JP3287661B2 - Thermosetting resin composition, cured product thereof, and image forming material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition having a small curing shrinkage, a cured product thereof, and an image forming material. In other words, when used as a molded product, it has excellent dimensional stability, has little residual stress and optical distortion, and when used as an adhesive component, has excellent dimensional stability and adhesiveness. It is a thermosetting resin composition that gives a film having a small amount of water.

[0002] The cured product of the present invention has hardness, solder heat resistance, transparency, adhesion, acid resistance, alkali resistance, solvent resistance, insulation resistance, electrolytic corrosion resistance and plating resistance, and a smooth coating film. Excellent in terms of sex. More specifically, a resin composition for a protective film of a color filter used for an insulating film / paint, an adhesive, a precision casting agent, a printing ink or a coating agent, particularly, a liquid crystal display device or an imaging device,
It is useful as a color filter ink and a color filter composed of these, and is also useful as a spacer material that is an insulating separator in a touch panel for inputting information installed on the upper part of a liquid crystal display screen, and as a touch panel using the same. .

[0003]

2. Description of the Related Art In general, curable resins such as (meth) acrylate resins, epoxy resins and unsaturated polyester resins always undergo curing shrinkage during curing, which causes cracks due to internal stress, poor adhesion and appearance. It is the cause of the failure. Among these curable resins, even the epoxy resin having the smallest curing shrinkage shows a volume shrinkage of about 3 to 6%, and causes various problems during curing.

Therefore, conventionally, as a measure for solving such a problem, an inorganic filler such as silica, calcium carbonate, alumina or the like is added to reduce the relative curing shrinkage. However, in this method, since the viscosity of the resin composition is increased by the addition of the filler, there is another problem that casting at a low temperature becomes difficult. Further, when the cured product requires transparency, it cannot be used. Further, an attempt has been made to prevent the volume shrinkage by adding a non-reactive resin compatible with the epoxy resin to the epoxy resin (Japanese Patent Publication No. 58-57,426).
However, this is not preferred because it often leads to a decrease in physical properties of the cured product, particularly a decrease in heat resistance.

On the other hand, apart from the above-mentioned method, studies are being made on reducing the shrinkage of the resin alone. Polymer, 2
7, 108 (1978), as a monomer that does not shrink during the polymerization reaction, 1,2 obtained by reacting ethylene oxide with γ-butyrolactone
4,6-Trioxaspiro (4,4) nonane is known. This compound undergoes ring-opening polymerization to give a thermoplastic resin, but is known to be a thermosetting resin when bifunctionalized [J. Macromol. Sci., Chem., A9, 84
9 (1975) and J. Polym. Sci., Polym. Shmp., 56, 117
(1976)]. According to these, boron trifluoride-diethyl ether complex is added as a catalyst to a bisspiro orthoester compound having a skeleton of hydroquinone or bisphenol A, and the ring is opened and cured at room temperature for 24 hours. According to this method, it is possible to reduce the shrinkage during curing to zero. However, cured products of such spiroorthoester compounds are known to have inferior heat resistance as compared with epoxy resins, and when used together with a diluent having a large curing shrinkage in applications requiring heat resistance. Is
There is a problem that the content of the spiroorthoester compound cannot be increased.

Also, a photopolymerizable compound obtained by adding a (meth) acrylate having a hydroxyl group to a copolymer of an addition product of an epoxy (meth) acrylate and an acid anhydride and a copolymer of maleic anhydride and a vinyl compound. (Special Publication 56-
40,329, JP-A-63-17,908, JP-A-4-345,608, JP-A-4-340,965,
Japanese Unexamined Patent Publications Nos. 2-247,654) are disclosed. These usually show a large curing shrinkage of 5% or more, and become a coating film having poor adhesion and moisture resistance only by light curing. Therefore, by forming a composition with an epoxy compound, photocuring, after development, heat-curing to react the epoxy group with the carboxyl group contained in the photopolymerizable compound, whereby the water absorption, physical properties such as alkali resistance Is being improved. However, as described above, curing shrinkage also occurs due to curing of the epoxy resin, leaving problems such as remaining internal stress and generation of cracks.

[0007] As a specific application of the above-mentioned alkali-developable photosensitive resin material, it is disclosed that the photosensitive resin material is used as a material for a color filter. The shrinkage is large, and still involves problems such as a decrease in the thickness of the protective film layer, a decrease in the pattern size of the color filter, and generation of cracks.

