JP4915500B2 - Thermosetting resin composition, method for forming color filter protective film, and color filter protective film - Google Patents

Abstract

Provided is a thermosetting resin composition, which is able to form cured films having high flatness on a substrate having low flatness, has high transparency and surface hardness and excellent various resistances, and is useful for protective films for optical devices. The thermosetting resin composition comprises (A) a copolymer of (a1) a polymerizable unsaturated compound having an oxyranyl group or oxetanyl group and (a2) other polymerizable unsaturated compound than the component (a1), (B) a compound having at least one carboxyl group and at least one (meth)acrylic group, and further (C) an adhesive aid consisting of a silane coupling agent having a reactive substituent.

Description

  The present invention relates to a thermosetting resin composition, a method for forming a color filter protective film from the composition, and a color filter protective film. More specifically, a composition suitable as a material for forming a protective film used in a color filter for a liquid crystal display element (LCD) and a color filter for a charge coupled device (CCD), and formation of a protective film using the composition The present invention relates to a method and a protective film formed from the composition.

Radiation devices such as LCD and CCD are subjected to immersion treatment of display elements with a solvent, acid or alkali solution during the manufacturing process, and when forming a wiring electrode layer by sputtering, the element surface is localized. Exposed to high temperatures. Therefore, in order to prevent the element from being deteriorated or damaged by such treatment, a protective film made of a thin film having resistance to these treatments is provided on the surface of the element.
Such a protective film has high adhesion to the substrate or lower layer on which the protective film is to be formed, and further to the layer formed on the protective film, the film itself is smooth and tough, transparent It has high heat resistance and light resistance, does not cause deterioration such as coloring, yellowing, and whitening over a long period of time, and has excellent water resistance, solvent resistance, and alkali resistance Performance is required. As a material for forming a protective film satisfying these various properties, for example, a thermosetting composition containing a polymer having a glycidyl group is known (see Patent Document 1 and Patent Document 2).
In addition, when such a protective film is used as a protective film for a color liquid crystal display device or a color filter of a charge coupled device, it is generally required that the step formed by the color filter formed on the base substrate can be flattened. The

Further, in a color liquid crystal display device, for example, a STN (Super Twisted Nematic) type or TFT (Thin Film Transistor) type color liquid crystal display element, a bead-like spacer is provided on the protective film in order to uniformly maintain the cell gap of the liquid crystal layer. The panels are pasted together after spraying. After that, the liquid crystal cell is sealed by thermocompression bonding with a sealing material, but the heat and pressure applied at that time show a phenomenon that the protective film in the part where the beads exist is recessed, and the cell gap may be distorted. It is a problem.
In particular, when manufacturing an STN color liquid crystal display element, the accuracy of bonding between the color filter and the counter substrate must be extremely strict, and the protective film has an extremely high level difference in leveling performance and Heat-resistant pressure resistance is required.
In recent years, as the glass substrate size is increased for TV applications, it has become one of the extremely important characteristics from the viewpoint of cost to regenerate defective color filters. In order to regenerate the color filter, a rework (film peeling) characteristic of the protective film is required. The rework characteristics are in a trade-off relationship with alkali resistance, and there has been no protective film that achieves both rework characteristics and alkali resistance.

For the formation of such a protective film, it is convenient to use a thermosetting composition having an advantage that a protective film having excellent hardness can be formed by a simple method. The protective film resin composition of the present invention has a reactive crosslinking group or catalyst that forms strong crosslinks, and therefore there is a problem that the shelf life of the composition itself is very short, and handling is very troublesome. Met. That is, not only the coating performance of the composition itself deteriorates with time, but also frequent maintenance and washing of the coating machine are required, and the operation is complicated.
In addition to satisfying general performance requirements for protective films such as transparency, materials that can easily form protective films that satisfy the various performances described above and have excellent storage stability as compositions are still known. Not.

Patent Document 3 discloses a thermosetting composition containing a latent carboxyl compound used for paints, inks, adhesives, and molded articles, but does not disclose any color filter protective film. Absent.
JP-A-5-78453 JP 2001-91732 A JP-A-4-218561

  The present invention has been made on the basis of the above circumstances, and its object is to form a cured film having high flatness on the substrate even if the substrate has low surface flatness. In addition, it is suitable for forming a protective film for optical devices having high transparency and high surface hardness, excellent heat resistance and pressure resistance, alkali resistance, reworkability, etc., and as a composition. It is an object to provide a composition having excellent storage stability, a method for forming a protective film using the composition, and a protective film formed from the composition.

The present invention provides a copolymer of A) (a1) a polymerizable unsaturated compound having an oxiranyl group or oxetanyl group and (a2) a polymerizable unsaturated compound other than the above (a1) (hereinafter referred to as “(A) copolymer”). And (B) a compound having one or more carboxyl groups and one or more (meth) acryl groups (hereinafter also referred to as “(B) compounds”). The present invention relates to a resin composition.
Here, the proportions of the component (a1) and the component (a2) constituting the copolymer (A) are (a1) 5 to 95% by weight, (a2) 95 to 5% by weight [provided that (a1) + ( a2) = 100 wt%].
Moreover, the compounding quantity of (B) compound is 10-200 weight part with respect to 100 weight part of (A) copolymer.
The thermosetting resin composition of the present invention may further contain (C) an adhesion assistant composed of a silane coupling agent having a reactive substituent.
Here, the blending amount of (C) the adhesion assistant is usually 3 to 40 parts by weight with respect to 100 parts by weight of (A) copolymer.
The thermosetting resin composition of the present invention may further contain (D) a surfactant.
Here, the compounding quantity of (D) surfactant is 0.01-1 weight part normally with respect to 100 weight part of (A) copolymers.
The above thermosetting resin composition of the present invention is useful for forming a protective film for a color filter.
Next, this invention relates to the formation method of the protective film of a color filter characterized by forming a coating film on the board | substrate using the said thermosetting resin composition, and then heat-processing.
Next, the present invention relates to a color filter protective film formed by the method for forming a color filter protective film.

