JPH0675108A - Resin composition for color filter protective film and color filter protective film - Google Patents

Abstract

PURPOSE:To improve transparency, heat resistance, chemical resistance, spatter resistance and adhesion without degrading physical properties by combining specific (meth)acrylic resins. CONSTITUTION:This resin compsn. contains an epoxy group-contg. (meth)acrylic polymer having 0.05 to 1 ultimate viscosity at 30 deg.C in diethylene glycol dimethyl ether as a component A and a (meth)acrylic polymer contg. >=1 kinds of carboxylic acid group and polyvalent carboxylic anhydride group having 0.05 to 1 ultimate viscosity at 30 deg.C in diethylene glycol dimethyl ether as a component B. The physical properties as the color filter protective film degrade if the ultimate viscosity is below 0.05. The solubility in solvents degrade and the range for selecting the solvents is narrowed and such is undesirable if the ultimate viscosity exceeds 1. The case where the component A is a copolymer essentially consisting of methyl methacrylate (MMA) and glycidyl methacrylate and the component B is a copolymer essentially consisting of the MMA and maleic anhydride is particularly preferable.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for a color filter protective film and a color filter protective film.

[0002]

2. Description of the Related Art As necessary properties of a color filter protective film, transparency, adhesion to a substrate, spatter resistance, coating property, heat resistance, etc. are required. A protective film made of a (meth) acrylic resin composition (for example, JP-A-60-216307).
(Patent Document 1), a protective film made of an epoxy resin composition (for example, JP 4-97102 A), a protective film made of a polyimide resin composition (for example, JP 1-222920 A).
3) has been studied. Of these (meta)
A protective film made of an acrylic resin composition has the highest transparency and has been widely studied.

However, these protective films including a protective film made of a (meth) acrylic resin composition have some problems in balancing adhesion, spatter resistance, heat resistance and the like. Many proposals have been made to improve these points. For example, the above-mentioned JP-A-60-21630.
Japanese Patent Laid-Open No. 7-97102 and Japanese Patent Laid-Open No. 4-97102 disclose a method of forming a protective film by mixing a polycarboxylic acid anhydride with an epoxy group-containing polymer and crosslinking by heating to form a protective film. Since the high molecular compound is reacted with the low molecular weight compound while being mixed, unreacted polyvalent carboxylic acid anhydride remains to form a heterogeneous layer, resulting in deterioration of physical properties, which is not preferable. On the other hand, a protective film made of a polyimide resin composition has a problem that it is inherently inferior in transparency and that high temperature heating is required when the film is cured.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, and does not lower the physical properties of the material, such as transparency, heat resistance, chemical resistance, spatter resistance and adhesion. (EN) An excellent color filter protective film and a resin composition for this protective film.

[0005]

As a result of various studies to solve the above-mentioned conventional problems, the present inventors have found that a specific (meta)
It was found that the resin composition for a color filter protective film and the color filter protective film for the above purposes can be obtained by the combination of acrylic resins, and the present invention has been completed. That is, the resin composition for a color filter protective film of the present invention is characterized by containing the following components (A) and (B). (A) An epoxy group-containing (meth) acrylic polymer having an intrinsic viscosity of 0.05 to 1 in diethylene glycol dimethyl ether at 30 ° C. (B) A (meth) acrylic polymer containing one or more of a carboxylic acid group and a polyvalent carboxylic anhydride group having an intrinsic viscosity of 0.05 to 1 in diethylene glycol dimethyl ether at 30 ° C. Further, the color filter protective film of the present invention is obtained by heating and curing the above resin composition. The component (A) is a copolymer containing methyl methacrylate (hereinafter sometimes abbreviated as “MMA”) and glycidyl methacrylate (hereinafter sometimes abbreviated as “GMA”) as main components,
Component (B) is MMA and maleic anhydride (hereinafter "MAH").
It may be abbreviated as ") is particularly preferable.

The components (A) and (B) used in the present invention can be easily synthesized by ordinary radical polymerization. The resin composition for a color filter protective film of the present invention can be obtained from both of these components.

The epoxy group-containing (meth) acrylic polymer in the component (A) used in the present invention is obtained, for example, by polymerizing an epoxy group-containing (meth) acrylic monomer in the presence of a radical initiator. You can In this case, in order to improve the properties such as solubility and adhesion of the obtained polymer, it is possible to add another acrylic monomer or a small amount of vinyl monomer for copolymerization.

The epoxy group-containing (meth) acrylic monomer can be represented by the following general formula (I).

[Chemical 1] (In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and m represents an integer of 1 to 4.)

