JP2001091732A - Composition for color filter protecting film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for a color filter protecting film and the protecting film having a high flattening property and excellent ability of hiding the projecting and recessing parts of a surface generated by a color ink pixel of an undercoating a black matrix or the like. SOLUTION: A composition for a color filter protecting film and the color filter protecting film formed by curing the composition are provided. The composition comprises a blocked carboxylic acid compound (A), an epoxy compound (B) having two or more epoxy groups in one molecule as indispensable components and a heat latent catalyst (C) exhibiting activity when the composition is thermally cured as an optional component. The blocked carboxylic acid compound (A) has two or more functional groups in one molecule, which is represented by the formula (1) (wherein R1, R2 and R3 each denotes a hydrogen atom or an organic group having carbon number of 1-18, R4 denotes an organic group having carbon number of 1-18 and may be bonded to R3 to form a heterocycle having Y as a hetero atom and Y denotes oxygen or sulfur atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for providing a color filter protective film having excellent flatness and a color filter protective film. More specifically, the present invention relates to an LCD color filter protective film containing an epoxy curing agent and an epoxy compound and a material thereof.

[0002]

2. Description of the Related Art A color filter protective film for a liquid crystal display (LCD) is required to have a high flattening property capable of concealing surface irregularities generated by a base color ink pixel and a black matrix. If the flatness is poor, display quality such as color unevenness will be reduced when incorporated into an LCD panel.

As a composition for a protective film of a color filter, for example, Japanese Patent Application Laid-Open No. 63-218773 discloses a composition for forming a protective film containing a hydrolyzate or a partial decomposition product of an organoalkoxysilane. I have. Further, Japanese Patent Publication No. 8-30167 discloses an amic acid compound containing a silicon atom having a hydrolyzable group, an imide compound,
A curable composition containing a disilazane compound is disclosed. Further, JP-A-4-345608 discloses a color filter material containing a compound having a bisphenolfluorene skeleton and a cured product thereof.

[0004] These compositions have the function of flattening the surface steps formed by the underlying color ink pixels and black matrix, and can be used as a protective film for LCDs. However, recently, in order to realize high-speed driving by the STN driving method and the IPS driving method, development of a protective film material having more excellent flattening properties has been required.

[0005] A composition containing an epoxy compound and an epoxy curing agent is also known from Japanese Patent Application Laid-Open No. 9-328534, but further improvement is desired in terms of its usability and the ability to hide irregularities. . As the epoxy curing agent, phenols, carboxylic acid compounds and amine compounds are generally used, and JP-A-4-218561 proposes a blocked carboxylic acid compound having a specific structure. Teach that it can be used in such fields. However, there is no description suggesting an application to a special technical field such as a composition for a color filter protective film.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for a color filter protective film having excellent flattening ability and excellent ability to conceal surface irregularities generated by a base color ink pixel, a black matrix and the like. The purpose is to provide a protective film.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, (A) a blocked molecule having two or more blocked carboxyl groups in one molecule. A composition comprising, as essential components, a carboxylic acid compound and (B) an epoxy compound having two or more epoxy groups in one molecule, or (D) one or more blocked carboxyl groups and one epoxy group in one molecule. The present inventors have found that flatness is remarkably improved by using a composition containing a self-crosslinking compound having at least one compound as an essential component, and completed the present invention.

That is, the present invention provides (A) a compound represented by the following general formula (1):

Embedded image (However, R ₁ , R ₂ and R ₃ in the formula are a hydrogen atom or a carbon atom 1
To 18 organic group, R ₄ is an organic group having 1 to 18 carbon atoms, R ₃
And R ₄ may combine with each other to form a heterocyclic ring having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. )), A blocked carboxylic acid compound having two or more functional groups represented by the formula (B), an epoxy compound having two or more epoxy groups in one molecule is contained as an essential component, and (C) heating is used if necessary. It is a composition for a color filter protective film, characterized by containing as an optional component a heat-latent catalyst exhibiting activity during curing. Further, the present invention, 5 to 95 wt% of said epoxy compound is represented by the following general formula (2), G-A - [- CH 2 -CH (OH) -CH 2 -A-] n -G (2) ( Where G is a glycidyl group, A is the following formula (3),

Embedded image Wherein n is the number of repetitions. The composition for a color filter protective film, which is the epoxy compound represented by the formula (1):

Further, the present invention relates to (D) a compound represented by the following general formula (1):

Embedded image (However, R ₁ , R ₂ and R ₃ in the formula are a hydrogen atom or a carbon atom 1
To 18 organic group, R ₄ is an organic group having 1 to 18 carbon atoms, R ₃
And R ₄ may combine with each other to form a heterocyclic ring having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) Containing as an essential component a self-crosslinking compound having one or more functional groups and one or more epoxy groups,
A composition for a color filter protective film, which further comprises, as an optional component, (C) a heat-latent catalyst which is active when heated and cured, if necessary. The present invention also provides the above-mentioned blocked carboxylic acid compound and / or
Alternatively, the composition for a color filter protective film further contains an epoxy compound.

