JP2005099404A - Thermosetting resin composition for planarization film of color filter and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which has excellent hardenability without using a hardening accelerator, is colorless and transparent in hardened matter, is little in discoloration under photoirradiation conditions of high temperature and high energy and is appropriate for a planarization film of a color filter. <P>SOLUTION: In the thermosetting resin composition for the planarization film of the color filter containing an epoxy group-containing resin (A) and a hardener (B), the hardener (B) is a compound obtained by bringing a carboxyl group of a cyclohexane tricarboxylic acid (b01) or its acid anhydride (b02) and a vinyl group of vinyl (thio)ether (b11) having one or more vinyl groups in one molecule into addition reaction. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermosetting resin composition for a planarizing film of a color filter and its use. More specifically, a thermosetting resin composition and resin curing that can be suitably used for flattening films of color filters used in various display devices such as liquid crystal display devices (LCD) and solid-state imaging devices (CCD). Product and its use.

In recent years, with the advancement of digital multimedia, image-related photographing devices and display devices have been remarkably popularized, and these devices are required to have higher functions. Various display devices such as color liquid crystal display devices (LCD), electroluminescence (EL) devices, plasma display panel (PDP) devices, light emitting polymer (LEP) devices, field emission display devices (FED), etc. In most cases, in a solid-state imaging device (CCD), a color filter is an essential component.
In general, the color filter uses the red (R), green (G), and blue (B) colored layers, and a planarizing film is formed to cover and protect the colored layers. This flattened film is required to have sufficient hardness and adhesion, excellent transparency so as not to adversely affect the color of the pixel, and excellent film thickness uniformity. Further, when the flattening film is in contact with the liquid crystal compound, the film has a passivation property and flatness that can prevent contamination of the liquid crystal compound (transfer of contaminants from the colored layer side to the liquid crystal). Non-contaminating properties such as non-eluting properties in which the chemical film itself does not elute into the liquid crystal are required. In addition, there are demands for the storage stability of the resin composition and the performance of the cured resin, such as excellent heat resistance, hardness, hot pure water resistance, and solvent resistance.
In particular, in CCD applications, further miniaturization and higher sensitivity are required. Thin films of the order of 1 to 5 μm, hardness, adhesion, transparency, film thickness uniformity, non-contamination, heat resistance, and temperature-resistant pure water Further, cured film properties such as solvent resistance are required, and performances such as storage stability are required for the resin composition.
The flattening film for the color filter requires excellent colorless transparency, and generally an epoxy group / acid anhydride curing system thermosetting resin is used. As a curing agent for such a thermosetting resin, alicyclic acid anhydrides such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride are generally used.

However, when the above alicyclic acid anhydride is used as a curing agent, the curing reactivity is low, and it is necessary to add a curing accelerator in order to sufficiently cure.
Examples of such a curing accelerator include triphenylphosphonium bromide (see Patent Document 1), 2-ethyl-4-methylimidazole (see Patent Document 2), and 1,8-diazabicyclo [5,4,0] undecene- 7 ethyl hexane salt (see Patent Document 3) or tetraphenylphosphonium bromide (see Patent Document 4).

On the other hand, in order to cure the thermosetting resin composition so that it can be used as a cured resin for the planarizing film of the color filter, it is necessary to maintain colorless transparency for a long period of time. However, COG (chip on glass) liquid crystal devices and the like are being widely used for overhead projectors in LCDs, and the cured resin of the color filter flattening film is exposed to light of higher temperature and higher energy. It has become difficult to maintain colorless transparency for a long period of time, such as coloring (yellowing) due to. As a cause of the coloring, a phenyl group in a curing agent component (for example, trimellitic acid anhydride) of an aromatic acid anhydride contained in a thermosetting resin composition (for example, one described in Patent Document 5). The chemical change is considered to be one of them, and from this point, the use of a curing agent having an aromatic group in the molecular structure is not preferred. In addition, since the phenyl group and nitrogen content of the curing accelerator are also considered as one of the coloring causes of the thermosetting resin composition, from the viewpoint of maintaining the colorless transparency of the thermosetting resin composition, It is not preferable to use a curing accelerator in the color filter flattening film coating solution.
Patent Document 6 suggests that various carboxyl group derivatives having a blocked carboxyl group and an acid anhydride group can be used as a general-purpose curing agent, and Patent Document 7 discloses a blocked carboxylic acid curing agent. Although a coating solution for a protective film of a color filter using a colorant is disclosed, aromatic carboxylic acid is preferably used in these techniques, and the cured product is colored by hydrogenating (hydrogenating) the aromatic ring. There is no description on the point that is suppressed.

JP 2000-344868 A JP 2001-114868 A JP 2002-97251 A Special Table 2003-26763 JP 2001-158816 A JP 11-246543 A JP 2001-350010 A

A first object of the present invention is a color filter having excellent curability without using a curing accelerator, a cured product being colorless and transparent, and being less colored under high temperature and high energy light irradiation conditions. Another object of the present invention is to provide a thermosetting resin composition suitable for the flattening film.
In addition, the second object of the present invention is to have excellent curability and storage stability, and is colorless and transparent after curing, less colored under high temperature and high energy light irradiation conditions, and further has passivation properties. A liquid crystal display (LCD), an electroluminescence (EL) device, a plasma display panel (PDP) device, a light emitting polymer (LEP) device, a field emission display (FED), and a solid having excellent physical properties such as flatness An object of the present invention is to provide a coating liquid capable of forming a flattening film for a color filter such as an image sensor (CCD).
A third object of the present invention is to provide a cured resin obtained by curing the resin composition, a color filter having these layers, a solid-state imaging device, and a display device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a cyclohexanetricarboxylic acid having a specific structure in a thermosetting resin composition containing an epoxy group-containing resin (A) and a curing agent (B). Alternatively, by using a reaction product of the anhydride and a vinyl (thio) ether group-containing compound as a curing agent, a cured product having good curability and excellent colorless transparency without using a curing accelerator can be obtained. Obtaining knowledge that a thermosetting resin composition is obtained, and obtaining knowledge that this resin composition is suitable for paints, adhesives, molded articles, and color filter flattening film coating liquids, The present invention has been completed.