  According to the present invention, even a substrate having low surface flatness can form a cured film having high flatness on the substrate, and has high transparency and surface hardness, heat resistance and pressure resistance, Resin composition that is suitably used to form a protective film for optical devices excellent in various resistances such as alkali resistance and reworkability, and excellent in storage stability as a composition, and protection using the resin composition A film forming method and a protective film formed from the composition are provided.

Hereinafter, each component of the resin composition of this invention is demonstrated.
(A) Copolymer The (A) copolymer of the present invention comprises (a1) a polymer unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and (a2) other than the polymer unit of (a1) above. The polymerization unit is derived from a polymerizable unsaturated compound.
(A) In the copolymer, (a1) the polymerizable unsaturated compound is not particularly limited as long as it has an oxiranyl group or oxetanyl group and a polymerizable unsaturated group. For example, oxiranyl group-containing polymerizable unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid- 3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned.
Examples of the oxetanyl group-containing polymerizable unsaturated compound include 3-methyl-3- (meth) acryloxymethyloxetane and 3-ethyl-3- (meth) acryloxymethyloxetane.
Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are copolymerized and have a protective film. Alternatively, it is preferably used from the viewpoint of increasing the heat resistance and surface hardness of the insulating film.

  In addition to (a1), the copolymer (A) further contains (a2) a polymer unit derived from a polymerizable unsaturated compound other than (a1). (A2) The polymerizable unsaturated compound is, for example, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclounsaturated compounds, maleimide Examples include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated compounds having an acetal structure, and a ketal structure.

  Specific examples of these (a2) polymerizable unsaturated compounds include, for example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) as (meth) acrylic acid alkyl ester. Acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl (meth) acrylate, methyl (meth) Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acryl , Tridecyl (meth) acrylate, n-stearyl (meth) acrylate, t-butoxy (meth) acrylate, 1-dimethyl (iso) propyl (meth) acrylate, 1-dimethyl (iso) butyl (meth) acrylate, 1 -Dimethyl (iso) octyl (meth) acrylate, 1-methyl-1-ethyl (meth) acrylate, 1-methyl-1-ethyl (iso) propyl (meth) acrylate, 1-methyl-1-ethyl (iso) butyl (Meth) acrylate, 1-methyl-1-ethyl (iso) octyl acrylate, 1-diethyl (iso) propyl (meth) acrylate, 1-diethyl (iso) butyl (meth) acrylate, 1-diethyl (iso) octyl ( (Meth) acrylate, etc .;

(Meth) acrylic acid cyclic alkyl ester includes cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, tricyclo [ 5.2.1.0 ^2,6 ] decan-8-yloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 1-methylcyclopropane (meth) acrylate, 1-methylcyclobutane (meth) acrylate, 1- Methylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-methylcycloheptane (meth) acrylate, 1-methylcyclooctane (meth) acrylate, 1-methylcyclononane (meth) acrylate, 1-ethylcyclo Deccan (meta ) Acrylate, 1-ethylcyclopropane (meth) acrylate, 1-ethylcyclobutane (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptane (meth) acrylate, 1-ethylcyclooctane (meth) acrylate, 1-ethylcyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1- (iso) propylcyclopropane (meth) acrylate, 1- (iso) propylcyclobutane (Meth) acrylate, 1- (iso) propylcyclopentyl (meth) acrylate, 1- (iso) propylcyclohexyl (meth) acrylate, 1- (iso) propylcycloheptane (meth) acrylate, 1- (iso Propylcyclooctane (meth) acrylate, 1- (iso) propylcyclononane (meth) acrylate, 1- (iso) propylcyclodecane (meth) acrylate, 1- (iso) butylcyclopropane (meth) acrylate, 1- ( Iso) butylcyclobutane (meth) acrylate, 1- (iso) butylcyclopentyl (meth) acrylate, 1- (iso) butylcyclohexyl (meth) acrylate, 1- (iso) butylcycloheptane (meth) acrylate, 1- (iso ) Butylcyclooctane (meth) acrylate, 1- (iso) butylcyclononane (meth) acrylate, 1- (iso) butylcyclodecanyl (meth) acrylate, 1- (iso) pentylcyclopropanyl (meth) acrylate, 1- (iso) pentylcyclo Tanyl (meth) acrylate, 1- (iso) pentylcyclopentyl (meth) acrylate, 1- (iso) pentylcyclohexyl (meth) acrylate, 1- (iso) pentylcycloheptanyl (meth) acrylate, 1- (iso) pentyl Cyclooctanyl (meth) acrylate, 1- (iso) pentylcyclononanyl (meth) acrylate, 1- (iso) pentylcyclodecanyl (meth) acrylate,