Further, the present invention is a color filter protective film obtained by curing the composition for a color filter protective film according to any one of the above.

First, the components or compounds used in the present invention will be described in detail. (A) A blocked carboxylic acid compound having two or more functional groups represented by the general formula (1) in one molecule (hereinafter, referred to as a component (A) or a blocked carboxylic acid compound (A)) is For example, JP-A-4-2185 discloses the chemical structure and production method thereof.
In addition to those described in JP-A-61-61 and the like, commercially available products can also be used. The blocked carboxylic acid compound (A) is decomposed by heating to produce a free carboxylic acid.

The component (A), that is, the blocked carboxylic acid compound (A) is, for example, a polyvalent carboxylic acid and the following general formula (4):

Embedded image (Wherein, R _{1 to} R ₄ and Y represent the same as those in the general formula (1)) with a vinyl ether compound or a vinyl thioether compound in the presence of an acid catalyst.
It can be obtained by reacting at room temperature to about 100 ° C.

The polycarboxylic acids used in this reaction include trimellitic acid, pyromellitic acid, phthalic acid,
Aromatic polycarboxylic acids such as naphthalenedicarboxylic acid,
Alicyclic polycarboxylic acids such as tetrahydrophthalic acid, aliphatic polycarboxylic acids such as adipic acid, succinic acid, and butanetetracarboxylic acid, and unsaturated aliphatic polycarboxylic acids such as maleic acid, fumaric acid, and itaconic acid And the like. Further, polyvalent carboxylic acids obtained by the following method can also be advantageously used. (1) Polyhydric carboxylic acids obtained by half-esterifying a polyol and an acid anhydride having two or more, preferably 2 to 50 hydroxyl groups, and (2) two or more, preferably 2 to 2, isocyanate groups.
Polyhydric carboxylic acids obtained by addition reaction of 50 polyisocyanates with hydroxycarboxylic acids or amino acids, (3) polyhydric carboxylic acids obtained by homopolymerizing or copolymerizing unsaturated carboxylic acids, (4) polyol and Polyester-type polyvalent carboxylic acids obtained by reacting a polyvalent carboxylic acid. The polyvalent carboxylic acid may have about 2 to 50, preferably about 2 to 10, and more preferably about 3 to 6 carboxyl groups in one molecule. As a specific example of a preferable polyvalent carboxylic acid, the number of carboxyl groups is 3 to
4 benzenecarboxylic acid.

The vinyl ether compound or vinyl thioether compound used in this reaction includes aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylcyclohexyl vinyl ether and cyclohexyl vinyl ether, and the corresponding vinyl ether compounds. And cyclic vinyl ether compounds such as dihydrofurans and dihydro-2H-pyrans, and cyclic vinyl thioether compounds corresponding thereto. Preferred compounds are lower alkyl vinyl ethers having 6 or less carbon atoms.

The blocked carboxylic acid compound (A) used in the present invention is not limited to those obtained by the above-mentioned production method, but may be those having two or more functional groups represented by the above general formula (1). The number of the functional groups is usually 1
About 2 to 10, preferably about 3 to 6 in the molecule,
The non-blocked carboxyl group should be absent or small, for example, 20% or less. Examples of R _{1 to} R ₄ and Y in the above general formula (1) are as follows:
It is possible to refer to the examples of the vinyl ether compound or the vinyl thioether compound, and preferable examples are also the same.

(B) The epoxy compound having two or more epoxy groups in one molecule (hereinafter referred to as component (B) or epoxy compound (B)) has two or more epoxy groups, preferably 2 to 50 epoxy groups. And more preferably an epoxy compound having 2 to 20 compounds in one molecule (including an epoxy resin). The epoxy group may have a structure having an oxirane ring structure, and examples thereof include a glycidyl group, an oxyethylene group, and an epoxycyclohexyl group. Examples of the epoxy compound (B) include known polyvalent epoxy compounds that can be cured with a carboxylic acid. Examples of such an epoxy compound include “Epoxy Resin Handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 1987), and these can be used. Specific examples include a phenol novolak type epoxy resin, a novolak type epoxy resin such as a cresol novolak type epoxy resin, a bisphenol type epoxy resin such as a bisphenol A type epoxy resin, and a cycloaliphatic type epoxy resin.