Further, such a photosensitive resin material which can be alkali-developed is not particularly mentioned, but may be used as a spacer as an insulating separator of a touch panel. However, even in such applications, the same problems as those in the application to the color filter described above are pointed out.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cured product obtained from a thermopolymerizable compound containing an ethylenically unsaturated double bond and a carboxyl group, while taking advantage of the heat resistance and other properties of the cured product. Is to provide a thermosetting resin composition having a low curing shrinkage by adding to a component of the composition. That is, the resin composition of the present invention is excellent in dimensional stability when used as a molded article, has little residual stress and optical distortion, and has dimensional stability and adhesiveness when used as an adhesive component. Excellent,
Further, when this is used as a coating agent, a coating film having excellent adhesion and little film loss is provided.

Therefore, by using the resin composition of the present invention, insulating coatings / paints, adhesives, precision casting agents,
In printing inks and coating agents, especially as resin compositions for protective films of color filters used in liquid crystal display devices or imaging devices, inks for color filters, and color filters composed of these, It is possible to obtain a spacer material that is an insulating separator in an installed information input touch panel, and a material suitable for a touch panel using the same.

[0011]

Means for Solving the Problems The present inventors have made intensive studies in view of these circumstances, and have found that a thermopolymerizable compound having a carboxyl group and a compound having an orthospiroester group which gives a small curing shrinkage. The present inventors have found that a resin composition has a small curing shrinkage and is excellent in dimensional accuracy and adhesiveness, and has arrived at the present invention.

That is, the present invention relates to a polymerization initiator (B) which generates a radical by heat per 100 parts by weight of (A) a thermopolymerizable compound having an ethylenically unsaturated double bond and a carboxyl group (component A). B)) in an amount of 0.1 to 10 parts by weight, and (C) the following general formula (1)

[0013]

Embedded image

(Wherein p is an integer of 3 to 5). A spiroorthoester compound (component C) having two or more spiroorthoester groups in one molecule represented by the following formula:
And 100 parts by weight.

Further, the present invention provides a cured product formed using such a thermosetting resin composition having a low curing shrinkage,
Materials for color filters, color filter inks, color filters, spacer materials for touch panels, and touch panels.

In the present invention, specific examples of the component A having both an ethylenically unsaturated double bond and a carboxyl group include the following. First, an epoxy (meth) acrylate adduct obtained by reacting an acid anhydride with a hydroxy group obtained by reacting an epoxy compound with (meth) acrylic acid (hereinafter, acrylic acid and methacrylic acid are collectively referred to as such) is obtained. is there.

Specific examples of the epoxy compound to be subjected to this reaction include bis (4-hydroxyphenyl) ketone and bis (4-hydroxy-3,5-dimethylphenyl) ketone as bisphenol component of epoxy as aromatic epoxy. , Bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) ) Sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-
3,5-dimethylphenyl) hexafluoropropane,
Bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-
Dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4
-Hydroxy-3,5-dibromophenyl) methane,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,
5-dichlorophenyl) propane, 2,2-bis (4-
(Hydroxy-3-methylphenyl) propane, 2,2-
Bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether ,Also,

[0018]

Embedded image

Examples of those containing 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene,
Bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-
Fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9
-Bis (4-hydroxy-3,5-dimethylphenyl)
Fluorene, 9,9-bis (4-hydroxy-3,5-
Dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene,
Further, there is an epoxy resin containing 4,4'-biphenol, 3,3'-biphenol and the like. Furthermore, phenol novolak type epoxy, cresol novolak type epoxy, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin and the like are also included. These include
Oligomer units are mixed during glycidyl etherification, but there is no problem in the performance of the resin composition of the present invention.

Examples of the polybasic acid or its anhydride which can react with the hydroxyl group in the epoxy (meth) acrylate molecule include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydroanhydride. Phthalic acid, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride,
Methyltetrahydrophthalic anhydride, or pyromellitic anhydride, benzophenonetetracarboxylic dianhydride,
Aromatic polycarboxylic anhydrides such as biphenyltetracarboxylic dianhydride and biphenylethertetracarboxylic dianhydride are exemplified.

Further, specific examples of the component A include monomers such as ethylene, propylene, isobutene, styrene, vinylphenol and ether derivatives or ester derivatives thereof which can be copolymerized with maleic anhydride, and monomers such as acrylic acid, acrylic acid ester and acrylamide. A half-esterified compound obtained by reacting an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate or an acrylate having an epoxy group such as glycidyl methacrylate with the maleic anhydride portion of the copolymer of And a compound obtained by further reacting (meth) acrylic acid with a hydroxyl group of a copolymer of (meth) acrylic acid ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate. That. These polymerizable compounds having an ethylenically unsaturated double bond and a carboxyl group,
It is not necessarily limited to those described above, and they may be used alone or as a mixture.