1- (iso) hexylcyclopropanyl (meth) acrylate, 1- (iso) hexylcyclobutanyl (meth) acrylate, 1- (iso) hexylcyclohexyl (meth) acrylate, 1- (iso) hexylcycloheptanyl ( (Meth) acrylate, 1- (iso) hexylcyclooctanyl (meth) acrylate, 1- (iso) hexylcyclononanyl (meth) acrylate, 1- (iso) hexylcyclodecanyl (meth) acrylate,
1- (iso) heptylcyclopropanyl (meth) acrylate, 1- (iso) heptylcyclobutanyl (meth) acrylate, 1- (iso) heptylcycloheptyl (meth) acrylate, 1- (iso) heptylcycloheptyl ( (Meth) acrylate, 1- (iso) heptylcycloheptanyl (meth) acrylate, 1- (iso) heptylcyclooctanyl (meth) acrylate, 1- (iso) heptylcyclononanyl (meth) acrylate, 1- (iso ) Heptylcyclodecanyl (meth) acrylate, 1- (iso) octylcyclopropanyl (meth) acrylate, 1- (iso) octylcyclobutanyl (meth) acrylate, 1- (iso) octylcyclooctyl (meth) acrylate 1- (iso) octylcyclooctyl (meth) Acrylate, 1- (iso) octylcycloheptanyl (meth) acrylate, 1- (iso) octylcyclooctanyl (meth) acrylate, 1- (iso) octylcyclononanyl (meth) acrylate, 1- (iso) octyl Cyclodecanyl (meth) acrylate, 2-ethyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl- (meth) acrylate, 2-methyltricyclo [3.3.1.1 ^{3 , 7} ] decan-2-yl- (meth) acrylate, 1-ethyltricyclo [3.3.1.1 ^3,7 ] decan-1-yl- (meth) acrylate, 1-ethyltricyclo [3. 3.1.1 ^3,7] decan-1-yl - (meth) acrylate 3-hydroxy-tricyclo [3.3.1.1 ^3,7] decane-1-yl - (meth) acrylates And the like;

  Here, the alkyl part of the acrylic acid cyclic alkyl ester may have a lactone structure, a lactam structure, or an acetal structure. Examples include 2-ethyl-γ-butyrolactone-2-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-2-yl- (meth) acrylate, 2-ethyl-γ-butyrolactone-3-yl- ( (Meth) acrylate, 2-methyl-γ-butyrolactone-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactone-4-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-4-yl- (Meth) acrylate, 2-ethyl-δ-valerolactone-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactone- 3-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- (meth) acrylate, 2-ethyl-δ-valerola Kuton-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-5-yl- (meth) acrylate, 2-ethyl Lactones such as -δ-valerolactone-5-yl- (meth) acrylate:

2-ethyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam-3-yl- (meth) acrylate 2-methyl-γ-butyrolactam-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam-4-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-4-yl- (meth) Acrylate, 2-ethyl-δ-valerolactam-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-3-yl -(Meth) acrylate, 2-ethyl-δ-valerolactam-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-4 -Yl- (meth) acrylate, 2-ethyl-δ-valerolactam-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-5-yl- (meth) acrylate, 2-ethyl-δ- Lactams such as valerolactam-5-yl- (meth) acrylate;

As an acetal or ketal structure, 1-ethoxyethyl (meth) acrylate, tetrahydro-2H-pyran-2-yl (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, 1- (2-methylpropoxy) ethyl (Meth) acrylate, 1- (1,1-dimethyl-ethoxy) ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate and the like;
As (meth) acrylic acid aryl ester, phenyl methacrylate, benzyl methacrylate, etc .;
As unsaturated dicarboxylic acid diesters, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;

Bicyclo unsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept. 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 '-Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5 Hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [ 2.2.1] hept-2-ene and the like;
As maleimide compounds, phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3- Maleimide propionate, N- (9-acridinyl) maleimide and the like;

Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like;
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene;
As unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc .;
As unsaturated dicarboxylic acids, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;
As unsaturated dicarboxylic acid anhydrides, the anhydrides of the above unsaturated dicarboxylic acids;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Of these, styrene, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1. ] Hept-2-ene, N-cyclohexylmaleimide, methacrylic acid, 1-ethylcyclopentyl methacrylate, 2-methyl-2-propenoic acid tetrahydro-2H-pyran-2-yl ester, etc., copolymerization reactivity, heat resistance, etc. From the point of view, it is preferable.
These may be used alone or in combination.

  (A) The copolymer is preferably (a1) 5 to 95% by weight and (a2) 95 to 5% by weight, in terms of monomer, of the structural unit derived from the polymerizable unsaturated compound monomer. More preferably (a1) 20 to 95% by weight, and (a2) 80 to 5% by weight, most preferably (a1) 30 to 90% by weight, and (a2) 70 to 10% by weight. When the content falls within this range, good planarization performance and heat resistance can be realized.

As a preferable specific example of the copolymer (A), for example,
Styrene / glycidyl methacrylate copolymer, styrene / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / glycidyl methacrylate copolymer Polymer, styrene / N-phenylmaleimide / glycidyl methacrylate copolymer, N-cyclohexylmaleimide / glycidyl methacrylate copolymer, N-phenylmaleimide / glycidyl methacrylate copolymer, styrene / tricyclomethacrylate [5.2 1.0 ^2,6 ] decan-8-yl / methacrylic acid / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / methacrylic acid / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / methacrylic acid / Metak Glycidyl toluate copolymer, styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / tricyclomethacrylate [5.2.1.0 ^2,6 ] Decan-8-yl / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate copolymer, styrene / N-fluoro Enylmaleimide / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate copolymer, styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer Styrene / N-cyclohexylmaleimide / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / tricyclomethacrylate [5. 2.1.0 ^2,6 ] decan-8-yl / tetrahydro-2H-pyran-2-yl ester / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / tetrahydro-2H -Pyran-2-yl ester / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / tetrahydro-2H-pyran-2-yl ester / glycidyl methacrylate copolymer, and the like.