That is, the present invention includes the following [1] to [7].
[1] A thermosetting resin composition for a planarizing film of a color filter containing an epoxy group-containing resin (A) and a curing agent (B), wherein the curing agent (B) is cyclohexanetricarboxylic acid ( b01) or an acid anhydride (b02) thereof and a compound obtained by addition reaction of a vinyl group of vinyl (thio) ether (b11) having one or more vinyl groups in one molecule. A thermosetting resin composition for a color filter planarizing film.
[2] The cyclohexanetricarboxylic acid (b01) is cyclohexane-1,2,4-tricarboxylic acid or cyclohexane-1,3,5-tricarboxylic acid, and the acid anhydride (b02) is cyclohexane-1,3,3. The thermosetting resin composition for a planarizing film of a color filter according to the above [1], which is 4-tricarboxylic acid-3,4-anhydride.
[3] A coating solution for a flattened film of a color filter comprising the thermosetting resin composition according to [1] or [2].
[4] A cured resin product obtained by curing the thermosetting resin composition according to [1] or [2].
[5] A color filter having a layer of a cured resin obtained by curing the thermosetting resin composition according to [1] or [2].
[6] A solid-state imaging device having a layer of a cured resin obtained by curing the thermosetting resin composition according to [1] or [2].
[7] A display device having a layer of a cured resin obtained by curing the thermosetting resin composition according to [1] or [2].

  The thermosetting resin composition of the present invention has good curability without adding a curing accelerator. This thermosetting resin composition is colorless and transparent when used for various display devices such as a liquid crystal display device (LCD) and a solid-state imaging device (CCD). A cured resin for a flattened film of a color filter with little discoloration under light irradiation can be obtained.

Hereinafter, the present invention will be described in more detail.
In the present invention, the term “for flattening film of a color filter” means broadly what is used for the flattening film of a solid-state imaging device and display device having a color filter. More specifically, 1) Color filter parts such as RGB, light emission Or directly touching the light receiving element portion, electrode portion, etc., and flattening with a protective film that protects them, 2) flattening these portions with a protective film that indirectly protects through other materials Means. (For example, an intermediate film used between a microlens of a solid development element (CCD) and a color filter, or an intermediate film used between a color filter and an electrode, etc.)
The thermosetting resin composition of the present invention contains an epoxy group-containing resin (A) and a curing agent (B), and the curing agent (B) is cyclohexanetricarboxylic acid (b01) or its acid anhydride (b02). ) And a vinyl (thio) ether (b11) having one or more vinyl groups in one molecule.
The curing agent (B) used in the thermosetting resin composition of the present invention is cyclohexanetricarboxylic acid (b01) or cyclohexanetricarboxylic anhydride having a hemiacetal ester structure of a carboxyl group represented by the following formula 1a or formula 1b: It is a derivative of (b02).
The said hardening | curing agent (B) can be used individually by 1 type or in mixture of 2 or more types.

^{Wherein, R 1, R 2, R} 3, R 1 ', R 2' and ^{R 3} 'are each hydrogen atom or an organic group having 1 to 18 carbon atoms, ^{R 4} and ^{R 5} are each 1 to carbon atoms 18 organic groups, Y ¹ and Y ¹ ′ are each an oxygen atom or a sulfur atom. R ³ and R ⁴ may be bonded to each other to form a heterocycle having Y ¹ as a hetero atom. R ¹ ′, R ² ′, R ³ ′ and Y ¹ ′ may be the same as R ¹ , R ² , R ³ and Y ¹ to which they correspond, respectively.

The compound (B) having a carboxyl group hemiacetal ester structure represented by the above formula 1a or 1b is a cyclohexane tricarboxylic acid (b01) or its acid anhydride (b02) carboxyl group and vinyl (thio) ether (b11). This is a compound in which the carboxyl group of cyclohexanetricarboxylic acid (b01) or its acid anhydride (b02) is blocked (protected) by reacting with the vinyl group.
Among these compounds (B), the compound having a functional group represented by the formula 1a is cyclohexanetricarboxylic acid (b01) or its acid anhydride (b02) and a vinyl (thio) ether represented by the following formula 2a ( obtained by reacting with b11). Here, the vinyl (thio) ether (b11) means a vinyl ether compound, a vinyl thioether compound, or a heterocyclic compound having a vinyl double bond having an oxygen atom or a sulfur atom as a hetero atom.

^Wherein, R ^1, R 2, ^{R 3} and ^{Y 1} are the same as the formula ^1a, R 1, ^{R 2} and ^{R 3} are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aryl group, alk It is an organic group such as a reel group, R ⁴ is an organic group such as an alkyl group having 1 to 18 carbon atoms, an aryl group, or an alkaryl group, and these organic groups may have an appropriate substituent. R ³ and R ⁴ may be bonded to each other to form a heterocycle having Y ¹ as a heteroatom.

  Specific examples of the compound represented by Formula 2a include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and the like. Aliphatic vinyl ether compounds and corresponding aliphatic vinyl thioethers, as well as 2,3-dihydrofuran, 3,4-didofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3 , 4-Dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4 -Dihydro-2H-pyran Such as 2-cyclic ether compounds such as carboxylate and the corresponding cyclic vinyl thioether compounds thereof.

  Among the compounds (B), the compound having a functional group represented by the formula 1b is cyclohexanetricarboxylic acid (b01) or its acid anhydride (b02) and a vinyl (thio) ether (b11 represented by the following formula 2b). ).

Here, R ¹ , R ² , R ³ , R ⁴ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , Y ¹ and Y ¹ ′ are the same as those in formula 1b, and R ¹ , R ² , R ³ , R ¹ ′, R ² ′ and R ³ ′ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ and R ⁵ are each an organic group having 1 to 18 carbon atoms, and Y ¹ and Y ¹ ′ Are each an oxygen atom or a sulfur atom. R ³ and R ⁴ may be bonded to each other to form a heterocycle having Y ¹ as a hetero atom. R ¹ ′, R ² ′, R ³ ′ and Y ¹ ′ may be the same as R ¹ , R ² , R ³ and Y ¹ to which they correspond, respectively.