Preferred as the epoxy compound (B) is the epoxy compound represented by the general formula (2), wherein n is the number of repetitions,
The preferred average number of repetitions is in the range of 0-5, though in the range of about 100. A is a fluorene ring-containing group represented by the above formula (3), and is preferably fluorene-9,9-bis (4-
Oxyphenyl) group. The epoxy compound represented by the general formula (2) is 100% of the epoxy compound (B).
Although it may be t%, it is advantageous to use it together with a novolak type epoxy resin. In this case, the ratio of the epoxy compound represented by the general formula (2) is
5 to 95 wt%, preferably 30 to 80 wt%.

(D) A self-crosslinking compound having one or more functional groups represented by the above general formula (1) and one or more epoxy groups in one molecule (hereinafter referred to as “component (D)” or “self-crosslinking compound”). (D) is a compound in which the functional group represented by the general formula (1) is decomposed by heat to generate a free carboxyl group, and the carboxyl group reacts with the epoxy group to be cured.

The functional group represented by the general formula (1) includes
The same as those exemplified in the description of the functional group in the component (A) can be used. Examples of the epoxy group include the same epoxy groups as those exemplified for the epoxy compound of the component (B). This self-crosslinking compound (D) has one carboxyl group in one molecule.
Or more, preferably 2 to 50 and one or more epoxy groups,
A compound having preferably 2 to 50 compounds is used as a starting material,
It can be produced by the same method as described in the method for producing the compound of the component (A). Alternatively, it can also be produced by copolymerizing an unsaturated compound having a functional group represented by the general formula (1) and an unsaturated compound having an epoxy group. And the ratio of the carboxyl group to the epoxy group is usually in the range of 1/5 to 5/1 (molar ratio). An advantageous method for producing the self-crosslinking type compound (D) is described in JP-A-4-218561, and the compound can be easily produced by following this method. Preferred self-crosslinking compounds (D) include those described in the above-mentioned publication.

(C) A heat latent catalyst exhibiting activity during heat curing (hereinafter, referred to as component (C) or heat latent catalyst (C))
When heated, it exhibits catalytic activity, accelerates the curing reaction, and gives the cured product good physical properties, and is added as necessary. This latent heat catalyst (C)
Is preferably a compound exhibiting an acid catalytic activity at a temperature of 60 ° C. or higher, such as a compound obtained by neutralizing a protic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, or a Lewis acid and a trialkyl phosphate. Mixtures, sulfonic acid esters, onium compounds and the like,
Various compounds as described in JP-A-4-218561 can be used. Specifically, (a) compounds obtained by neutralizing halogenocarboxylic acids, sulfonic acids, phosphoric acid mono- and diesters with various amines such as ammonia, monomethylamine, triethylamine, pyridine and ethanolamine, or trialkylphosphine, etc. , (B) BF ₃ , FeCl ₃ , Sn
A compound obtained by neutralizing a Lewis acid such as Cl ₄ , AlCl ₃ or ZnCl ₂ with the above-mentioned Lewis base; and (c) methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid or the like with a primary alcohol or a secondary alcohol. Ester compounds,
(D) Phosphoric acid monoester compounds and phosphoric acid diester compounds of primary alcohols and secondary alcohols. Examples of the onium compound include an ammonium compound [R ₃ NR ′] ⁺ X ⁻ , a sulfonium compound [R ₃ SR ′] ⁺ X ⁻ , and an oxonium compound [R ₃ OR ′] ⁺ X ⁻ . Here, R and R 'are alkyl, alkenyl, aryl, alkoxy and the like.

Next, the composition for a color filter protective film of the present invention will be described. The composition of the present invention comprises the above (A)
To (D) are obtained by using one or more of the components, a composition having the (A) and (B) components as essential components, and a composition having the (D) component as the essential components. It is roughly divided into things.

In the composition of the present invention comprising the components (A) and (B) as essential components, the blocked carboxylic acid compound (A) as the component (A) and the epoxy compound (B) as the component (B) ) Indicates the hardness, heat resistance,
The ratio is selected from the ratio of the carboxyl group (including the blocked carboxyl group; hereinafter the same in this section) and the epoxy group of each compound so that the physical properties such as chemical resistance satisfy the required characteristics. Here, the ratio is calculated, for example, such that the number of carboxyl groups in one molecule of the blocked carboxylic acid compound (A) is n and the number of the epoxy compound (B) is one.
Assuming that the number of epoxy groups in the molecule is m, n equivalent of carboxyl group, m
Calculated as having equivalent epoxy groups. Focusing on heat resistance, the equivalent ratio of carboxyl group / epoxy group is
The component (A) and the component (B) are preferably blended so as to be 0.4 to 1.4, preferably 0.6 to 1.2, and more preferably 0.8 to 1.0. If the equivalent ratio is less than 0.4, the heat resistance of the obtained cured product is low, and the adhesion to the glass substrate is low. On the other hand, if the equivalent ratio is more than 1.4, the heat resistance of the obtained cured product is low. Problems such as low resistance and low alkali resistance occur. For other characteristics,
The equivalent ratio of carboxyl group / epoxy group is set to 0.4 to 1.
4, preferably in the range of 0.6 to 1.2.