(A) The copolymer preferably has a polystyrene-equivalent weight average molecular weight (hereinafter sometimes referred to as “Mw”) measured by gel permeation chromatography (elution solvent: tetrahydrofuran), preferably 1,000 to 100,000. More preferably 2,000 to 50,000, and particularly preferably 3,000 to 40,000. In this case, if the Mw is less than 1,000, the coating property of the composition may be insufficient, or the heat resistance of the protective film to be formed may be insufficient. On the other hand, if the Mw exceeds 100,000, the composition may be flat. In some cases, the conversion performance becomes insufficient.
Further, the molecular weight distribution (Mw / Mn) of the copolymer (A) is preferably 5.0 or less, and more preferably 3.0 or less.

Such (A) copolymer comprises (a1) a polymerizable unsaturated compound and (a2) a polymerizable unsaturated compound other than (a1) described above in the presence of a suitable solvent and a suitable polymerization initiator. It can be synthesized by a known method such as radical polymerization.
For example, the radical polymerization may be carried out by using (a1) a polymerizable unsaturated compound such as glycidyl methacrylate in an amount of 5 to 95 parts by weight and (a2) a polymerizable unsaturated compound other than the above (a1) in an amount of 95 to 5 parts by weight [provided that , (A1) + (a2) = 100 parts by weight] is mixed with 100 to 400 parts by weight of a solvent such as ethyl cellosolve acetate or propylene glycol monomethyl ether acetate, and azobisisobutyronitrile (AIBN) is used as a polymerization initiator. ), A radical polymerization initiator such as 2,2′-azobis (2,4-dimethylvaleronitrile) is added in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the total amount of monomer components, and 70 to 100 It is obtained by polymerizing at a temperature of 3 to 10 hours.

(B) Compound having one or more carboxyl groups and one or more (meth) acryl groups Among the compounds (B) used in the present invention, as the acrylate compound,
For example, triacryloyloxypentaerythritol succinic acid {alias: 3-acryloyloxy-2,2-bisacryloyloxymethyl-propyl) ester}, diacryloyloxypentaerythritol succinic acid {alias: 3-acryloyloxy-2- Acryloyloxymethyl-propyl) ester}, pentaacryoyloxydipentaerythritol succinic acid {aka: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2-bis-acrylic Leuoxymethyl-propyl] ester}, tetraacylyloxydipentaerythritol succinic acid {also known as: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2-acryloyloxymethyl- Propyl] ester} That.

  In addition, as the compound (B), a polymerizable unsaturated compound having a carboxyl group and a polymerizable unsaturated compound having a hydroxyl group are polymerized by, for example, a radical reaction, and the isocyanate group and the polymerizable unsaturated group are bonded to the hydroxyl group. The same effect can be expected even when a compound having a urethanation reaction is urethanized. Examples of the polymerizable unsaturated compound having a carboxyl group include (meth) acrylic acid, and examples of the polymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. Examples of the compound having an isocyanate group and a polymerizable unsaturated group include (meth) acryloyloxyethyl isocyanate.

  (B) The compound having one or more carboxyl groups and one or more acrylic groups is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, per 100 parts by weight of the copolymer (A). . If it is less than 10 parts by weight, the reworkability and flatness are deteriorated. On the other hand, if it exceeds 200 parts by weight, the substrate adhesion is deteriorated, which is not preferable.

(C) Adhesion aid In the thermosetting resin composition of the present invention, (C) an adhesion aid can be added in order to improve the adhesion between the protective film to be formed and the substrate.
As such (C) adhesion aid, for example, a functional silane coupling agent having a reactive substituent can be used. Examples of the reactive substituent include a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
(C) Specific examples of the adhesion assistant include, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Examples thereof include glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
Such (C) adhesion assistant is usually used in an amount of 3 to 40 parts by weight, preferably 4 to 20 parts by weight, per 100 parts by weight of (A) copolymer. (C) If the amount of the adhesion assistant exceeds 30 parts by weight, the heat resistance of the protective film obtained may be insufficient.

(D) Surfactant (D) Surfactant can be added to the thermosetting resin composition of the present invention in order to improve the coating performance of the resin composition of the present invention.
Examples of such surfactants include fluorine surfactants, silicone surfactants, nonionic surfactants, and other surfactants.
Examples of the fluorosurfactant include, for example, trade names: BM-1000, BM-1100, manufactured by Dainippon Ink & Chemicals, Inc., trade names: Megafac F142D, F172, F173, and F183. Product name: FLORARD FC-135, FC-170C, FC-430, FC-431, Neos Co., Ltd. Product name: Footent 250, 251, 222F, FTX- 218, manufactured by Asahi Glass Co., Ltd. Trade names: Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, Commercial products such as SC-103, SC-104, SC-105, and SC-106 can be listed.

  As said silicone type surfactant, for example, Toray Dow Corning Silicone Co., Ltd. trade name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC- 190, PAINTAD19, FZ-2101, 77, 2118, L-7001, L-7002, manufactured by Big Chemie Japan, Byk-300, 306, 310, 335, 341, 344, 370, Shin-Etsu Chemical Co., Ltd. product name: KP341, Shin-Akita Kasei Co., Ltd. product name: Ftop EF301, EF303, EF352, and other commercial products.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, and the like.
Examples of the polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of polyoxyethylene aryl ethers include polyoxyethylene octylphenyl. Examples include ether and polyoxyethylene nonylphenyl ether. Examples of polyoxyethylene dialkyl esters include polyoxyethylene dilaurate and polyoxyethylene distearate.
As said other surfactant, Kyoeisha Chemical Co., Ltd. brand name: (meth) acrylic acid type copolymer polyflow No. 57, no. 90 or the like.

