JPH0578453A - Protecting film material - Google Patents

Abstract

PURPOSE:To obtain the subject material useful for a protecting film for optical devices, having excellent ITO sputtering resistance by blending a specific polymer with a polyfunctional carboxylic acid, etc., an acrylic compound and a compound containing an alkoxysilano group and epoxy group. CONSTITUTION:(A) A polymer containing 20wt.% (preferably 30-70wt.%) constituent unit of the formula (R is H or 1-5C alkyl; (m) is 1-8) is blended with (B) one or more compounds selected from $ polyfunctional carboxylic acid anhydrides (preferably aromatic polyfunctional carboxylic acid anhydride such as phthalic anhydride) and polyfunctional carboxylic acids (preferably phthalic acid) as curing agent, (C) an acrylic compound (preferably tri-or polyfunctional acrylic compound), (D) a compound (e.g. triglycidoxypropyltrimethoxysilane) and optionally a curing promoter, a surfactant, etc., to give the objective material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a protective film material composed of a thermosetting resin composition and suitable for an optical device.

[0002]

2. Description of the Related Art In a display device such as a liquid crystal display device, a dipping treatment is performed in a solvent, an acid or an alkaline solution or the like during the manufacturing process, and the surface of the wiring electrode layer is locally formed during film formation by sputtering. Exposed to high temperatures. Therefore, in order to prevent the element from being deteriorated or damaged by such a treatment, a thin protective film layer having resistance to these treatments is provided.

In such a protective film, the adhesiveness to the substrate or the lower layer and the layer formed thereon is high, and the film itself is smooth and tough, transparent, and has heat resistance and light resistance. It is required to have high performance such that it is free from deterioration such as coloring, yellowing and whitening over a long period of time, and has excellent water resistance, solvent resistance, acid resistance and alkali resistance. As a protective film material satisfying these various properties, for example, a thermosetting composition disclosed in JP-A-60-217230 is known.

[0004]

However, for example, in the case of a super twisted nematic (STN) type color liquid crystal display element, compared with the conventional twisted nematic (TN) type liquid crystal display element, the cell Since the uniformity of the gap is very important, the flatness of the substrate surface is required. This is because display unevenness occurs if the substrate surface is not flat.

Conventionally, the protective film layer has been often used mainly in the TN type liquid crystal panel, so that the flattening property is not often required and the protective film actually formed on the color filter substrate. When the layer was examined, surface irregularities caused by the production of the color filter were almost directly expressed on the surface of the protective film layer.

Therefore, in view of the above-mentioned drawbacks of the prior art, the present invention provides a protective film material capable of forming a protective film having an effect of reducing the unevenness on a color filter, particularly suitable for STN. With the goal.

[0007]

According to the present invention, (A) the following general formula (1)

[Chemical 2] [In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 8] A polymer containing at least 20% by weight of a structural unit represented by (Hereinafter referred to as “polymer A”), (B) at least one compound selected from polycarboxylic acid anhydrides and polycarboxylic acids, (C) an acrylic compound, and (D) an alkoxysilano group. There is provided a protective film material containing a compound having an epoxy group. This protective film material has a high ability to flatten the irregularities on the substrate because it can achieve a high concentration and low viscosity, and a high crosslink density can be obtained. Layers can be formed.

Component (A) A component which is a base component in the protective film material of the present invention.
As described above, the polymer A of (A) has a structural unit represented by the general formula (1). In this general formula (1), m
Is an integer of 1 to 8, preferably 1 to 4. Also R
Is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. The lower alkyl group may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and n-pentyl. Can be illustrated.

The monomer used for introducing the constitutional unit represented by the general formula (1) is, for example, (meth)
Glycidyl acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-
Glycidyl butyl acrylate, (meth) acrylic acid-
Examples include 3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl and the like. it can. Of these, glycidyl (meth) acrylate is particularly preferable. These monomers can be used alone or in combination of two or more.

The constituent unit represented by the general formula (1) introduced from these monomers is contained in the polymer A in an amount of at least 20% by weight in order to effectively carry out the crosslinking reaction in the coating film. However, it is particularly preferable that the content is 30 to 70% by weight.

The polymer A may contain a constitutional unit other than the constitutional unit represented by the general formula (1) in an amount of 80% by weight or less, particularly 70 to 30% by weight. Examples of the comonomer for introducing another structural unit include (meth)
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta (meth) acrylate Nyl, esters of (meth) acrylic acid such as dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate; vinyl aromatic systems such as styrene, α-methylstyrene, p-methylstyrene, vinylnaphthalene A compound can be mentioned.