The proportion of each monomer in the polymer is
Epoxy group-containing (meth) acrylic monomer is 30 to 10
0% by weight, other (meth) acrylic monomer is 0 to 70
% By weight and 0 to 30% by weight of vinyl monomer.
It is also possible to add a monomer having a carboxylic acid group or a polyvalent carboxylic acid anhydride group described below within a range of 10% by weight as a part of the other (meth) acrylic monomer or vinyl monomer.

The component (A) can be easily obtained by polymerizing each of the monomers in an organic solvent in the presence of a radical initiator by a conventional method. The degree of polymerization of the obtained polymer (A) was such that the intrinsic viscosity at 30 ° C. in diethylene glycol dimethyl ether was 0.05.
It is preferably in the range of -1. The intrinsic viscosity is 0.0
When it is less than 5, the physical properties as a color filter protective film are lowered, and when the intrinsic viscosity is more than 1, the solubility in a solvent is lowered and the selection range of the solvent is limited, which is not preferable.

The (meth) acrylic polymer containing at least one of the carboxylic acid group and the polyvalent carboxylic acid anhydride group in the component (B) used in the present invention is, for example, a carboxylic acid group or a polyvalent carboxylic acid group. It can be obtained by polymerizing an acid anhydride group-containing (meth) acrylic monomer in the presence of a radical initiator. In this case, in order to improve the properties such as solubility or adhesion of the obtained polymer, it is possible to add another (meth) acrylic monomer or a small amount of vinyl monomer to carry out the copolymerization.

Examples of the monomer having a carboxylic acid group or a polyvalent carboxylic acid anhydride group include (meth) acrylic monomers such as acrylic acid and methacrylic acid, maleic anhydride,
Citraconic anhydride, 2,3-dimethylmaleic anhydride,
Examples thereof include maleic anhydride derivatives such as 1-cyclohexane-1,2-dicarboxylic anhydride, ethylmaleic anhydride, 2-methyl-3-ethylmaleic anhydride and 2,3-diethylmaleic anhydride. Other (meth) acrylic monomers used in the synthesis of the component (A) or (B) include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethoxy acrylate. Ethyl, acrylic acid 2-
Acrylic esters such as hydroxyethyl, or methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, 2-hydroxy methacrylate. Examples thereof include methacrylic acid esters such as ethyl and 2-hydroxypropyl methacrylate.
As the vinyl-based monomer used in the synthesis of the component (A) or (B), N-vinylpyrrolidone, styrene, p
-Hydroxystyrene, α-methylstyrene and the like can be mentioned.

The proportion of each monomer in the polymer is
A monomer having a carboxylic acid group or a polycarboxylic acid anhydride group is 10 to 70% by weight, another (meth) acrylic monomer is 30 to 90% by weight, and a vinyl monomer is 0 to
It is 30% by weight. The epoxy group-containing (meth) acrylic monomer described above can be added within a range of 10% by weight as a part of the other (meth) acrylic monomer.

The component (B) can be easily obtained by polymerizing each of the monomers in an organic solvent in the presence of a radical initiator by a conventional method. The degree of polymerization of the obtained polymer is preferably such that the intrinsic viscosity at 30 ° C. in diethylene glycol dimethyl ether is in the range of 0.05 to 1. When the intrinsic viscosity is less than 0.05, the physical properties as the viscosity for the color filter protective film are lowered, and when the intrinsic viscosity is more than 1, the solubility in the solvent is lowered and the solvent selection range is limited. Not very good.

As the organic solvent used in the polymerization reaction for obtaining the component (A) or (B), ketones such as methyl ethyl ketone, methyl isobutyl ketone and methyl cyclohexanone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, Examples thereof include ethers such as diethylene glycol monoethyl ether, and esters such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.

As the radical initiator used in the polymerization reaction for obtaining the component (A) or (B), organic peroxides such as benzoyl peroxide, t-butylperoxybenzoate and lauroyl peroxide, or azobus isobutyro Nitrile etc. can be illustrated.

In the color filter protective film of the present invention, the obtained resin composition comprising the components (A) and (B) and, if necessary, a coupling agent or the like are dissolved in an organic solvent to form a coating solution, which is formed. It is obtained by applying, heating and curing. That is, the coating liquid can be obtained by dissolving at least one of each of the component (A) and the component (B) in an organic solvent. As this organic solvent,
The organic solvent used in the polymerization reaction for obtaining the component (A) or (B) can be used. The mixing ratio of the two is preferably such that the epoxy group in the component (A) and the carboxylic acid group in the component (B) (calculated as two carboxylic acid anhydride groups are two carboxylic acid groups) are close to equivalent, but not so much. It does not have to be strict. It is also possible to employ a so-called two-liquid mixing method in which the component (A) and the component (B) are separately dissolved in an organic solvent and the two are mixed immediately before use. The polymer concentration in the coating solution will be selected according to the required film thickness of the coating film, but it is generally in the range of 5 to 50% by weight.