  The added amount of these (D) surfactants is usually 0.01 to 1 part by weight, preferably 0.05 to 0.4 parts by weight, per 100 parts by weight of the (A) copolymer. When the amount of the surfactant exceeds 1 part by weight, the coating film may be easily roughened in the coating process.

(E) Polyhydric carboxylic anhydride An polyhydric carboxylic anhydride may be added to the thermosetting resin composition of the present invention in order to improve heat resistance and alkali resistance.
(E) Polyhydric carboxylic acid anhydrides include, for example, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Aliphatic dicarboxylic acid anhydride such as hymic anhydride; alicyclic polycarboxylic acid dianhydride such as 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride; Aromatic polycarboxylic acid anhydrides such as phthalic acid, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride; and ester group-containing acid anhydrides such as ethylene glycol bistrimellitic anhydride and glycerin tris anhydrous trimellitate Can do. Of these, aromatic polyvalent carboxylic acid anhydrides, particularly trimellitic anhydride, are preferable in that a cured film having high heat resistance can be obtained.

(F) Curing Accelerator As described above, when (E) a polyvalent carboxylic acid anhydride is added, (F) a curing accelerator may be added to accelerate curing.
(F) As a specific example of the curing accelerator,
2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolylundecylimidazolyl -(1 ')]-ethyl-S-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2, 4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine isocyanuric acid adduct Door can be.

(G) Thermosensitive acid generator (G) A thermosensitive acid generator can be added to the thermosetting resin composition of the present invention. Examples of the thermal acid generator include sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, etc. Among these, sulfonium salts and benzothiazonium salts are preferably used.
(G) The addition amount of the heat-sensitive acid generator is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the copolymer (A). When it exceeds 30 parts by weight, the hardness is significantly lowered.

Preparation of Resin Composition The thermosetting resin composition of the present invention is prepared by uniformly dissolving or dispersing each of the above components in an appropriate solvent. As the solvent to be used, a solvent in which each component of the composition is dissolved or dispersed and does not react with each component is preferably used.
Such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene Examples include glycol alkyl ether propionates, aromatic hydrocarbons, ketones, and esters.

Specific examples thereof include, for example, alcohols such as methanol, ethanol, benzyl alcohol and the like;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate;
Examples of diethylene glycol monoalkyl ethers include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
As diethylene glycol dialkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;
As propylene glycol monoalkyl ethers, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;
As propylene glycol alkyl ether acetates, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;
As propylene glycol alkyl ether propionates, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and the like;

Aromatic hydrocarbons such as toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone;
Esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, propoxy vinegar Methyl, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Butylate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Examples thereof include propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these, alcohols, diethylene glycols, propylene glycol alkyl acetates, ethylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers are preferred, and in particular, benzyl alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether. Acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate are preferred.

  The amount of the solvent used is preferably 1 to 50% by weight, more preferably 5% by weight, based on the total solid content in the composition of the present invention (the amount obtained by removing the amount of the solvent from the total amount of the composition including the solvent). It is the range which becomes -40 weight%.

A high boiling point solvent can be used in combination with the above solvent. Examples of the high boiling point solvent that can be used in combination here include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate , Phenyl cellosolve acetate and the like.
The amount of the high-boiling solvent used in combination is preferably 90% by weight or less, more preferably 80% by weight or less based on the total amount of the solvent.

  The composition prepared as described above can be used after being filtered using a Millipore filter having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm. .

Formation of Color Filter Protective Film Next, a method for forming a color filter protective film using the composition of the present invention will be described.
After applying the resin composition solution of the present invention to the substrate surface, pre-baking to remove the solvent to form a coating film, a heat treatment can be performed to form a protective film for the target color filter. .
Examples of the substrate that can be used include substrates such as glass, quartz, silicon, and resin. Examples of the resin include resins such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, and cyclic olefin ring-opening polymers and hydrogenated products thereof.

As a coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, a bar coating method, an ink jet method or the like can be adopted, and in particular, coating using a spin coater, a spinless coater, or a slit die coater. Can be suitably used.
The pre-baking conditions may vary depending on the types and blending ratios of the components, but usually conditions of about 70 to 90 ° C. for about 1 to 15 minutes can be employed. The thickness of the coating film is preferably 0.15 to 8.5 μm, more preferably 0.15 to 6.5 μm, and still more preferably 0.15 to 4.5 μm. In addition, the thickness of a coating film here should be understood as thickness after solvent removal.

  The heat treatment after the coating film is formed can be carried out by an appropriate heating device such as a hot plate or a clean oven. The processing temperature is preferably about 150 to 250 ° C., and the heating time can be 5 to 30 minutes when using a hot plate, and 30 to 90 minutes when using an oven.

When a radiation sensitive acid generator is used for the resin composition, the resin composition is applied to the substrate surface, the solvent is removed by pre-baking to form a coating film, and then a radiation irradiation treatment (exposure treatment). The target protective film can be formed by applying. If necessary, a heat treatment may be further performed after the exposure processing.
Examples of the radiation that can be used in the radiation treatment include visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray, and ultraviolet light containing light having a wavelength of 190 to 450 nm is preferable.
Energy of exposure generally, 100~20,000J / ^{m 2,} preferably 150~10,000J / ^{m 2.}
After the irradiation, a heat treatment may be optionally further performed. As heating temperature at this time, about 150-250 degreeC is preferable, and appropriate apparatuses, such as a hot plate and a clean oven, can be used as a heating apparatus, for example. As the heating time, a processing time of 5 to 30 minutes can be employed when using a hot plate, and 30 to 90 minutes when using an oven.