The molecular weight of the polymer A is not particularly limited as long as the solution of the protective film material of the present invention can be uniformly applied, and it depends on the thickness of the coating film to be formed, coating conditions, purpose and the like. Although appropriately selected, it is generally preferred that the polystyrene reduced weight average molecular weight is in the range of 5,000 to 300,000.
Further, the polymer A used in the present invention may be a random copolymer or block copolymer of each of the above-mentioned monomers as long as it has the above-mentioned constitutional unit.

Component (B) In the protective film material of the present invention, the polycarboxylic acid anhydride or polycarboxylic acid used as the component (B) acts as a curing agent for the polymer A.

Examples of the polycarboxylic acid anhydride include itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and anhydrous Aliphatic dicarboxylic acid anhydride such as hymic acid, alicyclic polycarboxylic acid dianhydride such as 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride Acids, pyromellitic dianhydride, trimellitic dianhydride, aromatic polycarboxylic acid anhydrides such as benzophenone tetracarboxylic acid anhydride, ethylene glycol bis anhydride trimellitate, ester group-containing acid anhydrides such as glycerin tris anhydride trimellitate You can Of these, aromatic polycarboxylic acid anhydrides are particularly preferable from the viewpoint of heat resistance.

Examples of polyvalent carboxylic acids include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid, hexahydrophthalic acid and 1,2-cyclohexane. Alicyclic polyvalent carboxylic acids such as dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,2,5 Aromatic polyvalent carboxylic acids such as 8,8-naphthalene tetracarboxylic acid can be exemplified. In particular, aromatic polyvalent carboxylic acids are preferable from the viewpoint of reactivity, heat resistance and the like.

These polyvalent carboxylic anhydrides or polycarboxylic acids as the component (B) can be used alone or in combination of two or more kinds, and usually 1 to 100 parts by weight per 100 parts by weight of the polymer A. It is preferably used in a proportion of 3 parts by weight, especially 3 to 50 parts by weight. If it is less than this, the cross-linking density of the protective film formed is not sufficient and various resistances are reduced, and if it is too large, a large amount of unreacted curing agent component remains in the protective film, resulting in poor film properties. It becomes stable and the adhesiveness decreases.

[0017] While acrylic compound component (C) Component (C) also acting as a curing agent, in particular gives a flattening function on the protective film. Such acrylic compounds include monofunctional, difunctional, or trifunctional or higher-functional polyfunctional compounds, and usually an esterified product capable of radical reaction by heat is used.

As the monofunctional acrylic compound, phenoxy polyethylene glycol (meth) acrylate,
There are nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate and the like, and these are, for example, Aronix M-101, M-111 and M-114 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), Commercially available under the trade names of V158 and V2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the bifunctional acrylic compound include polyethylene glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, and hexamethylene glycol di (meth) acrylate. These are, for example, Aronix M- 210, M-240, M-6200 (manufactured by Toagosei Chemical Industry Co., Ltd.),
KAYARAD HDDA, HX-220, R-604, R-629
(Nippon Kayaku Co., Ltd.), V260, V-312, V-335H
It is commercially available under the trade name of P (Osaka Organic Chemical Industry Co., Ltd.) and the like.

Examples of trifunctional or higher polyfunctional acrylic compounds include dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. Etc. These are, for example, Aronix M-400.
, The same M-405, the same M-450, the same M-7100, the same M-803
0, same M-8060 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD
TMPTA, DPCA-20, DPCA-30, DPC
A-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), VG
It is marketed under the trade name of PT (Osaka Organic Chemical Industry Co., Ltd.) and the like.

Among these acrylic compounds, trifunctional or higher functional acrylic compounds are preferable, and trifunctional or higher functional acrylic compounds containing no oxyalkylene structure such as oxyethylene are particularly preferable. Commercially available products thereof include, for example, Aronix M-400, M-405, M-450 and M-.
7100, M-8030, M-8060, KAYARAD TMPTA and the like.

These acrylic compounds of component (C) can be used alone or in combination of two or more, and the amount thereof is usually 5 to 200 parts by weight, particularly 10 to 10 parts by weight per 100 parts by weight of component (A). A range of 100 parts by weight is preferred. If it is less than the above range, sufficient flatness cannot be obtained, and if it is more than the above range, film roughness and phase separation may occur during the formation of the protective film, or the heat resistance of the film may deteriorate.