  In the molecule of the divinyl ether compound or divinyl thioether compound represented by the above formula 2b, there are two vinyl structures capable of protecting the carboxyl group. Therefore, when a polycarboxylic acid, particularly dicarboxylic acid, is reacted with the divinyl ether compound or divinyl thioether compound represented by the above formula 2b, a compound having the functional group represented by the above formula 1b as a main chain constituent unit is obtained. .

  Examples of the compound represented by Formula 2b include 1,4-cyclohexanedimethanol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,4- Divinyl ether compounds such as butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, bisphenol A divinyl ether, hydrogenated bisphenol A divinyl ether, and corresponding divinyl thioethers Compounds.

Examples of cyclohexanetricarboxylic acid (b01) include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, and the like. Moreover, as cyclohexanetricarboxylic acid anhydride (b02), cyclohexane-1,2,4-tricarboxylic acid-2,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane -1,2,3-tricarboxylic acid-2,3-anhydride and the like. In the present invention, among these, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid or cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is used. It can be preferably used. Since the viscosity of the composition becomes lower, cyclohexanetricarboxylic acid (b01) can be more preferably used than cyclohexanetricarboxylic acid anhydride (b02).
These compounds can be used individually by 1 type or in combination of 2 or more types as appropriate. These compounds can be synthesized, for example, by hydrogenation of benzenetricarboxylic acid such as trimellitic acid.

  Usually, the cyclohexanetricarboxylic acid (b01) or cyclohexanetricarboxylic anhydride (b02) and the vinyl-type double bond-containing compound represented by the formula 2a or the formula 2b are mixed at room temperature to 100 ° C. in the presence of an acid catalyst. By reacting at a temperature to protect (block) the carboxyl group, a compound having a hemiacetal ester structure of the carboxyl group represented by Formula 1a or Formula 1b is obtained. Moreover, the said compound may have both group represented by Formula 1a and Formula 1b.

  At this time, an acid catalyst can be used for the purpose of promoting the reaction. An example of such a compound is an acidic phosphate compound represented by Formula 3.

Here, R is an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group, and m is 1 or 2.

  More specifically, examples of the acidic phosphate compound include primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol and 2-ethylhexanol, and isopropanol, 2 -Phosphoric monoesters or phosphoric diesters of secondary alcohols such as butanol, 2-hexanol, 2-octanol and cyclohexanol.

An organic solvent can be used for the purpose of making the reaction system uniform and facilitating the reaction. Examples of such organic solvents include benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso # 100 (registered trademark of Exxon Chemical), Solvesso # 150 (registered by Exxon Chemical) An aromatic hydrocarbon such as dioxane and tetrahydrofuran; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, monomethyl ether, Esters and ether esters such as methoxybutyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, mesityl oxide, methyl isoamyl ketone, ethyl butyl ketone, ethyl amylke Ketones such as styrene, diisobutyl ketone, diethyl ketone, methyl propyl ketone and diisopropyl ketone; phosphate esters such as trimethyl phosphate, triethyl phosphate and tributyl phosphate; aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide Triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monoethyl ether acetate, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, dipropylene glycol, diethylene glycol-2-ethylhexyl ether, tetra Ethylene glycol dimethyl Glycol derivatives such as ethers.
More preferably, propylene glycol monomethyl ether acetate is used.
An organic solvent can be used individually by 1 type or in combination of 2 or more types. Although the usage-amount of the said organic solvent is not specifically limited, It is 5-95 weight part normally with respect to 100 weight part of reaction raw materials, Preferably, it is 20-80 weight part.

  Further, in the present invention, together with the cyclohexanetricarboxylic acid or cyclohexanetricarboxylic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrohydride, and the like within a range not impairing the curability of the thermosetting resin composition and the transparency of the cured product. Alicyclic acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride can be used.

  Examples of the epoxy group-containing resin (A) used in the thermosetting resin composition of the present invention include an epoxy resin (a01) or a polymer having an epoxy group (a02). These may be used alone or in combination of two or more. Can be used.

  Examples of the epoxy resin (a01) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, Naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, DPP (di-n-pentylphthalate) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, 3,4-epoxycyclohexylmethyl Of alicyclic epoxy resins such as -3 ', 4'-epoxycyclohexanecarboxylate and vinylcyclohexene diepoxide, and bisphenol A ethylene oxide adducts Polyglycidyl esters of polybasic acids such as glycidyl ether, diglycidyl ether of bisphenol A propylene oxide adduct, cyclohexanedimethanol diglycidyl ether, polyglycidyl ether of aliphatic polyhydric alcohol, diglycidyl ester of hexahydrophthalic anhydride, butyl Examples thereof include alkyl glycidyl ethers such as glycidyl ether and lauryl glycidyl ether, glycidyl ethers having one epoxy group such as phenyl glycidyl ether and cresyl glycidyl ether. Moreover, the nuclear hydrogenated product of the said epoxy resin can also be used.

  These compounds can be used alone or in combination of two or more. In particular, an alicyclic epoxy resin or a nuclear hydrogenated epoxy resin is preferable from the viewpoint of further improving the colorless transparency of a cured product obtained from a resin composition comprising these.

  The polymer having an epoxy group is composed of at least a structural unit represented by the following formula 4 and a structural unit represented by the following formula 5, and includes two or more glycidyl groups contained in the structural unit represented by the formula 5. What has it is mentioned.

Wherein, ^{R 5} is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, ^{R 6} is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or each main ring structure alicyclic having 3 to 12 carbon atoms, A hydrocarbon group, an aryl group, an aryloxy group, an aromatic hydrocarbon group, and an aromatic polyalkylene glycol residue.

Here, R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

  The structural unit represented by Formula 4 is derived from a monomer represented by Formula 6 below. The structural unit represented by Formula 5 is derived from a monomer represented by Formula 7 below.

Wherein, ^{R 5} is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, ^{R 6} is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or each main ring alicyclic structure having 3 to 12 carbon atoms carbide, A hydrogen group, an aryl group, an aryloxy group, an aromatic hydrocarbon group, and an aromatic polyalkylene glycol residue.