In the composition of the present invention, component (A) and / or component (B) may be one type of blocked carboxylic acid compound (A) and one type of epoxy compound (B), or two or more types. Or a blocked carboxylic acid compound (A) or an epoxy compound (B). And
When using a mixture of two or more epoxy compounds,
It is preferable to use a combination of epoxy compounds that does not leave unreacted epoxy groups. For example, a carboxyl group /
Even if the equivalent ratio of epoxy groups satisfies the above range,
If an epoxy with a significantly different reactivity is used, a highly reactive epoxy reacts preferentially, and an epoxy group with a low reactivity may remain unreacted. Will be.

In the composition of the present invention, in addition to using the block carboxylic acid compound as the component (A) alone, one or more polycarboxylic acids and anhydrides of polycarboxylic acids may be used. It is also advantageous to use together with a polyvalent carboxylic acid compound. Here, as the polyvalent carboxylic acid compound, the polyvalent carboxylic acids and their acid anhydrides described above as the raw material for the block carboxylic acid compound (A) can be used. When the block carboxylic acid compound (A) and the polyvalent carboxylic acid compound are used together, the ratio of the block carboxylic acid compound (A) to the polyvalent carboxylic acid compound is 5:95 to 95: 5 by weight, preferably 10:95. : 90-90: 1
It is preferable to set the range to 0. Block carboxylic acid compound
If the proportion of (A) is less than 5 wt%, the flatness intended in the present invention cannot be obtained, and in order to obtain better flatness,
It is preferable to contain 10 wt% or more. In this case, the equivalent of the carboxyl group is in the above-described equivalent ratio of carboxyl group / epoxy group.

In the composition of the present invention comprising the components (A) and (B) as essential components, the heat latent acid catalyst (C) as the component (C) is used for accelerating the curing and improving the physical properties of the cured product. It is also advantageous to mix for the purpose. The blocked carboxylic acid compound (A) as the component (A) decomposes at a certain temperature to produce a free carboxylic acid.
This thermal latent acid catalyst (C) is effective for accelerating the decomposition rate. Also in this case, one type of component (C) may be used, or two or more types may be used. The amount is (A)
It is usually selected in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total of the component and the component (B). In addition, in these weight calculations, non-solid components such as a solvent which may be contained in the component (A) or the component (B) are not calculated. Further, in addition to the above components, various components may be blended in the composition of the present invention as described later.

Next, the composition of the present invention containing the component (D) as an essential component will be described. The ratio of the blocked carboxyl group to the epoxy group in the self-crosslinking type compound (D) which is the component (D), that is, the equivalent ratio of the carboxyl group to the epoxy group, is determined by making the above-mentioned components (A) and (B) the essential components. Can be said to be the same as the equivalent ratio described in the composition, but as described later, the blocked carboxylic acid compound (A)
In the case where the epoxy compound (B) is blended, the equivalent ratio calculated as a whole may be within the above-mentioned range, so that it can be changed over a wider range.

The composition of the present invention containing component (D) as an essential component may be added, if necessary, to a blocked carboxylic acid compound (A) as component (A) and / or an epoxy compound as component (B). One or more of (B) can be blended. Also in this case, it is preferable that the ratio of the component (D), the component (A), and the component (B) is such that the equivalent ratio of the carboxyl group / epoxy group is in the above-mentioned range.
When two or more epoxy compounds are used as a mixture, it is preferable to use a combination of epoxy compounds that does not leave unreacted epoxy groups. Component (D) 1
The total amount of component (A) and component (B) relative to 0 parts by weight can vary over a wide range, but is preferably in the range of 1 to 100 parts by weight. Further, when the equivalent ratio of the carboxyl group / epoxy group of the component (D) is out of the preferable range, the component (D) can be prepared by using one of the component (A) and the component (B) in a large amount. It can be used to advantage. When the component (D) corresponds to either the component (A) or the component (B), it is treated as the component (D).

The composition of the present invention containing the component (D) as an essential component may, if necessary, be used as the component (C) for the purpose of accelerating the curing reaction and imparting better flatness. A heat-latent acid catalyst (C) which is active during curing can be contained. The component (C) may be one type or two or more types. The mixing amount is (D) 100
When component (A) or component (B) is blended with respect to parts by weight, the total of component (D), component (A) and component (B) is 100
It is usually selected in the range of 0.01 to 10 parts by weight with respect to parts by weight.