Among them, the component A is obtained by reacting a reaction product of an epoxy compound and (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof, considering the compatibility with the component C described later. The product used is preferably used. Furthermore,
When an acid dianhydride is present as a polybasic acid or an acid anhydride to be reacted with an epoxy (meth) acrylate,
The cured product becomes more excellent in heat resistance.

That is, the following general formulas (2) and (3)

Embedded image [However, in the general formulas (2) and (3), R ₁ and R
₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, R ₃ is a hydrogen atom or a methyl group, and X is —CO—, —SO ₂ —, —C (CF ₃ )
_{2 -, - Si (CH 3} ) 2 -, - CH 2 -, - C (CH
₃ ) _2- , -O-,

Embedded image Y represents an acid anhydride residue, Z represents
Represents a residue of an acid dianhydride, and the structural unit m: n is a compound mainly having a unit structure represented by a molar ratio of 0/100 to 100/0).

Specific examples of the epoxy compounds which can give these general formulas (2) and (3) include two or more epoxy groups in one molecule derived from the above-mentioned various bisphenols, phenol novolaks, cresol novolaks and the like. There are aromatic epoxy compounds contained.

Examples of the acid anhydride compound into which the residue Y can be introduced include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, Methylendmethylenetetrahydrophthalic acid, chlorendic anhydride,
Methyltetrahydrophthalic anhydride and the like, and as the acid dianhydride compound of Z, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenylethertetracarboxylic dianhydride and the like And aromatic polycarboxylic anhydrides of the formula (1).

Further, regarding the molecular weight of a product mainly comprising the compounds represented by the general formulas (2) and (3), a solution obtained by dissolving 0.5 g of this compound in 100 ml of N-methylpyrrolidone was measured at 30 ° C. Inherent viscosity (η _inh )
Is 0.1 dl / g or more, preferably 0.15 dl / g or more, and gives a favorable result as tack-free after drying of the coating film.

The acid anhydride and the dianhydride used at this time may be used in any ratio. In consideration of alkali developability, it is preferable that the acid anhydride (m) and the acid dianhydride ( n) with a molar ratio (m / n) of 5/95 to 95 /
5 is good.

A compound obtained by reacting (meth) acrylate with a polybasic acid or an acid anhydride thereof can be produced as follows. For example, first, a bisphenolfluorene-type epoxy compound represented by the following general formula (5) obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with epichlorohydrin, and the following general formula (6) By reacting with (meth) acrylic acid represented by the following formula, a bisphenolfluorene-type epoxy acrylate resin represented by the following general formula (7) is synthesized, and then the above acid anhydride, ethyl cellosolve acetate, and butyl cellosolve acetate It is manufactured by heating in a cellosolve-based solvent such as The reaction temperature at this time is desirably quantitatively reacted so that the acid anhydride is モ ル mol per mol of OH groups of the epoxy acrylate resin, and is preferably 90 to 130 ° C., preferably 95 to 125 ° C.
It is. For this reaction, general formulas (2) and (3)
The same applies to the entire compound having the unit structure of

[0029]

Embedded image

The thermosetting resin composition of the present invention contains the above (meth) acrylate compound, but also contains a radical polymerization initiator for curing it by heating. Therefore, the resin composition of the present invention is cured by heating. The radical polymerization initiator of the B component used for curing the A component of the present invention generates a radical by heating, and is used not only for the A component but also for a heat-polymerizable (meta- ) It is also used as a polymerization initiator for a polymerizable unsaturated compound such as an acrylic monomer or a (meth) acrylic oligomer.

As the radical polymerization initiator of the component B used for such a purpose, a known peroxide initiator or an azobis initiator can be used. Here, specific examples of the peroxide-based initiator include ketone peroxide-based ones such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexane ketone peroxide, and acetylacetone peroxide, and isobutyl peroxide. Oxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o
-Methylbenzoyl peroxide, bis-3,5,5
Diacyl peroxides such as -trimethylhexanoyl peroxide and 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and the like. Hydroperoxides, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t- Dialkyl peroxides such as butyl cumyl peroxide,
1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-di- (t-butylperoxy) butane, 4,4-di-t-butylperoxyvaleric acid-n- Butyl ester and other peroxyketal compounds, 2,4,4-trimethylpentylperoxyphenoxyacetate, α-cumylperoxyneodecanoate, t-butylperoxybenzoate, di-t-butylperoxytrimethyl Alkyl peresters such as adipate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl)
Examples thereof include percarbonate-based compounds such as peroxydicarbonate and diisopropylperoxydicarbonate, and other acetylcyclohexylsulfenylperoxydicarbonate and t-butylperoxyallylcarbonate.