Here, R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

By using the monomer represented by Formula 6, sufficient hardness and transparency can be imparted to the protective film. In Equation 6, an alicyclic hydrocarbon group main ring structure carbon atoms 3-12 represented by R ^6, additional structure, for example endocyclic double bond, a side chain hydrocarbon group, side spiro ring It may contain a chain, an intra-ring bridged hydrocarbon group or the like.

In Formula 6, R ⁵ is preferably hydrogen or a methyl group, and R ⁶ is preferably an unsubstituted or cyclohexyl group substituted with an alkyl group having 1 to 5 carbon atoms.

  Specific examples of the monomer represented by the formula 6 include methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxylated cyclodecatriene acrylate, para-t-butylcyclohexyl (meta ) Acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol ( Examples include meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, and phenyl (meth) acrylate. Here, (meth) acrylate means that either acrylate or methacrylate may be used.

The monomer represented by Formula 7 is used for introducing an epoxy group (epoxy reaction point) into the polymer.
In Formula 7, R ⁷ is preferably hydrogen or a methyl group. Specific examples of the monomer represented by Formula 7 include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. Among them, glycidyl methacrylate (GMA) is available. It is preferable from the aspect of sex.

  The polymer having an epoxy group may be a random copolymer or a block copolymer. Moreover, the polymer which has an epoxy group can contain main chain structural units other than Formula 4 or Formula 5. The proportion of the structural unit of formula 4 and the structural unit of formula 5 in the polymer having an epoxy group is the charged weight of the monomer that derives the structural unit of formula 4 and the monomer that derives the structural unit of formula 5 The ratio (monomer deriving from Formula 4: monomer deriving from Formula 5) is preferably in the range of 10:90 to 90:10. If the amount of the structural unit of Formula 4 is within the above range, the curing reaction point is sufficient and a high crosslinking density can be obtained, while if the amount of the structural unit of Formula 5 is within the above range, the bulky is high. Curing shrinkage due to a small skeleton can be suppressed. The molecular weight is preferably in the range of 3,000 to 100,000 when expressed in terms of polystyrene-converted weight average molecular weight. If the molecular weight of the polymer having an epoxy group is within the above range, the occurrence of tackiness (stickiness) of the coating film can be prevented, and a uniform film thickness can be easily obtained.

The synthesis of the polymer having an epoxy group can be performed, for example, as follows.
A solvent is charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and the temperature is raised to 80 ° C. while stirring. Next, a mixture of the monomer represented by the above formula 5, the monomer represented by the above formula 6 and, if necessary, a combination of other monomers and a polymerization initiator (dropping component) is added to the dropping funnel over 2 hours. Drop more uniformly. After completion of the dropping, the reaction is terminated when the temperature of 80 ° C. is maintained for 5 hours, whereby a polymer having an epoxy group is obtained.

The blending ratio of the epoxy group-containing resin (A) and the curing agent (B) used in the present invention is not particularly limited as long as a predetermined effect is obtained.
Equivalent ratio = (number of equivalents of carboxyl groups in resin / number of equivalents of epoxy groups in resin)
In the range of 0.1 to 3.0, preferably 0.3 to 1.5. Curing progress is sufficient by setting the corresponding amount ratio to 0.1 or more, and by setting it to 3.0 or less, the glass transition temperature (Tg) of the cured product, hygroscopicity, and colorless transparency are prevented from being lowered. And it is preferable at the point which can prevent coloring under high temperature conditions or high energy light irradiation.
Here, the number of carboxyl groups in the resin is determined by neutralization titration or the like. Further, the equivalent number of epoxy groups is calculated by epoxy equivalent.

In the present invention, good curability can be obtained without using a curing accelerator, but a curing accelerator can be appropriately used as long as the colorless transparency of the cured product is not impaired. Examples of the curing accelerator that can be added include tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl- Imidazoles such as 4-methylimidazole and 1-benzyl-2-methylimidazole; Organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; Quaternary compounds such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide Phosphonium salts; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; Tetraethylammoni Arm bromide, quaternary ammonium salts such as tetrabutylammonium bromide; boron trifluoride, boron compounds such as triphenyl borate; zinc chloride, metal halides such as stannic chloride. Furthermore, high melting point dispersion type latent accelerators such as amine addition type accelerators added to epoxy resins such as high melting point imidazole compounds, dicyandiamide and amines; the surfaces of imidazole, phosphorus and phosphine accelerators are coated with a polymer. Microcapsule type latent accelerator; Latent curing represented by amine salt type latent curing accelerator, high temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt, Bronsted acid salt, etc. Accelerators can also be used.
The curing accelerator is preferably a halogen-free acidic catalyst from the viewpoint of liquid crystal non-contamination of the cured product. Furthermore, in view of the storage stability of the resin composition, among the halogen-free acidic catalysts, specifically, a Lewis acid salt high-temperature dissociation type latent curing accelerator is more preferable. -1 and Nocure LC-2 (both are trade names, manufactured by NOF Corporation).
These curing accelerators can be used singly or in appropriate combination of two or more.
The said hardening accelerator is normally mix | blended with 0.01-10 weight part with respect to a total of 100 mass parts of (A) component and (B) component.

  In the thermosetting resin composition of the present invention, an aliphatic polyol such as ethylene glycol or propylene glycol, an aliphatic or aromatic carboxylic acid compound, a phenol compound, etc. Carbon dioxide generation inhibitor, flexibility imparting agent such as polyalkylene glycol, antioxidant, plasticizer, lubricant, silane-based coupling agent, surface treatment agent such as inorganic filler, flame retardant, antistatic agent , Colorants, leveling agents, ion trapping agents, slidability improving agents, various rubbers, impact resistance improving agents such as organic polymer beads, glass beads, glass fibers, etc., thixotropic agents, surfactants Additives such as surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusing agents, UV absorbers, antioxidants, mold release agents, fluorescent agents, conductive fillers, etc. .