In the composition of the present invention, in addition to the above components, various additives, solvents and the like may be blended in order to satisfy the performance required for the material for a color filter protective film. For the purpose of applying the composition of the present invention using a coating device such as a spin coater, a roll coater, or a bar coater, a solvent for adjusting the viscosity to a required viscosity is used. The solvent is required to dissolve the component (A), the component (B) and / or the component (D) contained in the composition satisfactorily, and to provide a smooth and flat coating film without uneven evaporation. It is preferably a solvent that gives good storage stability. Examples of such a solvent include ether solvents, acetal solvents, ketone solvents, ester solvents, and the like. The solid content concentration of the composition of the present invention can be arbitrarily adjusted within a range in which each component to be dissolved is stably dissolved in accordance with a coating apparatus to be used and a target thickness of a coating film.

The composition of the present invention may contain necessary additives for the purpose of improving the physical properties required for the composition for a protective film. Additives include a silane coupling agent that improves adhesion to the glass substrate, a silicon-based or fluorine-based surfactant that eliminates uneven evaporation of the solvent and improves the smoothness and flatness of the coating, and the storage stability of the composition Vinyl ether compounds for improving the properties. Here, the vinyl ether compound preferably has a boiling point of 40 ° C. or higher for the purpose of preventing evaporation during storage. In addition, various organic compounds such as resins, inorganic compounds, and the like can be added as necessary.

The composition of the present invention has excellent storage stability because the reactive carboxyl group is blocked, but the component (A) is used for the purpose of further improving the storage stability at room temperature. It is possible to obtain a desired composition by storing the two compositions each containing the blocked carboxylic acid compound used as the component and the epoxy compound used as the component (B) alone and mixing them when used. is there.

The method for curing the composition of the present invention may be in accordance with a usual production process for a color filter protective film, and is not limited. A typical curing method is to sufficiently remove the solvent at a temperature of 120 ° C. or lower to make the coating film tack-free (prebaked), and then to cure at a temperature in the range of 150 to 240 ° C. to 5 to 60 ° C.
This is a method in which curing is completed by heating for about a minute (post bake). Here, the pre-bake temperature is 120
If the temperature is higher than 0 ° C, the flatness may decrease, and the temperature is preferably 100 ° C or less. Post bake temperature is 150 ° C
If the temperature is lower, the heat resistance of the obtained protective film may be insufficient, and it is preferably 180 ° C or higher, more preferably 200 ° C or higher. The post-baking time depends on the post-baking temperature, but is preferably 15 minutes or more, more preferably 30 minutes or more when the post-baking temperature is 200 ° C. Post-baking may be completed at one temperature, but it is preferable to use multi-stage baking in order to further improve flatness. here,
Multi-stage baking refers to performing curing at two or more different temperatures. For example, curing at 150 ° C. and then completing the curing at 200 ° C. (two-stage baking). The composition for a color filter protective film of the present invention is provided with a layer of ink of each color, a black resist or the like in a predetermined pattern on a substrate, then applied and cured to form a color filter protective film of the present invention.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In Examples, unless otherwise specified, parts represent parts by weight, and% represents% by weight. The preparation of the color filter protective film and the evaluation of the flatness are performed by the following methods unless otherwise specified.

(Preparation of Color Filter Protective Film) A composition for a color filter protective film is coated with a dummy color filter or SiO ₂ for flatness evaluation under spin coating conditions so that the film thickness after post-baking is 2 ± 0.05 μm. The solution was applied to a glass substrate that had been pre-baked, the solvent was evaporated at 80 ° C. for 10 minutes, and then cured at 200 ° C. for 60 minutes in post-baking to form a protective film.

(Evaluation of Flatness) Using a dummy color filter for evaluating flatness, the difference in height between the central portions of red and green pixels (step difference between pixels) was determined. Subsequently, according to the method for forming the color filter protective film described above, the film thickness was 2 ± 0.05.
After forming a μm coating film, the difference in height between the center of the red pixel and the center of the green pixel in the same portion was determined. The following equation (1)
The ratio R of the step between pixels (d1) before the application of the protective film and the step (d2) between the pixels after the application of the protective film is determined according to the following formula. evaluated. R = (d2) / (d1) (1) That is, when R is> 0.4, when R is 0.4 to 0.3, when R is 0.3 to 0.2, 0.2 to 0 .1 and <0.1. The evaluation indicates that the flattening performance is low, and that the flattening performance is high.

(Adhesion Test) A color filter protective film (coating film) was formed on a glass plate coated with SiO ₂ in accordance with the method for forming a color filter protective film described above. The coating film was cross-cut so as to form at least 100 cross-cuts, and then a peeling test (cross-cut test) was performed using a cellophane tape, and the state of the cross-cut was visually evaluated.