Specific examples of the azobis initiator include 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2 ' -Azobis- (4-methoxy-
2,4-dimethylvaleronitrile), 2,2′-azobis- (methyl isobutyrate), α, α′-azobis-
(Isobutyronitrile), 4,4'-azobis- (4-
Cyanovaleic acid) and the like.

Any of these radical polymerization initiators can be used alone, or can be used as a mixture of two or more kinds. The amount of the C component is 0.1 to 100 parts by weight of the A component. It is blended in an amount of 10 to 10 parts by weight. If the compounding ratio of the component C is less than 0.1 part by weight with respect to 100 parts by weight of the component A, the polymerization rate becomes slow. Is reduced.

Further, in order to improve the moisture resistance, adhesion and electrical insulation stability of the cured product, the following general formula (1)

Embedded image (Where p is an integer of 3 to 5) A compound (C component) having two or more orthospiroester groups in one molecule represented by 5 to 100 parts by weight based on 100 parts by weight of the A component Mix within the range.

In the resin composition of the present invention, due to the effect of the component C, the curing shrinkage before and after the heat treatment is small, and when used as a coating material, the film loss is reduced, and the dimensional stability of a pattern obtained by a printing method or the like is reduced. The effect of improving the adhesiveness to glass, ITO (indium tin oxide), and other transparent electrodes is exhibited. Also, when it is used as an adhesive, dimensional accuracy and adhesiveness are improved, and when used as a molding material, the size is improved. A cured product having excellent moisture resistance, transparency, surface hardness, flatness, heat resistance, and chemical resistance, such as improved stability, reduced residual stress and optical distortion, is formed. The heating temperature and the heating time under the heating and curing conditions at this time are, for example, 80 to 200 ° C. and 10 to 10, respectively.
120 minutes.

Examples of the spiroorthoester constituting the resin composition of the present invention include γ-butyrolactone and δ-butyrolactone.
Spiroorthoesters produced by reacting a lactone such as valerolactone or ε-caprolactone with the aforementioned epoxy compound are used. Specific examples of such epoxy compounds include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5
-Dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,
5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4
-Hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-Dimethylphenyl) propane, 2,2-bis (4-hydroxy-
3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-chlorophenyl)
Propane, bis (4-hydroxyphenyl) ether,
Bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, and

[0037]

Embedded image

Examples of those containing 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene
Bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-
Fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9
-Bis (4-hydroxy-3,5-dimethylphenyl)
Fluorene, 9,9-bis (4-hydroxy-3,5-
Dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene,
Further, phenolic compounds such as 4,4'-biphenol, 3,3'-biphenol, resorcinol, phenol novolak, cresol novolak, naphthol novolak, and resins obtained by condensing phenol or naphthol with 1,4-benzenedimethanol. There is an aromatic polyfunctional epoxy resin having an average of more than two glycidyl ether groups in a molecule, which is obtained by reacting epichlorohydrin. Also, a polycarboxylic acid glycidyl ester obtained by reacting a compound having a carboxylic acid group such as adipic acid, sebacic acid, phthalic acid, and hexahydrophthalic acid with epichlorohydrin, EHP manufactured by Daicel Chemical Industries, Ltd.
There are aliphatic polyfunctional epoxy resins such as E3150, and polyol polyglycidyl esters, alicyclic epoxy resins having an average of two or more internal epoxy groups in the molecule,
For example, Chisso Knox 201, 2
21, 289, 206, 207 and 1221; Celloxide 2021P manufactured by Daicel Chemical Industries, Ltd .; and nitrogen-containing heterocycles obtained from epoxidized olefins, epoxidized polybutadienes, epoxy isocyanurate, hydantoin derivatives, imidazoline derivatives, and the like. Epoxy and the like are also included.

The mixing ratio of the above spiroorthoester compound is preferably 5 to 100 parts by weight based on 100 parts by weight of the component A. If the blending ratio of component B is less than 5 parts by weight with respect to 100 parts by weight of component A, the effect of adding the spiroorthoester compound is not remarkable. Conversely, if it exceeds 100 parts by weight, sufficient heat resistance may be obtained depending on the type of spiroorthoester. The nature is not exhibited.