Color filter protective film The protective film formed in this manner preferably has a thickness of 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm. In addition, when the protective film of this invention is formed on the board | substrate which has the level | step difference of a color filter, said film thickness should be understood as the thickness from the uppermost part of a color filter.
As is clear from the examples described below, the protective film of the present invention satisfies adhesiveness, surface hardness, transparency, heat resistance, light resistance, solvent resistance, and the like, and also with a load in a heated state. It is suitable as a protective film for an optical device that is excellent in performance of flattening the step of the color filter formed on the base substrate without being recessed.
In particular, since the protective film of the present invention may be exposed to heating exceeding 250 ° C. in the panel manufacturing process, sufficient dimensional stability at 270 ° C. has sufficient heat resistance even in that case. Guaranteed by having.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

(A) Copolymer Production Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, after 70 parts by weight of glycidyl methacrylate and 30 parts by weight of styrene were charged and purged with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The resulting polymer solution had a solid content concentration of 33.1% by weight.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 80 parts by weight of (3-ethyl-3-oxyethanyl) methyl methacrylate and 20 parts by weight of styrene were charged and purged with nitrogen, and then gently stirred. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). The solid content concentration of the obtained polymer solution was 32.9% by weight.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide, and 20 parts by weight of methacrylic acid were charged and purged with nitrogen, and then gently stirred. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). The solid content concentration of the obtained polymer solution was 29.7% by weight.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydro-2H 2-methyl-2-propenoate -After 20 parts by weight of pyran-2-yl ester was charged and purged with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-4). The resulting polymer solution had a solid content concentration of 30.1% by weight.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and 20 parts by weight of 1-ethylcyclopentyl methacrylate were charged. After the replacement, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-5). The solid content concentration of the obtained polymer solution was 29.8% by weight.

Production synthesis example 6 of component (B)
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, and 60 parts by weight of 2-hydroxyethyl methacrylate were charged and purged with nitrogen, and then gently stirring was started. The solution temperature was raised to 70 ° C. and kept at this temperature for 5 hours. Thereafter, 70 parts by weight of methacryloyloxyethyl isocyanate was dropped, and a urethanization reaction was performed to obtain a polymer solution containing the copolymer (B-3). The solid content concentration of the obtained polymer solution was 32.9% by weight.

Preparation and Evaluation of Resin Composition Example 1
A solution containing copolymer (A-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by weight (solid content) of copolymer (A-1)) and (B) triacryloyloxypentaerythritol. 80.0 parts by weight of succinic acid (TAPS), 5.0 parts by weight of (C) γ-glycidoxypropyltrimethoxysilane, (D) SH-28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) as a surfactant ) Add 0.1 parts by weight, and further add propylene glycol monomethyl ether acetate (S-1) and diethylene glycol ethyl methyl ether (S-2) at a weight ratio of 8 to 2 so that the solid content concentration is 20% by weight. And then filtered through a Millipore filter having a pore size of 0.5 μm to prepare a resin composition.
After applying the above composition on a SiO ₂ dip glass substrate using a spinner, pre-baking is performed on a hot plate at 80 ° C. for 5 minutes to form a coating film, and further, heat treatment is performed in an oven at 230 ° C. for 60 minutes. Thus, a protective film having a thickness of 2.0 μm was formed.

Evaluation of Protective Film (1) Evaluation of Transparency About the substrate having the protective film formed as described above, using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)), 400 to 800 nm. The transmittance of was measured. Table 1 shows the minimum transmittance of 400 to 800 nm. When this value is 95% or more, it can be said that the transparency of the protective film is good.

(2) Evaluation of heat resistance (heat-resistant dimensional stability) The substrate having the protective film formed as described above was heated in an oven at 250 ° C. for 1 hour, and the film thickness before and after heating was measured. The heat-resistant dimensional stability calculated according to the following formula is shown in Table 1. When this value is 95% or more, it can be said that the heat-resistant dimensional stability is good.
Heat-resistant dimensional stability = [(film thickness after heating) / (film thickness before heating)] × 100 (%)

(3) Evaluation of alkali resistance (alkali resistance dimensional stability) The substrate having the protective film formed as described above was immersed in a 5% aqueous sodium hydroxide solution heated to 40 ° C. for 30 minutes, pulled up, The film was washed with pure water and dried on a hot plate heated to 120 ° C. for 2 minutes, and the film thickness before and after the alkali immersion was measured. The alkali resistance dimensional stability calculated according to the following formula is shown in Table 1. When this value is 95% or more, it can be said that the alkali-resistant dimensional stability is good.
Alkali resistance dimensional stability = [(film thickness after alkali immersion) / (film thickness before alkali immersion)] x 100 (%)

(4) Evaluation of heat-resistant color change About the board | substrate which has a protective film formed as mentioned above, it heated at 250 degreeC in oven for 1 hour, and the transparency before and behind a heating was measured similarly to said (1). The heat discoloration calculated according to the following formula is shown in Table 1. When this value is 5% or less, the heat discoloration is good.
Heat discoloration property = transmittance before heating−transmittance after heating (%)

(5) Measurement of surface hardness About the board | substrate which has a protective film formed as mentioned above, the surface hardness of the protective film was measured by 8.4.1 pencil scratch test of JISK-5400-1990. This value is shown in Table 1. When this value is 3-4H or harder, it can be said that the surface hardness is good.