Production Examples 1 to 3 Production of Component (A) (SK-1 to 3) In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, put the solvent, raw material and 0.8 parts of Table 1 respectively. (Apachi-8, trade name of Daihachi Chemical Industry Co., Ltd.) and stirred at 50 ° C. When the acid value of the mixture became 5 or less, the reaction was terminated, and the solvent and excess vinyl ether were distilled off with a vacuum pump to obtain three kinds of properties shown in Table 1 as the blocked carboxylic acid compound (A). Compounds SK-1 to SK-3 were obtained. In addition,
The acid equivalent is a value obtained by dividing the molecular weight of the blocked carboxylic acid compound (A) by the number of blocked carboxyl groups in one molecule. The effective component corresponds to the purity.

[0038]

[Table 1]

Production Examples 4 and 5 Production of Component (A) (SK-4 to 5) In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, put each of the raw materials, solvent and 0.8 parts in Table 2 (Apachi-8, trade name of Daihachi Chemical Industry Co., Ltd.) and stirred at 50 ° C. After the reaction was terminated when the acid value of the mixture became 5 or less, the solvent and excess vinyl ether were distilled off under reduced pressure with a vacuum pump to obtain a compound SK-4 having the properties shown in Table 2, respectively.
SK-5 was obtained.

[0040]

[Table 2]

Production Example 6 Production of Component (A) (SK-6) (1) Production of Polycarboxyl Compound In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, 102.6 parts of pentaerythritol, 521.3 parts of melitic acid and 415.2 parts of methyl isobutyl ketone were charged and heated with stirring, and the reflux temperature was maintained for 6 hours. Thereafter, the acid value of the mixture (pyridine / water weight ratio = 9/1)
The polycarboxy compound solution was obtained by continuing to heat and stir until the solution diluted about 50-fold with the mixed solution and heat-treated at 90 ° C. for 30 minutes was titrated with potassium hydroxide standard solution to 305 or less.

(2) Production of Compound SK-6 Using the polycarboxyl compound solution obtained by the above method, 1039.1 parts of the polycarboxyl compound solution, n-propyl vinyl ether 6
06.9 parts and 0.8 parts of the same phosphoric acid ester catalyst were charged and stirred at 50 ° C. After the reaction was completed when the acid value of the mixture became 12 or less, the solvent and excess vinyl ether were distilled off under reduced pressure by a vacuum pump to obtain a characteristic value of 97.0% of an effective component and an acid equivalent of 160.5 g / mol. Compound SK-6 having the following formula: was obtained.

Production Example 7 Production of Component (D) (PSK-1) (1) Production of α, β-Unsaturated Compound Methacrylic acid 86.0 was placed in a four-necked flask equipped with a thermometer, reflux condenser and stirrer. , 103.2 parts of n-propyl vinyl ether and 0.1 part of the above-mentioned phosphoric acid ester catalyst, and the mixture was stirred at 50 ° C. The acid value of the mixture is 30
The reaction was terminated when the following conditions were reached, and after standing to cool, the product was transferred to a separating funnel. The obtained product was washed with 100 parts of a 10 wt% aqueous solution of sodium bicarbonate in a separating funnel with alkali, and then repeatedly washed with 200 parts by weight of deionized water until the pH of the washing solution became 7 or less. After that, molecular sieve 4A1 / 16 (Wako Pure Chemical Industries, Ltd.)
(Trade name), and the mixture was stirred at room temperature for 3 days to obtain an α, β-unsaturated compound having an effective content of 95.3%.
The effective components were determined by gas chromatography.

(2) Production of Compound PSK-1 A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with the initially charged solvent xylene 5 shown in Table 3.
59.2 parts were charged and heated under stirring to keep the temperature at 80 ° C. Next, at a temperature of 80 ° C., a mixture of α, β-unsaturated compound, glycidyl methacrylate and a polymerization initiator (dropping component) having the composition shown in Table 3 was dropped at a constant rate from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature of 80 ° C. was maintained for 1 hour, and a polymerization initiator solution (additional catalyst) shown in Table 3 was added.
The reaction was terminated when the temperature of 0 ° C. was maintained for 2 hours.
Compound PSK-1 having the described properties was obtained. The nonvolatile content was measured at 50 ° C. and 0.1 mmHg for 3 hours, and the viscosity was Gardner viscosity (25 ° C.).
SK-5400 (1979) 4.2.2 (Raw viscometer).