[0023] Component (D) a compound having an alkoxy silanol groups and epoxy groups of component (D), as well as providing a flattening action on the protective film together with the component (C), to impart adhesion to the protective film.

Examples of such compounds include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ
-Glycidoxypropyldiethoxysilane and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The amount of the component (D) compound used is generally 0.1 to 200 parts by weight, preferably 5 to 150 parts by weight, per 100 parts by weight of the component (A). If it is less than the range, sufficient adhesion cannot be obtained between the protective film and the substrate,
In addition, sufficient flatness cannot be obtained. Further, if it exceeds the above range, the alkali resistance, solvent resistance, etc. of the protective film may be deteriorated.

Other compounding agents In the protective film material of the present invention, in addition to the above-mentioned components (A) to (D), other compounding agents such as a curing accelerator, a surfactant and an ultraviolet absorber may be added if necessary. Etc. can be blended.

The curing accelerator is composed of the components (A) and (D) and (B).
It is used to accelerate the reaction with the components, and generally, a compound having a heterocyclic structure containing a secondary nitrogen atom or a tertiary nitrogen atom is used. Specific examples include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, benzimidazole and isocyanuric acid. Among these, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 4-methyl-2-phenylimidazole, 1
-Benzyl-2-methylimidazole, 2-ethyl-4
-Methyl-1- (2'-cyanoethyl) imidazole,
Imidazole derivatives such as 2-ethyl-4-methyl-1- [2 '-(3 ", 5" -diaminotriazinyl) ethyl] imidazole and benzimidazole are preferred, and most preferably 2-ethyl- 4-Methylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole are used. These curing accelerators are
They may be used alone or in combination of two or more kinds, and it is generally desirable to use them in an amount of 0 to 30 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the component (A).

As the surface active agent, fluorine type and silicone type can be preferably used. As the fluorinated surfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain and side chain is suitable, and specifically,
1,1,2,2-Tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-Tetrafluorooctylhexyl ether, Octaethylene glycol di (1,
1,2,2-Tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl)
Ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate , 1,1,
2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3
-Hexafluorodecane and the like can be mentioned. Moreover, as these commercial products, BM-1000, BM-1100 (BM Ch
(Made by emie), MegaFac F142D, F172, F173
, F183 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

Examples of silicone-based surfactants include Torre silicone DC3PA, SH7PA, D
C11PA, SH21PA, SH28PA, SH29P
A, SH30PA (manufactured by Torre Silicone Co., Ltd.), TS
F-4440, TSF-4300, TSF-4445, TSF-444
6, commercially available products such as TSF-4460 and TSF-4445 (manufactured by Toshiba Silicone Co., Ltd.) can be mentioned.

These surfactants can be used alone or in combination of two or more, and the amount thereof used is
Although it depends on the type and concentration of each component (A) to (D), the range of 0 to 5 parts by weight, particularly 0.001 to 2 parts by weight, is preferable per 100 parts by weight of the component (A). ..

Protective Film Material The protective film material of the present invention can be easily prepared by uniformly mixing the above-mentioned components, and is dissolved in an appropriate solvent and used in the form of a solution. The solvent to be used is not particularly limited as long as it can dissolve each component uniformly and does not react with each component, but in general, from the ease of forming a coating film, a cellosolve acetate system and a diglyme system are used. Are preferred, particularly ethyl cellosolve acetate, ethyl carbitol acetate, diethylene glycol dimethyl ether and diethylene glycol diethyl ether. These solvents may be used alone or in combination of two or more. The concentration of the solution of this composition is not particularly limited and can be appropriately selected according to the purpose of use, but it is usually used at a solid concentration of about 5 to 50% by weight.

In the present invention, a desired protective film can be formed by applying the solution of the above-mentioned protective film material on the surface of a predetermined substrate and curing it by heating. The coating method on the surface of the substrate is not particularly limited, and various methods such as a spray method, a roll coating method and a spin coating method can be adopted. The conditions for thermosetting the protective film material of the present invention are usually at 150 to 250 ° C. for about 0.2 to 1.5 hours, although they vary depending on the specific type and mixing ratio of each component.