The flattening film coating solution is prepared by diluting a thermosetting resin composition with a solvent. As the diluting solvent, it is preferable to use a solvent containing no hydroxyl group. When the solvent contains a hydroxyl group, the blocking agent dissociation of the blocked compound is promoted to generate a carboxyl group. Therefore, the epoxy group-containing polymer (a02) and the epoxy resin (a01) have an epoxy group Since it reacts and storage stability (viscosity stability) is impaired, it is not preferable.
The same applies when water is mixed in the solvent. Therefore, in order to substantially remove moisture from the acid-epoxy crosslinking reaction system, it is preferable to prepare a coating solution using a solvent having low miscibility with water. From this viewpoint, the solubility of the solvent for preparing the coating liquid in water is preferably 20 parts by weight or less with respect to 100 parts by weight of water having a liquid temperature of 20 ° C.

  Examples of the solvent for preparing the flattening film coating solution include 3-methoxybutyl acetate, 3-ethoxyethyl propionate, methyl-β-methoxyisobutyrate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl. Examples include ether acetate, dibasic acid dimethyl ester mixture (trade name DBE, manufactured by DuPont), propylene glycol monoethyl ether acetate, and the like. Among these, 3-methoxybutyl acetate is particularly preferable because it not only contains no hydroxyl group but also has a low solubility of 6.5 parts by weight with respect to 100 parts by weight of water.

  There are no particular restrictions on the order of introduction and working conditions when each material including the polymer (a02) having an epoxy group is dissolved and dispersed in a solvent. However, if the liquid temperature of the solvent is too high, the protective group of the compound is removed and the carboxyl group is regenerated at the stage of preparing the coating solution, so the liquid temperature of the solvent is such that the carboxyl group of the compound is not regenerated. It is prepared at a temperature, usually in the range of about 20-30 ° C.

  In the coating liquid for the flattening film of the color filter prepared in this way, a hardly soluble polybasic carboxylic acid is dissolved by blocking (cap, protecting) the carboxyl group of the polybasic carboxylic acid. Dissolve and disperse in high compound form. Accordingly, the reactive sites of the carboxyl group can be present in the coating solution at a high concentration with the epoxy group. When such a coating solution is applied and dried, a coating film is formed and heated, a high crosslinking density is obtained. It is done. Further, the B component curing agent does not regenerate the carboxyl group unless heated to a predetermined temperature or higher according to the curing agent. Therefore, despite the high reaction point concentration of each carboxyl group and epoxy group, it is very excellent in storage stability in the state of the coating solution, and maintains good coating properties for a long period from immediately after preparation. to continue. Preferably, the initial viscosity immediately after preparation is 0.1 to 1000 mPa · s, and immediately after preparation, the viscosity after being left in a sealed container for 40 days at 20 ° C. can be suppressed to less than twice the initial viscosity. .

  The reaction method (curing method) between the epoxy group-containing resin (A) and the curing agent (B) is not particularly limited, and a curing device such as a closed curing furnace or a tunnel furnace capable of continuous curing can be employed. . The heating source is not particularly limited, and can be performed by a method such as hot air circulation, infrared heating, high frequency heating or the like. The curing temperature and curing time are preferably in the range of 80 to 250 ° C. for 30 seconds to 10 hours. If you want to reduce the internal stress of the cured product, after pre-curing under conditions of 80-120 ° C, 0.5 hours to 5 hours, post-curing under conditions of 120-180 ° C, 0.1 hours to 5 hours Is preferred. When aiming at short-time curing, curing is preferably performed under conditions of 150 to 250 ° C. and 30 seconds to 30 minutes.

  Since the coating liquid of the present invention is excellent in stability, the viscosity does not increase while it is coated on the colored layer and the initial good coating property is maintained, and the coating liquid is applied during the coating operation. There is no need to change the conditions frequently. Accordingly, it is possible to form a highly uniform coating film at high speed and continuously under the coating conditions set at the start of the operation. Then, when the coating film is heated after the coating is completed, the protective group of the aforementioned compound contained in the coating film is removed, the carboxyl group is regenerated from the functional group of formula 1a or 1b, and a polymer having an epoxy group ( A crosslinking reaction occurs with the epoxy groups in a02) and the epoxy resin (a01), and the coating film is cured.

  Since the stability of the coating liquid of the present invention is high as described above, the residual liquid of the coating liquid that has been once used for use has not yet deteriorated in a short operation. Therefore, such residual liquid can be collected or reused by adding a fresh coating liquid, which is economical.

  The thermosetting resin composition of the present invention is used for liquid crystal displays, CCDs, EL displays, etc., because the cured product obtained from the composition is colorless and transparent and has little coloration under long-term high-temperature conditions and high-energy light irradiation. It can be suitably used for a color filter planarizing film coating solution.

The mixing order in the case of preparing the thermosetting resin composition of the present invention by melt mixing is not particularly limited. For example, all the components are simultaneously dissolved in a solvent to prepare the composition solution of the present invention. Alternatively, if necessary, each component may be separately dissolved in the same or different solvent to form two or more solutions, and these solutions may be mixed to prepare a solution of the composition of the present invention.
Mixing can be performed by stirring with a stirring bar of a motor equipped with a stirring blade or a magnetic stirrer, or by mixing each component in a gallon container and then rotating the container together with a mix rotor.

Next, a method of using the color filter protective film coating solution of the present invention will be described below.
The color filter covers a black matrix formed in a predetermined pattern on a transparent glass substrate, a red (R) / green (G) / blue (B) colored layer formed in a predetermined pattern, and the colored layer. The protective film formed in the. A transparent electrode for driving liquid crystal may be formed on the protective film as necessary. Further, columnar spacers may be formed on the transparent electrode plate, the colored layer, or the protective film in accordance with the region where the black matrix layer is formed.
As described above, the thermosetting resin composition is used as a coating liquid, which is applied to the surface of the color filter on which the colored layer is formed by a method such as spin coater, roll coater, spraying, printing, etc. The obtained coating film is dried, further pre-baked as necessary, and then heated to form a protective layer.
When using a spin coater, the number of revolutions is usually set within a range of 500 to 1500 revolutions / minute. In general, the protective film is formed to a thickness of about 0.5 to 3.0 μm (after completion of curing).