[0045]

[Table 3]

Production Examples 8 to 11 Production of Component (C) (CAT-1, 4 to 7) In a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a cooling tube, 100 g of zinc 2-ethylhexylate was added. 0 parts were charged and stirred at room temperature. Then, the dropping components shown in Table 4 were dropped from the dropping funnel over 30 minutes. After the addition, the reaction was carried out for 1 hour to obtain a heat latent catalyst having the characteristic values shown in Table 4.
In Table 4, the effective component is 2-amine in the amine adduct.
Shows the amount of zinc ethylhexylate.

[0047]

[Table 4]

Example 1 A sample bottle (200 ml) was charged with a rotor coated with Teflon (registered trademark) and placed on a magnetic stirrer.
37 g of cyclohexanone and 52 g of diethylene glycol dimethyl ether were placed in a sample bottle. While stirring, an epoxy resin (B1) as a component (B1); ESF-300 (manufactured by Nippon Steel Chemical Co., Ltd .: bisphenol fluorene type epoxy resin represented by the general formula (2), epoxy equivalent 231 g /
eq) 8 g, (B2) epoxy resin; 2 g of EHPE3150 (manufactured by Daicel Chemical Industries, Ltd .: an alicyclic solid epoxy resin having 9 epoxy groups in the molecule and an epoxy equivalent of 170 g / eq), (B3)
Epoxy resin: EOCN-1020 (orthocresol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 200)
g / eq) 15 g was added and completely dissolved. Continued
As the component (A), 15.1 is the SK-1 obtained in the above Production Example.
g, and after sufficiently stirring and dissolving, 0.12 g of the heat latent catalyst CAT-1 obtained in the above Preparation Example was added. Further, 1.4 g of a silane coupling agent (S-510, manufactured by Chisso) and a surfactant (Flolard FC-430, manufactured by Sumitomo 3M Limited) were added.
After adding 12 g and sufficiently stirring and dissolving, this was filtered,
The desired composition for a color filter protective film (V-1) was obtained.

Using the obtained protective film composition (V-1), a protective film was formed on a dummy color filter for flatness evaluation according to the method for evaluating flatness described above. The flatness of the obtained protective film was evaluated by the method described above. Table 5 shows the composition of the protective film composition (V-1) and the evaluation results of flatness. Table 5 confirms that the composition for a protective film (V-1) has excellent flatness.

Examples 2 to 13 According to the method described in Example 1, the types and amounts of the components (A), (C) and (D) obtained in the above Production Examples are shown in Table 5. Using them, compositions for protective films (V2 to V13) were prepared. The type and amount of the component (B), solvent, silane coupling agent and surfactant were the same as in Example 1. The flatness of the obtained composition for a protective film was evaluated by the method described above. Table 5 shows the results. From Table 5, it can be confirmed that the composition for a protective film (V2 to V13) has excellent flatness.

Example 14 Using the protective film composition (V-1) obtained in Example 1,
According to the above-described method for forming a protective film, a coating film was formed on a glass plate coated with SiO ₂ . When an adhesion test was performed on the obtained coating film in accordance with the above-described method, there was no peeling in a grid pattern, and it was confirmed that the adhesion was excellent. Further, the obtained coating film was N-methyl-2-
10% in pyrrolidone (NMP) and 4% potassium hydroxide aqueous solution
After immersion for a minute, an adhesion test was performed. There was no cross-cut peeling, and it was confirmed that it had excellent chemical resistance. Furthermore,
The spectral transmittance at 400 nm of the obtained coating film was 95% or more, and it was confirmed that the coating film had excellent transparency. And the surface hardness of the obtained coating film was 3H in pencil hardness. From the above, it is confirmed that the coating film formed using the composition for a protective film (V-1) has the required adhesion, chemical resistance, transparency, and surface hardness required for the protective film material.

Comparative Example 1 According to the method of Example 1, a Teflon-coated rotor was placed in a sample bottle (200 ml) and set on a magnetic stirrer. 28 g of cyclohexanone and 39 g of diethylene glycol dimethyl ether were placed in a sample bottle. While stirring, as the epoxy resin of component (B), 8 g of (B1) epoxy resin; ESF-300 (manufactured by Nippon Steel Chemical Co., Ltd.);
2) Epoxy resin; EHPE3150 (Daicel Chemical Industries, Ltd.)
2g, (B3) epoxy resin; EOCN-1020 (Nippon Kayaku)
(Manufactured by Co., Ltd.) was added and completely dissolved. Continued
After adding 6.2 g of trimellitic anhydride (TMAn) and sufficiently stirring and dissolving, further, a silane coupling agent; S-510
1.4 g (manufactured by Chisso Corporation), surfactant; Florard FC
0.12 g of -430 (manufactured by Sumitomo 3M Limited) was added, and the mixture was sufficiently stirred to obtain a composition (R-1). The resulting composition (R
-1) The flatness was evaluated by the method described above. Table 5 shows the results. From Table 5, it is confirmed that the composition (R-1) is inferior in flatness.

