacers, the composition for color filter protective films, or the coloring composition for color filters which consists of a composition of Claim 8 or 9.