When a spiroorthoester is selected for the purpose of improving heat resistance, two spiroorthoester groups are added to the molecule.
Compounds having a bulky aromatic ring, for example, those having a fluorene skeleton in the following general formula (4)

[0041]

Embedded image

[Where A in the formula is

Embedded image (Wherein, R ₁ and R ₂ represent the same as those in formulas (2) and (3)), q is 0 or an integer of 1 to 10, and p is the same as in formula (1). The heat resistance can be expressed without significantly increasing the crosslinking density.

As specific examples, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-) Chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-
Fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9
-Bis (4-hydroxy-3,5-dimethylphenyl)
Fluorene, 9,9-bis (4-hydroxy-3,5-
There are spiroorthoesters obtained by reacting epoxy compounds such as dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene with lactones.

With regard to the same effect, an aromatic compound containing three or more spiroorthoester groups in the molecule is preferable. Specific examples include phenol novolak, cresol novolak, naphthol novolak, and an epoxy resin obtained by reacting a phenolic compound such as a resin obtained by condensing phenol or naphthol with 1,4-benzenedimethanol and epichlorohydrin. Polyfunctional spiroorthoester compounds. These also have the effect that curing shrinkage can be reduced with a small amount of addition.

The combination of the above components A and C is effective in any combination as long as the compatibility is not hindered during the preparation of the resin composition, and is selected according to the use.

The resin composition of the present invention may further contain, in addition to the above-mentioned component A, a monomer or oligomer having an ethylenically unsaturated group capable of being thermally polymerized within a predetermined range according to the intended use. Can be. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth)
Monomers having a hydroxyl group such as acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol li (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) (Meth) acrylates such as acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. It can be mentioned. One of these compounds can be used alone, or two or more of them can be used in combination.

These compounds are required to be in a range that does not impair the properties of the resin composition of the present invention and the cured product thereof, and are usually used in an amount of 50 parts by weight or less based on 100 parts by weight of the component A. Is done. If the amount used exceeds 50 parts by weight, a problem arises in tackiness after precuring.

Further, the resin composition of the present invention contains the above C
An epoxy resin suitable for the purpose can be added as long as the unreacted epoxy resin at the time of the preparation of the component is contained or the physical properties of the cured product are not impaired. In this case, in order to exhibit a decrease in curing shrinkage due to the spiroorthoester compound (component C), the amount is less than 50 parts by weight, more preferably less than 40 parts by weight, per 100 parts by weight of the component C.

The thermosetting resin composition may further contain a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler,
Additives such as a solvent, a leveling agent and an antifoaming agent can be blended. Examples of the curing accelerator for the spiroorthoester group include amine compounds, imidazole compounds, 1,8-diaza-bicyclo (5,4,0) undecene-7 and salts thereof, boron trifluoride amine complex, and heat. Organic sulfonium salts that generate Lewis acids, carboxylic acids, phenols, quaternary ammonium salts or methylol group-containing compounds, and the like, and a cured product obtained by heating the coating film in combination with a small amount of them. Heat-resistant,
Various properties such as solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, and hardness can be improved.

Further, examples of the above-mentioned thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Fillers include glass fiber, silica,
Mica, alumina, carbon black, silver powder and the like can be added according to the purpose.

When the resin composition of the present invention is used as a coating agent or an adhesive, it may be diluted with a solvent for the purpose of adjusting viscosity or the like. In that case, as a solvent,
For example, methyl ethyl ketone, ketones such as methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve,
Cellosolves such as butyl cellosolve and cellosolve acetate; lactones such as γ-butyrolactone; Examples of the antifoaming agent and the leveling agent include silicon-based, fluorine-based, and acrylic-based compounds.

Uses of the resin composition of the present invention include molding materials, insulating coatings / paints, adhesives, printing inks and coating agents, and the like, but due to the effect of the C component, curing shrinkage before and after heat treatment is small. When used as a coating material, effects such as a reduction in film loss, an improvement in dimensional stability of a pattern, and an improvement in adhesion to a transparent electrode such as glass or ITO (indium tin oxide) are exhibited. Sometimes, dimensional accuracy and adhesion are improved, and when used as a molding material,
A cured product excellent in moisture resistance, transparency, surface hardness, flatness, heat resistance, and chemical resistance, such as improved dimensional stability, reduced residual stress, and optical distortion, can be formed.

When the thermosetting resin composition of the present invention is used as a coating material, the resin composition is applied as a solution to a substrate surface, followed by pre-curing at 50 to 80 ° C. to dry the solvent. A post-baking at 80 to 220 ° C. yields a cured film. Further, a pattern can be formed by screen printing or the like.