  The thermosetting resin composition of the present invention is not limited to the above-mentioned applications, but includes other adhesives such as liquid crystal, resin for stereolithography, surface coating agents such as plastic, glass and metal, and decorative materials. It can also be used for applications that require transparency.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, “part” means part by mass unless otherwise specified.

Polymerization example 1
<Synthesis of a polymer having an epoxy group>
In a 500 mL four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 40.0 g of propylene glycol monomethyl ether acetate was charged and heated to 80 ° C. while stirring. Next, at a temperature of 80 ° C., 28.4 g of glycidyl methacrylate, 21.6 g of methyl methacrylate, 4.0 g of a peroxide-based polymerization initiator “Perbutyl O” manufactured by NOF Corporation, and 6.0 g of propylene glycol monomethyl ether acetate What was previously mixed uniformly (dropping component) was dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropping, the reaction was terminated after maintaining the temperature at 80 ° C. for 5 hours. A polymer solution (a-1) having an epoxy group with a weight average molecular weight (Mw) of 15,000, a solid content of 54.1%, a viscosity of 7.06 Pa · s (25 ° C.) and an epoxy equivalent of 462 of the solution was obtained. The weight average molecular weight (Mw) was measured by GPC. The solid content is based on the residual rate calculated from the change in weight before and after drying after precisely weighing 1 g of the solution and drying it at 170 ° C. for 1 hour with a thermostat. The viscosity was measured at a temperature of 20 ° C. using a vibratory viscometer Viscomate VM-1G (trade name) manufactured by CBC Materials Co., Ltd. equipped with a circulating constant temperature water bath. The epoxy equivalent was measured according to JIS K7236-1986.

Synthesis example 1
<Synthesis of Blocked Carboxylic Acid Compound (b-1)>
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 40.92 g of propylene glycol monomethyl ether acetate, cyclohexane-1,2,4-tricarboxylic acid (hereinafter referred to as CHTA) manufactured by Mitsubishi Gas Chemical Co., Ltd. 22.10 g, n-propyl vinyl ether 36.93 g and acidic phosphoric acid ester catalyst (mono-2-ethylhexyl phosphate and di-2-ethylhexyl phosphate, trade name: AP-8, Daihachi Chemical Industry Co., Ltd.) 0.05 g) was added and heated with stirring to raise the reflux temperature (about 67 ° C.). Next, stirring was continued while maintaining the reflux temperature, and the reaction was terminated when the acid value of the mixture became 2.0 mgKOH / g or less, and the blocked carboxylic acid compound solution (b- 1) was obtained. The acid value of the solution was calculated by titration with a 0.1N KOH ethanol solution. Moreover, the total acid equivalent of a carboxyl group and an acid anhydride group was computed by performing titration similar to a solution acid value after hydrolysis based on the hydrolysis acid value measurement (total acid value measurement) of JIS K0070.

Synthesis example 2
<Synthesis of Blocked Carboxylic Acid Compound (b-2)>
Synthesis of blocked carboxylic acid (b-1) except that 20.26 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (hereinafter abbreviated as CHTAn) was used instead of 22.10 g of CHTA The reaction was conducted in the same manner as in (1). The reaction was terminated when the acid value of the mixture became 2.0 mgKOH / g or less, and a blocked carboxylic acid compound solution (b-2) having an acid value of 0.25 mgKOH / g of the solution was obtained.

Synthesis example 3
<Synthesis of Blocked Carboxylic Acid Compound (b-3)>
The reaction was the same as in the synthesis of the blocked carboxylic acid (b-1) except that 21.49 parts of 1,2,4-trimellitic acid was used instead of 22.10 g of cyclohexane-1,2,4-tricarboxylic acid. Went. The reaction was terminated when the acid value of the mixture became 2.0 mgKOH / g or less, and a blocked carboxylic acid compound solution (b-3) having an acid value of 1.6 mgKOH / g of the solution was obtained.

<Curability evaluation>
First, evaluation about sclerosis | hardenability of a thermosetting resin composition was performed in Examples 1-4 and Comparative Examples 1-3 using the compound obtained by the above polymerization example and the synthesis example.
Example 1
26.0 parts of the blocked cyclohexane-1,2,4-tricarboxylic acid (b-1) described in Synthesis Example 1 above, and a nuclear hydrogenated product of bisphenol A type epoxy resin (a-2, Japan epoxy resin ( A thermosetting resin composition prepared by uniformly mixing with 16.3 parts of Epicoat YX8000 (trade name) manufactured by Co., Ltd. and epoxy equivalent 205) was 170 in a lab plast mill (LABO PLASTOMILL 30C150 manufactured by Toyo Seiki Seisakusho Co., Ltd.). The torque rise start time at ° C. was measured to evaluate curability. The blending ratio and results are shown in Table 1.

Example 2
Instead of 26.0 parts of blocked cyclohexane-1,2,4-tricarboxylic acid (b-1), the blocked cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride obtained in Synthesis Example 2 was used. A cured product was prepared in the same manner as in Example 1 except that 26.1 parts of the product (b-2) was used, and the obtained cured product was evaluated. The blending ratio and results are shown in Table 1.

Example 3
Instead of 16.3 parts of the nuclear hydrogenated product (a-2) of bisphenol A type epoxy resin, 36.8 parts of the polymer solution (a-1) having an epoxy group obtained in Polymerization Example 1 was used. Prepared a cured product in the same manner as in Example 1, and evaluated the obtained cured product. The blending ratio and results are shown in Table 1.

Example 4
The amount of the bisphenol A type epoxy resin nuclear hydrogenated product (a-2) used is changed from 16.3 parts to 3.6 parts, and the polymer solution (a-1) having an epoxy group obtained in Polymerization Example 1 is used. A cured product was prepared in the same manner as in Example 1 except that 28.7 parts were used, and the obtained cured product was evaluated. The blending ratio and results are shown in Table 1.

Comparative Example 1
Instead of 26.0 parts of blocked cyclohexane-1,2,4-tricarboxylic acid (b-1), methylhexahydrophthalic anhydride (b′-4, Rikacid MH700 (trade name) manufactured by Shin Nippon Rika Co., Ltd.) ) A cured product was prepared in the same manner as in Example 1 except that 6.7 parts were used, and the obtained cured product was evaluated. The blending ratio and results are shown in Table 1.