If necessary, a polymer of
It is also possible to add a cross-linking aid and a coupling agent in an amount of up to wt%. As the crosslinking aid, compounds containing a hydroxyl group, a carboxyl group and an amino group are used. The coupling agent is used to improve the adhesion to the substrate, and as the coupling agent, silane, aluminum and titanate compounds are used. Specific examples of these include 3-aminopropyltriethoxysilane, 3-aminophenyltriethoxysilane, and 3
-Glycidoxypropyltrimethoxysilane, silane-based such as 3-methacryloxypropyltrimethoxysilane,
Examples thereof include aluminum-based materials such as acetoalkoxyaluminum diisopropylate and titanate-based materials such as tetraisopropylbis (dioctylphosphite) titanate.

The obtained coating solution is applied onto a color filter by a conventionally known method such as spin coating, printing, dipping or roll coater method to form a coating film, and the coating film is formed on a hot plate, an electric furnace or a centrifugal furnace. The color filter protective film of the present invention can be obtained by crosslinking and curing by heating by a conventionally known heating method such as infrared irradiation. The heating conditions for the coating film are 150 to 250.
C., preferably 170 to 220.degree. C. for several minutes to 2 hours.

Epoxy group-containing (meth) component (A)
Since the component (B), which will crosslink the acrylic copolymer, is also a (meth) acrylic copolymer, the mutual compatibility is good, and therefore the obtained color filter protective film of the present invention is transparent. Excellent in required properties such as chemical resistance, heat resistance and spatter resistance.

[0021]

[Examples] Hereinafter, synthesis examples, examples and comparative examples
The present invention will be described in more detail, but the present invention is not limited to these examples.

Synthesis of Epoxy Group-Containing (Meth) Acrylic Polymer Synthesis Example 1 70 parts by weight of GMA (hereinafter abbreviated as "part"), MMA
30 parts of azobisisobutyronitrile (hereinafter referred to as "AIB
1 part of N) is dissolved in 300 parts of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and polymerized at 60 ° C. for 4 hours and then at 80 ° C. for 12 hours. The polymer was transferred to n-heptane to precipitate the polymer, which was separated by filtration and dried under reduced pressure in a vacuum dryer at 50 ° C. for one day to obtain a copolymer (this copolymer is referred to as “AI”). . The intrinsic viscosity of this copolymer measured at 30 ° C. in a diethylene glycol dimethyl ether solution was 0.092.

Synthesis Example 2 60 parts of GMA, 30 parts of MMA, 10 parts of styrene,
And 0.8 parts of AIBN to 300 parts of diethylene glycol dimethyl ether (hereinafter abbreviated as "DIG")
A copolymer having an intrinsic viscosity of 0.32 was obtained by the same synthesis as in Synthesis Example 1 except that the copolymer was dissolved therein (A-II).

Synthesis of (meth) acrylic polymer containing one or more of carboxylic acid group and polycarboxylic acid anhydride group Synthesis Example 3 30 parts of MAH, 70 parts of MMA and 1 part of AIBN are added to MEK. The copolymer was synthesized in the same manner as in Synthesis Example 1 except that the copolymer was dissolved in 300 parts to obtain a copolymer having an intrinsic viscosity of 0.12 (B-
I).

Synthesis Example 4 30 parts of MAH, 65 parts of MMA, 5 parts of GMA and A
A copolymer having an intrinsic viscosity of 0.088 was obtained in the same manner as in Synthesis Example 1 except that 1 part of IBN was dissolved in 350 parts of MEK. (B-II)

Synthesis Example 5 20 parts of MAH, 70 parts of MMA, 10 parts of methacrylic acid
Parts and 1 part of AIBN were dissolved in 300 parts of DIG, and synthesis was carried out in the same manner as in Synthesis Example 1 above, and the intrinsic viscosity was 0.38.
To obtain a copolymer (B-III).