The protective film formed from the protective film material of the present invention is excellent in various properties and flatness, as is clear from the following examples, and is extremely useful as a protective film for optical devices such as color filters. It is suitable. EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention will be described in more detail, but the present invention is not limited to these Examples.

[0034]

Examples Examples 1 to 5 (1) Synthesis of polymer A: Monomers shown in the column of component (A) in Table 1 were used in a weight ratio shown in the column of component (A) in the column. The total amount of 100 parts by weight is mixed with 300 parts by weight of ethyl cellosolve acetate, 0.5 part by weight of azobisisobutyronitrile (AIBN) is added as a polymerization initiator, and the mixture is polymerized at 80 ° C. for 3 hours. A solution having a concentration of polymer A of 25% by weight was obtained.

(2) Preparation of protective film material; the above polymer solution 1
After diluting 00 parts by weight (polymer A: 25 parts by weight) with 25 parts by weight of ethyl cellosolve acetate, (B) to (D) and other components were added according to the formulation shown in Table 1.
After sufficiently stirring, a protective film material was obtained.

(3) Formation of protective film; (3-1) Protective film for evaluation of various resistances The above-mentioned protective film material was applied onto a glass substrate so that the film thickness was 2 μm, and then in a clean oven at 200 ° C. It was heat-cured for 1 hour to form a protective film. (3-2) Protective film for evaluation of adhesion and flatness Using a solution of gelatin and potassium dichromate on a glass substrate (Corning 7059, Douglas Dow Corning), striped red, blue, and A substrate with three color filters of green was created (stripe width 1
50 μm). When the surface irregularities of this substrate were examined by α-step (manufactured by Tencor Co., Ltd.), it was 1.0 μm. On this substrate, as in (3-1) above, apply the protective film material,
It was heat-cured to form a protective film.

(4) Evaluation of protective film The protective film obtained in (3-1) and (3-2) above was evaluated as follows, and the results are shown in Table 2.

Adhesiveness JIS K-5400 (1900) 8.5 Of the adhesiveness, 100 pieces are adhered to the protective film prepared in (3-1) and (3-2) above according to the 8.5 / 2 cross-cut tape method. The cross-cuts were formed with a cutter knife, and the adhesion was evaluated. The adhesiveness was evaluated according to the following criteria based on the number of cross-cut grids. ○: 5 or less △: 6 to 49 ×: 50 or more

Surface hardness JIS K-5400 (1990) 8.4 of the pencil scratch test, 8.4
According to the 1 test method, the surface hardness of the protective film prepared in (3-1) was evaluated by the scratches formed on the protective film.

20% by weight of the protective film made of acid resistant (3-1) together with the substrate
Evaluation was carried out by changing the appearance after immersion in a hydrogen chloride aqueous solution at 40 ° C. for 10 minutes.

A protective film made of alkali resistance (3-1) is used together with the substrate in an amount of 10% by weight.
Evaluation was performed by changing the appearance after immersion in an aqueous sodium hydroxide solution at 40 ° C. for 60 minutes.

The transmission spectrum (400 to 70) before and after the heat treatment (250 ° C. × 60 minutes in a clean oven) of the protective film formed by heat resistance (3-1)
It was evaluated by comparing (0 nm). The evaluation criteria are as follows. ○: Within 1% of spectrum change ×: Over 1% of spectrum change

The surface roughness of the CF substrate having the protective film formed by the flattening property (3-2) was examined by α-step, and the flattening rate (%) was calculated by the following formula.
Was calculated and evaluated.

[0044]

[Equation 1]

Comparative Example 1 A protective film material and a protective film were prepared in the same manner as in Example 1 except that the component (C) among the components used in Example 1 was not used. An evaluation was done. The results are shown in Table 2.

Comparative Example 2 A protective film material and a protective film were prepared in the same manner as in Example 1 except that the component (D) among the components used in Example 1 was not used. An evaluation was done. The results are shown in Table 2.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

INDUSTRIAL APPLICABILITY The protective film material of the present invention forms a protective film which is excellent not only in various resistances but also in flattening property for reducing unevenness or steps on the color filter surface.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C09D 163/00 PJK 8416-4J (72) Inventor Yasuaki Yokoyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (A) The following general formula (1): [In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 8] A polymer containing at least 20% by weight of a structural unit represented by , (B) at least one compound selected from polycarboxylic acid anhydrides and polycarboxylic acids, (C) an acrylic compound, and (D) a compound having an alkoxysilano group and an epoxy group, Protective film material.