Comparative Example 2
Instead of 26.0 parts of blocked cyclohexane-1,2,4-tricarboxylic acid (b-1), methylhexahydrophthalic anhydride (b′-4, Rikacid MH700 (trade name) manufactured by Shin Nippon Rika Co., Ltd.) 6.7 parts of polymer solution (a-1) having an epoxy group obtained in Polymerization Example 1 instead of 16.3 parts of bisphenol A type epoxy resin nuclear hydrogenated product (a-2) ) A cured product was prepared in the same manner as in Example 1 except that 37.0 parts were used, and the obtained cured product was evaluated. The blending ratio and results are shown in Table 1.

Comparative Example 3
Instead of 26.0 parts of blocked cyclohexane-1,2,4-tricarboxylic acid (b-1), methylhexahydrophthalic anhydride (b′-4, Rikacid MH700 (trade name) manufactured by Shin Nippon Rika Co., Ltd.) 6.7 parts of bisphenol A type epoxy resin nuclear hydrogenated product (a-2) 3.6 parts, polymer solution having epoxy group obtained in Polymerization Example 1 (a-1) 28 A cured product was prepared in the same manner as in Example 1 except that 9 parts were used, and the obtained cured product was evaluated. The blending ratio and results are shown in Table 1.

In addition, the symbol in Table 1 shows the following.
a-1: Polymer having an epoxy group obtained in Polymerization Example 1, epoxy equivalent of 462 g / eq.
a-2: Nuclear hydrogenated product “Epicoat YX8000” (trade name) of bisphenol A type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 205 g / eq.
b-1: Blocked cyclohexane-1,2,4-tricarboxylic acid obtained in Synthesis Example 1, total acid equivalent of solution, 325.8 g / eq.
b-2: Blocked cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride obtained in Synthesis Example 1, total acid equivalent of 326.9 g / eq of solution.
b′-4: Methylhexahydrophthalic anhydride (MH700) “Licacid MH700” (trade name), manufactured by Shin Nippon Rika Co., Ltd., total acid equivalent of 84.1 g / eq.

Examples 5-8, Comparative Examples 4-7
As shown in Table 2, the coating liquids of Examples 5 to 8 and Comparative Examples 4 to 7 were blended by the following preparation methods using various materials. Evaluation was performed using these samples.
<Preparation of coating solution>
A rotor coated with tetrafluoroethylene resin was placed in a sample bottle and placed on a magnetic stirrer. In this sample bottle, according to the blending ratio shown in Table 2, after adding various materials and sufficiently stirring and dissolving, adding a diluting solvent for adjusting the viscosity, stirring and dissolving, this is filtered to obtain a coating solution. Obtained.

<Creation of coating film>
A well-cleaned glass substrate was spin-coated using the coating solution, sufficiently dried, and finally cured at 230 ° C. for 30 minutes on a hot plate to obtain a coating film. The coating film performance test was done about the obtained coating film. The blending ratio and results are shown in Table 2.

Each test method in Table 2 is as follows.
<Storage stability>
When the initial viscosity of the coating liquid was 0.1 to 1000 mPa · s, and the viscosity after leaving the coating liquid in a sealed container at 20 ° C. for 40 days was not more than twice the initial viscosity, it was determined to be good.
<Transparency>
When the transmittance in the visible region of 400 to 700 nm was 90% or more, it was judged good.
<Light resistance>
The test piece for which the transparency was determined was irradiated with light at an illuminance of 50 million lux for 500 hours in air (temperature 75 ° C.) using a high-pressure mercury lamp as a light source, and the transparency was similarly determined.
<Hardness>
Among the mechanical properties of the coating film specified in JIS K5600-5-4-scratch hardness (pencil method), it was determined to be good when it showed a pencil hardness of 2H or higher by the hand-scratching method.
<Heat resistance>
The color filter provided with the protective film was judged to be good when the decrease in the thickness of the protective film after being allowed to stand at 250 ° C. for 1 hour was 10% or less and the color difference before and after being left was 1 or less. The color difference was determined by the ΔEab color difference formula established in 1976 by the CIE (International Commission on Illumination). Actual measurement was performed with a spectrocolorimeter (Spectrocolorimeter CM-3500d manufactured by Minolta Co., Ltd.).
<Solvent resistance>
It is calculated by immersing a color filter provided with a protective film in each of three solvents of isopropyl alcohol, N-methylpyrrolidone and γ-butyrolactone at a liquid temperature of 40 ° C. for 1 hour and then measuring the film thickness of the protective film. When the film thickness reduction was 10% or less even when immersed in any solvent, it was judged good.
<Adhesion after heat-resistant pure water test>
The result of performing the mechanical property-adhesiveness (cross-cut method) test method of the coating film prescribed in JIS K5600-5-6 after the color filter provided with the protective film was immersed in pure water at 80 ° C. for 1 hour. It was determined to be good when the classification was 0 to 2 in the same method.

In addition, the symbol in Table 2 shows the following.
a-1: Polymer having an epoxy group obtained in Polymerization Example 1, epoxy equivalent of 462 g / eq.
a-2: Nuclear hydrogenated product “Epicoat YX8000” (trade name) of bisphenol A type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 205 g / eq.
b-1: Blocked cyclohexane-1,2,4-tricarboxylic acid obtained in Synthesis Example 1, total acid equivalent of solution, 325.8 g / eq.
b-2: Blocked cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride obtained in Synthesis Example 1, total acid equivalent of 326.9 g / eq of solution.
b′-1: cyclohexane-1,2,4-tricarboxylic acid (CHTA), total acid equivalent 72.1 g / eq.
b′-2: Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (CHTAn), total acid equivalent 66.1 g / eq.
b′-3: Blocked trimellitic acid obtained in Synthesis Example 3, total acid equivalent of the solution 323.7 g / eq.
b′-4: Methylhexahydrophthalic anhydride (MH700) “Licacid MH700” (trade name), manufactured by Shin Nippon Rika Co., Ltd., total acid equivalent of 84.1 g / eq.
LC-1: Thermal latent catalyst “LC-1” (trade name), PEGMMA manufactured by NOF Corporation: Propylene glycol monomethyl ether acetate.