The method of applying the resin composition solution to the substrate in the present invention may be any of known methods such as a solution dipping method and a spray method, and a roller coater machine, a land coater machine or a spinner machine. Can be adopted. After applying to the desired thickness by these methods,
If the solvent is removed, a film is formed. The substrate to be applied is made of glass, a transparent film (eg, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) on which a transparent electrode such as ITO or gold is deposited and patterned, or a metal such as aluminum or steel. .

After drying the solvent, the temperature is 80 to 220 ° C. and 10 to 12
A heat treatment for 0 minutes is performed. Here, the spiroorthoester compound of the component C has a small shrinkage upon curing, contributes to the dimensional stability of the resist pattern, and further improves the hygroscopicity, chemical resistance, adhesion, electrical insulation and the like of the coating film.

The thermosetting resin composition of the present invention can be suitably used as a coating material. In particular, a resin composition for a protective film of a color filter used for a liquid crystal display device or a photographic device, an ink for a color filter, Further, the present invention is useful as a color filter composed of the above, and is also useful as a spacer material that is an insulating separator in a touch panel for inputting information installed on an upper portion of a liquid crystal display screen, and as a touch panel using the same. For example, when the resin composition of the present invention is a protective film for a color filter, the composition may be mainly composed of the components A, B and C.

In the case of a color filter ink, a pigment is used as a D component for coloring a coating film in addition to the above A component, B component and C component. Pigments used include organic pigments and inorganic pigments. Examples of the organic pigment include azo lake-based, insoluble azo-based, phthalocyanine-based, quinacdrine-based, dioxazine-based, isoindolinone-based, berynone-based, anthraquinone-based, perylene-based, and the like, and mixtures thereof. Examples of inorganic pigments include Miloli blue, iron oxide, cobalt-based, manganese-based, ultramarine, navy blue, cobalt blue, cerulean blue,
Pyridian, emerald green, cobalt green,
And mixtures thereof. For these pigments, the pigment is preferably dispersed in a particle size of 0.4 μm or less, which is the lower limit of the wavelength of visible light, in order to color the coating film while maintaining the transparency of the coating film. 0.2-0.3μ
It is practically preferable to have an average particle diameter of not more than m. If the compounding amount is less than 10 parts by weight based on 100 parts by weight of the total of the components A and C, the desired spectral characteristics cannot be obtained. It is not preferable because the property is lowered.

Further, the thermosetting resin composition of the present invention comprises:
As described above, in addition to a color filter of a color liquid crystal display and a protective film thereof, it is also used as a protective film and various multicolor display ink materials such as a color liquid crystal display device, a color facsimile, and an image sensor.

When the resin composition of the present invention is used as a spacer material for a touch panel, the substrate to be applied varies depending on the form and environment used as the touch panel, but may be made of glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polystyrene). A transparent electrode such as ITO or gold is deposited and patterned on ether sulfone. For any of the substrates, it is possible to provide a spacer for a touch panel excellent in similar adhesion, transparency, surface hardness, flatness, moisture resistance, electrical insulation, heat resistance, and chemical resistance.

A pattern is formed using the spacer material of the present invention, and subsequently cured by heating to produce a spacer as an insulating separator for a touch panel. The form of the touch panel in which the spacer of the present invention is used can be used in any method as long as the electrodes are opposed to each other via the spacer using two transparent conductive films or transparent conductive substrates. it can. For example, as a configuration of a transparent touch panel, “Manufacture and Application of Transparent Conductive Film, Chapters 11 to 13” (published by CMC, supervised by Saburo Tabata, 1986) is exemplified. As described above, the spacer patterned on the transparent conductive substrate or the transparent conductive film is used as an insulating separator, and the opposing transparent conductive film is laminated thereon to form a transparent touch panel.

[0061]

The present invention will be described below in detail based on Synthesis Examples, Examples and Comparative Examples. First, Synthesis Examples 1 to 14 show the synthesis of the thermopolymerizable compound as the component A of the present invention.

Synthesis Example 1 In a 500 ml four-necked flask, 231 g of bisphenol fluorene type epoxy resin (epoxy equivalent 231),
Triethylbenzylammonium chloride 450m
g, 2,6-di-isobutylphenol 100 mg and acrylic acid 72.0 g were mixed and heated and dissolved at 90 to 100 ° C. while blowing air (25 ml / min.). Next, the temperature was gradually raised while the solution remained cloudy, and heated to 120 ° C. to completely dissolve the solution. The solution gradually became transparent and viscous, and stirring was continued as it was. The acid value of this solution was measured, and heating and stirring were continued until the acid value became less than 2.0 mgKOH / g. It took 8 hours for this acid value to reach the target (acid value 0.8). Thereafter, the mixture was cooled to room temperature to obtain a colorless and transparent solid.