(6) Measurement of dynamic micro hardness About a substrate having a protective film formed as described above, a ridge angle 115 ° triangular indenter (Helkovic type) using a Shimadzu dynamic micro hardness meter DUH-201 (manufactured by Shimadzu Corporation) As a result of the indentation test, the dynamic microhardness of the protective film was determined as follows: load: 0.1 gf, speed: 0.0145 gf / sec. , Holding time: 5 sec. The temperature was measured under the measurement conditions of 23 ° C and 140 ° C. The results are shown in Table 1.

(7) Evaluation of adhesion After performing a pressure cooker test (120 ° C., humidity 100%, 4 hours) on the substrate having the protective film formed as described above, 8.5 of JIS K-5400-1990. .3 Adhesiveness Adhesiveness of the protective film (adhesiveness to SiO ₂ ) was evaluated by a cross-cut tape method. Table 1 shows the number of remaining grids out of 100 grids.
In addition, as an evaluation of adhesion to Cr, a protective film having a thickness of 2.0 μm was formed in the same manner as described above except that a Cr substrate was used instead of the SiO ₂ dip glass substrate, and the above-mentioned cross-cut tape method was used. Evaluation was performed in the same manner. The results are shown in Table 1.

(8) Evaluation of planarization property A pigment-based color resist (trade names “JCR RED 689”, “JCR GREEN 706”, “CR 8200B”, above, manufactured by JSR Corporation) is applied to a spinner on a SiO ₂ dip glass substrate. And prebaked at 90 ° C. for 150 seconds on a hot plate to form a coating film. Thereafter, ghi line (intensity ratio of wavelengths 436 nm, 405 nm, 365 nm = 2.7: 2.5: 4.8) is used through a predetermined pattern mask using an exposure machine Canon PLA501F (manufactured by Canon Inc.). Irradiated with an exposure dose of 2,000 J / m ^{2 in} terms of i-line, developed with 0.05% aqueous potassium hydroxide solution, rinsed with ultrapure water for 60 seconds, and further in an oven at 230 ° C. Heat treatment was performed for 30 minutes to form a striped color filter (stripe width 100 μm) of three colors of red, green, and blue.
The unevenness on the surface of the substrate on which the color filter was formed was measured with a surface roughness meter “α-step” (trade name: manufactured by Tencor), and found to be 1.0 μm. However, the measurement was performed with a measurement length of 2,000 μm, a measurement range of 2,000 μm square, and a measurement point n = 5. That is, the measurement direction is two directions of the stripe line minor axis direction of red, green and blue directions and the stripe axis major axis direction of red, red, green, green, blue and blue, and n = 5 for each direction. Measured (total n number is 10).
On this, the composition for forming a protective film is applied with a spinner, pre-baked on a hot plate at 90 ° C. for 5 minutes to form a coating film, and further heated in an oven at 230 ° C. for 60 minutes. A protective film having a thickness of 2.0 μm from the upper surface of the color filter was formed. However, the film thickness mentioned here means the thickness from the uppermost surface of the color filter formed on the substrate.
About the board | substrate which has a protective film on the color filter formed as mentioned above, the unevenness | corrugation on the surface of a protective film was measured with the contact-type film thickness measuring apparatus alpha-step (made by Tencor Japan Co., Ltd.). However, the measurement was performed with a measurement length of 2,000 μm, a measurement range of 2,000 μm square, and a measurement point n = 5. That is, the measurement direction is two directions of the stripe line minor axis direction of red, green and blue directions and the stripe axis major axis direction of red, red, green, green, blue and blue, and n = 5 for each direction. Measured (total n number is 10). Table 1 shows the average value of 10 times of the difference in height (nm) between the highest and lowest portions for each measurement. When this value is 300 nm or less, it can be said that the flatness is good.

(9) Evaluation of reworkability A protective film having a thickness of 2.0 μm from the upper surface of the color filter produced in (8) was formed. A color filter stripping solution (SemiCleanDF-7, manufactured by Yokohama Oil & Fats) was heated to 50 ° C., and the color filter with the protective film was immersed therein. After 10 minutes and 20 minutes, the substrate was pulled up, washed with pure water while being rubbed with a sponge, and it was visually determined whether or not the protective film (including the pigment-based color resist) was peeled off. A sample that could be peeled off in 10 minutes was marked with ◯, a sample that could be peeled off in 20 minutes was indicated by Δ, and a sample that could not be peeled off even in 20 minutes was indicated as ×. Those having a short peeling time can be judged to have good reworkability.

(10) Evaluation of Storage Stability The viscosity of the protective film-forming resin composition prepared in Example 1 was measured using an ELD viscometer manufactured by Tokyo Keiki Co., Ltd. Thereafter, the solution viscosity at 25 ° C. was measured every day while the composition was allowed to stand at 25 ° C. The number of days required to increase the viscosity by 5% based on the viscosity immediately after the preparation was determined, and the number of days is shown in Table 1. When this number of days is 15 days or more, it can be said that the storage stability is good.

Examples 2 to 18, Reference Examples 1 to 4 and Comparative Examples 1 to 3
Resin composition in the same manner as in Example 1 except that the type and amount of each component of the composition are as shown in Table 1, and the solvent shown in Table 1 was used to match the solid content concentration shown in Table 1. A product was prepared.
Using the protective film-forming resin composition prepared as described above, a protective film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Examples 19-24 and Reference Examples 5-7
Resin composition in the same manner as in Example 1 except that the types and amounts of the respective components of the composition are as shown in Table 2, and the solvents shown in Table 2 were used to match the solid content concentrations shown in Table 2. A product was prepared.
A resin composition was prepared in the same manner as in Example 1 except that a slit die coater was used instead of the spin coater, and a protective film was formed and evaluated. The results are shown in Table 2.