Next, application evaluation to the flattening film and the protective film of the color filter was performed using the coating liquids of the present invention in Examples 9 and 10 and the commercial coating liquid of Comparative Example 8.
Example 9
In the same manner as in Example 5, each raw material was blended and dissolved uniformly to obtain a thermosetting resin composition. 3 cc of the above thermosetting resin composition is dropped on a glass substrate on which an RGB dye layer is formed between black matrix partitions prepared in advance, and spin-coated at 900 rpm to form a uniform coating film on the substrate. Formed. This substrate was put in an oven at 80 ° C. and pre-baked for 5 minutes, and was thermally cured at 200 ° C. for 60 minutes to obtain a liquid crystal protective film. The flatness of the formed protective film layer is good, and an ITO electrode for driving a liquid crystal is formed on this protective film-formed substrate at about 0 ° C. with H ₂ O / O ₂ introduced at 120 ° C. using a sputtering apparatus. When sputtering was performed with a thickness of 13 μm, a surface resistance value of 20Ω / □ as designed was obtained uniformly.

Example 10
In the same manner as in Example 5, each raw material was blended and dissolved uniformly to obtain a thermosetting resin composition. A silicon wafer on which an image sensor having a pixel pitch of 5 μm, a light receiving portion width of 1.5 μm, and a surface level difference of 2 μm is applied is applied to a final film thickness of 1.5 μm, and heated on a hot plate having a surface temperature of 200 ° C. As a result, a planarization layer was obtained. The surface flatness at this time was 0.2 μm. A green pigment dispersion resist was applied to the flattened film in a thickness equivalent to about 1 μm, prebaked for 3 minutes on a hot plate at 80 ° C., and then irradiated with 500 mJ ultraviolet rays through a predetermined pattern photomask. Subsequently, after developing with 0.1% aqueous solution of tetramethylammonium hydride, washing with water and drying, it was post-baked on a hot plate at 200 ° C. for 5 minutes to form green fine pixels. In the same manner, a solid-state imaging device in which red and blue fine pixels were formed and a color filter was directly attached was obtained. When this was observed from directly above with a microscope, residue contamination on the underlying planarization layer was not observed. Further, the thermosetting resin composition was applied thereon to a thickness equivalent to about 1 μm, and heated on a hot plate having a surface temperature of 200 ° C. for 5 minutes to form a protective film. The surface flatness at this time was 0.08 μm. When the adhesiveness of the protective film was evaluated by a cross-cut peel test, all of them were confirmed to have strong adhesiveness with a peel number of 0/100.

Comparative Example 8
On the same substrate as the semiconductor substrate used in Example 10, a resin (trade name: TP-10) manufactured by Fuji Pharmaceutical Co., Ltd. is used for the planarizing film, and a resin manufactured by Fuji Pharmaceutical Co., Ltd. is used for the protective film. A planarizing film, a color filter, and a protective film were formed in the same manner as in Example 10 except that (trade name: TOC-1) was used. At this time, the flatness of the flattening film was 0.63 μm, and the flatness of the protective film was 0.25 μm.

The flatness test methods of Example 10 and Comparative Example 8 are as follows.
<Flatness>
The surface roughness was measured with a surface roughness meter (Full Corder ET4000 (trade name) manufactured by Kosaka Laboratory Ltd.).

  From the result of Examples 1-4, since the torque rise which shows the start of hardening is seen in 1.5-11 minutes under the heating of 170 degreeC, the thermosetting resin composition of this invention adds a hardening accelerator. Even if it does not do, it turns out that it is excellent in curability. On the other hand, in Comparative Examples 1-3, it turns out that the system of the used epoxy resin and methylhexahydrophthalic anhydride is slow and is not practical.

Moreover, from the results of Table 2, in the case of Examples 5 to 8, flatness, transparency, hardness, residual film ratio and color difference after heat resistance test, residual film ratio after solvent resistance test, warm pure water resistance test It was excellent in later adhesion and storage stability.
On the other hand, Comparative Examples 4, 5 and 7 did not use the blocked carboxylic acid, and thus the storage stability of the coating solution was remarkably inferior. In Comparative Example 6, since the blocked carboxylic acid contained an aromatic, the transparency of the final cured film was inferior.

  Furthermore, it is shown that the applicability of the color filter to the protective film in general in Example 9 and the applicability to the color filter flattening film and protective film for use in the imaging device are extremely excellent in Example 10. . In the case of Example 10, the final surface flatness on the color filter could be reduced to 0.1 μm or less despite the thin film of 2.5 μm in total of the planarizing film and the two protective films. On the other hand, in the case of Comparative Example 8 using a commercially available coating liquid that is not the present invention, the surface flatness is 0.25 μm, and it is understood that the flatness under the required thinning conditions cannot be obtained.

Claims (7)

  A thermosetting resin composition for a planarizing film of a color filter containing an epoxy group-containing resin (A) and a curing agent (B), wherein the curing agent (B) is cyclohexanetricarboxylic acid (b01) or It is a compound obtained by addition reaction of a carboxyl group of the acid anhydride (b02) and a vinyl group of vinyl (thio) ether (b11) having one or more vinyl groups in one molecule. A thermosetting resin composition for a color filter flattening film.   The cyclohexanetricarboxylic acid (b01) is cyclohexane-1,2,4-tricarboxylic acid or cyclohexane-1,3,5-tricarboxylic acid, and the acid anhydride (b02) is cyclohexane-1,3,4- The thermosetting resin composition for a flattened film of a color filter according to claim 1, which is tricarboxylic acid-3,4-anhydride.   A coating solution for a flattened film of a color filter comprising the thermosetting resin composition according to claim 1.   A cured resin obtained by curing the thermosetting resin composition according to claim 1.   A color filter having a layer of a cured resin obtained by curing the thermosetting resin composition according to claim 1.   A solid-state imaging device having a layer of a cured resin obtained by curing the thermosetting resin composition according to claim 1. The display apparatus which has a layer of the resin cured material formed by hardening | curing the thermosetting resin composition of Claim 1 or 2.