Next, 2 kg of cellosolve acetate was added to 303 g of the bisphenol fluorene type epoxy acrylate resin obtained above to form a solution.
38 g of 3,6-tetrahydrophthalic anhydride, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are added, mixed, gradually heated, and reacted at 110 to 115 ° C. for 2 hours to obtain a compound. 1
(M / n = 50/50). The reaction of this acid anhydride was confirmed by disappearance of the 1780 cm ^-1 peak in the IR spectrum. The inherent viscosity of the obtained compound was 0.3 dl / g (η _inh = 0.3).

Synthesis Example 2 Using 303 g of the bisphenolfluorene-type epoxy acrylate resin prepared in Synthesis Example 1, 2 kg of cellosolve acetate was added to form a solution, and then 121.6 g of 1,2,3,6-tetrahydrophthalic anhydride and benzophenone 64.6 g of tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are added and mixed, gradually heated, and reacted at 110 to 115 ° C. for 2 hours to obtain compound 2 (m / m
n = 80/20). The reaction of the acid anhydride was confirmed by IR spectrum in the same manner as in Synthesis Example 1. The inherent viscosity of the obtained compound was 0.2 dl / g (η _inh = 0.2).

Synthesis Example 3 Using 303 g of the bisphenol fluorene type epoxy acrylate resin produced in Synthesis Example 1, 2 kg of cellosolve acetate was added to form a solution, and then 3.8 g of 1,2,3,6-tetrahydrophthalic anhydride, benzophenone 153.8 g of tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added and mixed, gradually heated, and reacted at 110 to 115 ° C. for 2 hours to obtain compound 3 (m / n
= 0.5 / 99.5). The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.3 dl / g (η _inh =
0.3).

Synthesis Example 4 Using 303 g of the bisphenol fluorene type epoxy acrylate resin produced in Synthesis Example 1, 2 kg of cellosolve acetate was added to form a solution, and then 144.4 g of 1,2,3,6-tetrahydrophthalic anhydride and benzophenone 16.1 g of tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are added and mixed, gradually heated, and reacted at 110 to 115 ° C. for 2 hours to obtain compound 4 (m / m
n = 95/5). The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.2 dl / g (η _inh = 0.2).

Synthesis Example 5 An acid anhydride was prepared in the same manner as in Synthesis Example 1 except that 153 g (epoxy equivalent: 153) of a biphenyl type epoxy resin was used instead of the bisphenol fluorene type epoxy resin in Synthesis Example 1. The reacted compound 5 (m
/ N = 50/50). The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.2 dl / g (η _inh = 0.2).

Synthesis Example 6 Instead of the bisphenol fluorene type epoxy resin in Synthesis Example 1, 163 g of a benzophenone type epoxy resin
Compound 6 reacted with an acid anhydride by operating in the same manner as in Synthesis Example 1 except that (epoxy equivalent 163) was used.
(M / n = 50/50). Reaction of acid anhydride is IR
Confirmed by spectrum. The inherent viscosity of the obtained compound was 0.3 dl / g (η _inh = 0.
3).

Synthesis Example 7 An acid anhydride was prepared in the same manner as in Synthesis Example 1 except that 181 g of a sulfone type epoxy resin (epoxy equivalent weight: 181) was used in place of the bisphenol fluorene type epoxy resin in Synthesis Example 1. The reacted compound 7 (m /
n = 50/50). The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.3 dl / g (η _inh = 0.3).

Synthesis Example 8 An acid anhydride was obtained in the same manner as in Synthesis Example 1 except that 221 g of hexafluoropropane type epoxy resin (epoxy equivalent 221) was used instead of the bisphenolfluorene type epoxy resin in Synthesis Example 1. Compound 8 (m / n = 50/50) reacted with the compound was obtained. The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.4 dl / g (η _inh =
0.4).

Synthesis Example 9 163 g of a dimethylsilane type epoxy resin was used in place of the bisphenol fluorene type epoxy resin in Synthesis Example 1.
Compound 9 reacted with an acid anhydride by operating in the same manner as in Synthesis Example 1 except that (epoxy equivalent 163) was used.
(M / n = 50/50). Reaction of acid anhydride is IR
Confirmed by spectrum. The inherent viscosity of the obtained compound was 0.2 dl / g (η _inh = 0.
2).

Synthesis Example 10 Biphenylmethane type epoxy resin 156 was used instead of bisphenol fluorene type epoxy resin in Synthesis Example 1.
Compound 10 (m / n = 50/50) reacted with an acid anhydride was obtained in the same manner as in Synthesis Example 1 except that g (epoxy equivalent: 156) was used. The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.4 dl / g (η _inh = 0.
4).