Comparative Example 2 In Comparative Example 1, 1,1 was used instead of trimellitic anhydride.
6.8 g of 2,4-trimellitic acid (TMA) was added. One,
2,4-Trimellitic acid is a carboxylic acid species of the blocked carboxylic acid used in Example 1. Although an attempt was made to sufficiently dissolve and stir, 1,2,4-trimellitic acid remained without dissolving a considerable portion, and the desired composition could not be obtained.

Table 5 summarizes the compositions and results of the examples and comparative examples. In Table 5, the C / E equivalent ratio indicates an equivalent ratio between a carboxyl group (C) containing a blocked carboxyl group and an epoxy group (E). The amount of the solvent is
It was adjusted so that the solid content concentration was 31%.

[0055]

[Table 5]

Example 15 According to the method of Example 1, the amounts of component (A) SK-1 and trimellitic anhydride (TMAn) obtained in the above Production Example were used and protected as shown in Table 6. Composition for membrane (V-14 to V-1
7) created. The type and amount of component (B), solvent, silane coupling agent and surfactant were the same as in Example 1. The component (C) was not used. The flatness of the obtained protective film composition was evaluated by the method described above. Table 6 shows the results. When the component (A) and the polycarboxylic acid compound are used in combination as a curing agent for the epoxy resin, a composition for a protective film containing the component (A) in an amount of 5% by weight or more based on the total amount.
(V-14 to V-17) confirms that the flatness is excellent.

Example 16 In accordance with the method of Example 1, the components (A), (B), (C) and the type and amount of the polycarboxylic acid compound were used as shown in Table 6 to form the protective film composition. Products (V-18 to V-19) were prepared. However, each of B2 and B3 as the component (B) is 10 g.
And 15 g were used. The flatness of the obtained protective film composition was evaluated by the method described above. Table 6 shows the results. From Table 6,
It can be confirmed that the composition for a protective film (V-18 to V-19) has excellent flatness.

[0058]

[Table 6]

[0059]

According to the present invention, an LCD having excellent flattening properties is provided.
The composition for a color filter protective film can be supplied. Further, the protective film after curing using the composition for a protective film is a cured product excellent in flatness, and enables the production of the above-described LCD color filter excellent in flatness.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Yamamoto 7-21-11 Nishigotanda, Shinagawa-ku, Tokyo Nippon Steel Chemical Co., Ltd. (72) Inventor Hiroshi Sato 21-1-34 Kumano, Taketoyocho, Chita-gun, Aichi Prefecture (72) Inventor Atsushi Sato 447-1 Shimokuratacho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture -Lucane Yoshi 102 (72) Inventor Masahiro Ishidoya 5-9-5-502 Nanko, Chigasaki City, Kanagawa Prefecture

Claims (6)

[Claims] (A) A molecule represented by the following general formula (1): (However, R ₁ , R ₂ and R ₃ in the formula are a hydrogen atom or a carbon atom 1
To 18 organic group, R ₄ is an organic group having 1 to 18 carbon atoms, R ₃
And R ₄ may combine with each other to form a heterocyclic ring having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. )), A blocked carboxylic acid compound having two or more functional groups represented by the formula (B), an epoxy compound having two or more epoxy groups in one molecule is contained as an essential component, and (C) heating is used if necessary. A composition for a color filter protective film, characterized by containing a heat latent catalyst having an activity at the time of curing as an optional component. (B) 5-95 wt% of an epoxy compound having two or more epoxy groups in one molecule is represented by the following general formula (2): GA-[-CH ₂ -CH (OH) -CH _2- A-] _n -G (2) (where G is a glycidyl group, A is the following formula (3), Wherein n is the number of repetitions. The composition for a color filter protective film according to claim 1, which is an epoxy compound represented by the formula: (D) one molecule represented by the following general formula (1): (However, R ₁ , R ₂ and R ₃ in the formula are a hydrogen atom or a carbon atom 1
To 18 organic group, R ₄ is an organic group having 1 to 18 carbon atoms, R ₃
And R ₄ may combine with each other to form a heterocyclic ring having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. ) Containing as an essential component a self-crosslinking compound having one or more functional groups and one or more epoxy groups,
A composition for a color filter protective film, which comprises, as an optional component, (C) a heat-latent catalyst which is active when heated and hardened, if necessary. 4. The composition for a color filter protective film according to claim 3, further comprising the blocked carboxylic acid compound and / or the epoxy compound according to claim 1. 5. The composition for a color filter protective film according to claim 1, further comprising at least one polyvalent carboxylic acid compound selected from polycarboxylic acids and acid anhydrides of the polycarboxylic acids. . 6. A color filter protective film obtained by curing the composition for a color filter protective film according to claim 1.