In Tables 1 and 2, (B) a compound having one or more carboxyl groups and one or more acrylic groups, (C) an adhesion assistant, (D) a surfactant, (E) a polyvalent carboxylic acid anhydride The abbreviations such as the product, (F) curing accelerator, and (S) solvent represent the following.
B-1: triacryloyloxypentaerythritol succinic acid {alias: 3-acryloyloxy-2,2-bisacryloyloxymethyl-propyl) ester, abbreviation: TAPS}
B-2: Pentaaclioyloxydipentaerythritol succinic acid {also known as: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2-bis-acryloyloxymethyl-propyl ] Esters, abbreviations: PADPS}
C-1: γ-glycidoxypropyltrimethoxysilane D-1: Silicone surfactant (trade name: SH-28PA manufactured by Toray Dow Corning Silicone Co., Ltd.)
D-2: Silicone-based surfactant (BIC Chemie Japan Co., Ltd., trade name: BYK-344),
D-3: Fluorine-based surfactant (manufactured by Neos Co., Ltd., trade name: FTX-218),
D-4: Silicone surfactant (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: PAINTAD19),
E-1: Trimellitic anhydride F-1: 2-Phenyl-4-methylimidazole S-1: Propylene glycol monomethyl ether acetate S-2: Diethylene glycol ethyl methyl ether S-3: Methyl 3-methoxypropionate a-1 : Bisphenol A novolac type epoxy resin (product name: Epicoat 157S65, abbreviation: EP157S65, manufactured by Japan Epoxy Resin Co., Ltd.)
b-1: Triacryloyloxyethyl isocyanuric acid (product name: Aronix M-315M, manufactured by Toagosei Co., Ltd.)
b-2: Dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)

The resin composition of the present invention can form a cured film having high flatness on the substrate even when the substrate has low surface flatness, and has high transparency and surface hardness, heat resistance and pressure resistance. It has excellent resistance to various properties such as alkali resistance, alkali resistance, and reworkability, and is useful as a protective film for optical devices such as color filters for liquid crystal display elements (LCD) and color filters for charge coupled devices (CCD).

Claims (9)

(A) (a1) a polymerizable unsaturated compound having an oxiranyl group or oxetanyl group and (a2) a copolymer with a polymerizable unsaturated compound other than (a1) above, (B) one or more carboxyl groups and one A thermosetting resin composition comprising a compound having one or more (meth) acrylic groups , (C) an adhesion assistant comprising a silane coupling agent having a reactive substituent, and (D) a surfactant. ,
The (a2) compound is styrene, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2. 2.1] selected from the group of hept-2-ene, N-cyclohexylmaleimide, methacrylic acid, 1-ethylcyclopentyl methacrylate and 2-methyl-2-propenoic acid, tetrahydro-2H-pyran-2-yl ester At least one,
The compound (B) is selected from the group of triacryloyloxypentaerythritol succinic acid, diacryloyloxypentaerythritol succinic acid, pentaacryoyloxydipentaerythritol succinic acid, and tetraacryoyloxydipentaerythritol succinic acid. And at least one thermosetting resin composition.   (A) The ratio of the component (a1) and the component (a2) constituting the copolymer is (a1) 5 to 95% by weight, (a2) 95 to 5% by weight [where (a1) + (a2) = 100% by weight] The thermosetting resin composition according to claim 1.   (B) The compounding quantity of the compound which has a 1 or more carboxyl group and a 1 or more (meth) acryl group is 10-200 weight part with respect to 100 weight part of (A) copolymers. The thermosetting resin composition as described. The thermosetting resin composition according to any one of claims 1 to 3 , wherein the compounding amount of (C) the adhesion assistant is 3 to 40 parts by weight with respect to 100 parts by weight of (A) copolymer. (D) The compounding quantity of surfactant is 0.01-1 weight part with respect to 100 weight part of (A) copolymers, The thermosetting resin composition in any one of Claims 1-4 . The copolymer (A) is a styrene / glycidyl methacrylate copolymer, styrene / tricyclomethacrylate [5.2.1.0]. ^2,6 ] Decan-8-yl / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / glycidyl methacrylate copolymer, N-cyclohexylmaleimide / glycidyl methacrylate Copolymer, styrene / tricyclomethacrylate [5.2.1.0 ^2,6 ] Decan-8-yl / methacrylic acid / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / methacrylic acid / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / methacrylic acid / glycidyl methacrylate copolymer , Styrene / tricyclo methacrylate [5.2.1.0 ^2,6 ] Decan-8-yl / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexyl maleimide / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-ethyl Cyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / tricyclo methacrylate [5.2.1.0 ^2,6 ] Decan-8-yl / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-ethyl Cyclopentyl methacrylate / glycidyl methacrylate copolymer, styrene / tricyclo methacrylate [5.2.1.0 ^2,6 ] Decan-8-yl / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexyl maleimide / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-methyl Cyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / tricyclo methacrylate [5.2.1.0 ^2,6 Decan-8-yl / tetrahydro-2H-pyran-2-yl ester / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / tetrahydro-2H-pyran-2-yl ester / glycidyl methacrylate copolymer and Thermosetting according to any one of claims 1 to 5, which is at least one selected from the group consisting of styrene / N-phenylmaleimide / tetrahydro-2H-pyran-2-yl ester / glycidyl methacrylate copolymer. Resin composition. A protective film formed of the color filter according to claim 1-6 thermosetting resin composition according to any one. A method for forming a protective film for a color filter, comprising: forming a coating film on the substrate using the thermosetting resin composition according to claim 7 , and then performing a heat treatment. A protective film for a color filter formed by the method for forming a protective film for a color filter according to claim 8 .