Regarding the protective films obtained in Examples and Comparative Examples, transparency, which is a characteristic required as a color filter protective film,
The following characteristics were evaluated with respect to the adhesion to the substrate, chemical resistance, heat resistance and spatter resistance. The results are shown in Table 1. Transparency: Shimadzu Corporation spectrophotometer (UV-210
The light transmittance was measured according to A), and the light transmittance (%) at a wavelength of 400 nm was shown. Heat resistance: Shows the transparency after heat treatment at 250 ° C. for 3 hours, that is, the light transmittance (%) at a wavelength of 400 nm. Chemical resistance: N-methyl-2-pyrrolidone solution at room temperature for 30
It was fixed vertically and soaked for a minute, and it was judged whether the boundary line between the part submerged in the liquid and the part not so submerged could be visually discerned. The case where the boundary line was visible was evaluated as ×, and the case where it was not possible was evaluated as ◯. Spatter resistance: Film thickness of 2 at 200 ° C due to sputtering
When a 00 angstrom ITO film (indium oxide film) was formed on the protective film, the presence or absence of wrinkles in the film was examined. The case where there were wrinkles was evaluated as ×, and the case where there were no wrinkles was evaluated as ○. Adhesion: A cut was made on the protective film to make 100 square pieces of 1 mm each, and cellophane tape was attached to the surface and immediately peeled off. At that time, when the protective film was peeled off together with the cellophane tape, it was evaluated as x, and when not, it was evaluated as o.

Example 1 13 parts of the polymer (AI) obtained in Synthesis Example 1 and Synthesis Example 3
A resin composition was prepared from the polymer obtained in (1) and 12 parts of BI. 25 parts of the resin composition and 2.5 parts of a silane coupling agent (manufactured by Chisso Corporation) were used as an organic solvent. A coating solution was prepared by dissolving it in 75 parts of DIG, which was prepared as follows: The coating solution was applied on a glass plate having a length of 200 mm and a width of 100 mm, and heated in an oven kept at 200 ° C. for 1 hour to cure. Then, a protective film having a film thickness of 2 μm was formed.

[Table 1]

Examples 2 to 6 As shown in Table 1, the polymers (AI, A-II) obtained in Synthesis Examples 1 and 2 and the polymers (B obtained in Synthesis Examples 3 to 5)
-I, B-II, B-III) to prepare a resin composition. Protective films were formed in the same manner as in Example 1 except that the combination of the resin composition and the coupling agent and the mixing ratio were changed, and the transparency and the like of these protective films were measured. The results are shown in Table 1.

Comparative Examples 1 and 2 (when Component (B) is not Contained) As shown in Table 1, the copolymer (AI) obtained in Synthesis Example 1
And trimellitic anhydride or MAH and DIG,
Protective films were formed in the same manner as in Example 1 in combination with a coupling agent, and the transparency and the like of these protective films were measured. The results are shown in Table 1.

As is clear from the results shown in Table 1, the protective films of Examples 1 to 6 are excellent in all of transparency, heat resistance, chemical resistance, spatter resistance and adhesion. I understand. On the other hand, the protective films of Comparative Examples 1 and 2 are
It is particularly inferior in terms of heat resistance, chemical resistance and spatter resistance, and is therefore unsuitable as a color filter protective film.

[0032]

The resin composition for a color filter protective film of the present invention is most suitable for use as a color filter protective film. The color filter protective film of the present invention is excellent in all of the necessary properties of the color filter protective film, such as transparency, heat resistance, chemical resistance, spatter resistance and adhesion.

Claims (4)

[Claims] 1. A resin composition for a color filter protective film, which contains the following components (A) and (B). (A) An epoxy group-containing (meth) acrylic polymer having an intrinsic viscosity of 0.05 to 1 in diethylene glycol dimethyl ether at 30 ° C. (B) A (meth) acrylic polymer containing one or more of a carboxylic acid group and a polyvalent carboxylic anhydride group having an intrinsic viscosity of 0.05 to 1 in diethylene glycol dimethyl ether at 30 ° C. 2. The epoxy group-containing (meth) acrylic polymer is a copolymer containing methyl methacrylate and glycidyl methacrylate as main components, and the carboxylic acid group and polyvalent carboxylic acid anhydride group are The resin composition for a color filter protective film according to claim 1, wherein the (meth) acrylic polymer containing at least one kind is a copolymer containing methyl methacrylate and maleic anhydride as main components. 3. A color filter protective film obtained by heating and curing a resin composition containing the following component (A) and component (B). (A) An epoxy group-containing (meth) acrylic polymer having an intrinsic viscosity of 0.05 to 1 in diethylene glycol dimethyl ether at 30 ° C. (B) A (meth) acrylic polymer containing one or more of a carboxylic acid group and a polyvalent carboxylic anhydride group having an intrinsic viscosity of 0.05 to 1 in diethylene glycol dimethyl ether at 30 ° C. 4. The epoxy group-containing (meth) acrylic polymer is a copolymer containing methyl methacrylate and glycidyl methacrylate as main components, and the epoxy group-containing (meth) acrylic polymer of the carboxylic acid group and polyvalent carboxylic acid anhydride group The color filter protective film according to claim 3, wherein the (meth) acrylic polymer containing at least one kind is a copolymer containing methyl methacrylate and maleic anhydride as main components.