Synthesis Example 11 Biphenyl propane type epoxy resin 17 was used in place of bisphenol fluorene type epoxy resin in Synthesis Example 1.
Synthesis Example 1 except that 0 g (epoxy equivalent 170) was used.
Compound 11 (m / n = 50/50) reacted with the acid anhydride was obtained in the same manner as described above. The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.4 dl / g (η _inh =
0.4).

Synthesis Example 12 An acid anhydride was obtained in the same manner as in Synthesis Example 1 except that 157 g (epoxy equivalent weight: 157) of biphenyl ether type epoxy resin was used instead of the bisphenol fluorene type epoxy acrylate resin in Synthesis Example 1. Compound 12 (m / n = 50/50) reacted with the compound was obtained. The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound was 0.3 dl / g (η _inh = 0.3).

Synthesis Example 13 Using 303 g of the bisphenol fluorene type epoxy acrylate resin produced in Synthesis Example 1, 2 kg of cellosolve acetate was added to form a solution, and 76.0 g of 1,2,3,6-tetrahydrophthalic anhydride and 76.0 g of odor were added. 1 g of tetraethylammonium bromide and gradually heated to 95-10
The mixture was allowed to react at 0 ° C. for 4 hours to give compound 13 (m / n = 100 /
0) was obtained. The reaction of the acid anhydride was confirmed by an IR spectrum. The inherent viscosity of the obtained compound is 0.15.
dl / g (η _inh = 0.15).

Synthesis Example 14 An acid anhydride was prepared in the same manner as in Synthesis Example 13 except that 153 g (epoxy equivalent: 153) of a biphenyl type epoxy resin was used instead of the bisphenol fluorene type epoxy resin in Synthesis Example 1. Compound 14 reacted
(M / n = 100/0) was obtained. Reaction of acid anhydride is IR
Confirmed by spectrum. The inherent viscosity of the obtained compound was 0.16 dl / g (η _inh = 0.1
6).

Next, Synthesis Examples 15 to 19 of the spiroorthoester compound as the component C will be described. Synthesis Example 15 A four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 50 g of methylene chloride and 17.2 g (0.2 mol) of γ-butyrolactone, and the obtained solution was cooled to 10 ° C. , Boron trifluoride-diethyl ether complex 0.80mol (0.0062mo
l) was added. Next, a mixture of 26.0 g (0.1 equivalent) of bisphenol fluorene type epoxy resin (epoxy equivalent 260) and 200 g of methylene chloride was added dropwise with stirring over 5 hours while maintaining the reaction solution temperature at 5 to 10 ° C. Then, the reaction was performed. After completion of the dropwise addition, the mixture was further stirred for 3 hours while keeping the temperature constant. Then, 0.72 g (0.0072 mol) of triethylamine (reaction terminator) was added, and then the reaction solution was removed to remove excess γ-butyrolactone. Was washed twice with 500 ml of a 6% aqueous sodium hydroxide solution twice and further twice with 500 ml of distilled water. The organic layer was separated, dehydrated with magnesium sulfate, and then desolvated to obtain a γ-butyrolactone cardo type adduct (compound 15). The yield of the product obtained is 30.4 g.
(88% yield).

Synthesis Example 16 Compound 16 was obtained in the same manner as in Synthesis Example 15 except that ε-caprolactone was used instead of γ-butyrolactone. The yield was 79%.

Synthesis Example 17 Compound 17 was prepared in the same manner as in Synthesis Example 15 except that bisphenol A glycidyl ether type epoxy resin (Epicoat 828 manufactured by Yuka Shell, epoxy equivalent: 190) was used instead of the bisphenol fluorene type epoxy acrylate resin.
I got

Synthesis Example 18 A compound 18 was obtained in the same manner as in Synthesis Example 15 except that glyceryl ether type epoxy resin of cresol novolak was used instead of bisphenol fluorene type epoxy acrylate resin and ε-caprolactone was used instead of γ-butyrolactone.

Synthesis Example 19 An alicyclic epoxy resin (2021 manufactured by Daicel Chemical Industries, Ltd.) was used in place of the bisphenol fluorene type epoxy acrylate resin.
P) and ε- instead of γ-butyrolactone
Compound 19 was obtained in the same manner as in Synthesis Example 15 using caprolactone.

Examples 1 to 22 and Comparative Examples 1 and 2 The components (A) and (B) obtained in Synthesis Examples 1 to 14 and the component (C) obtained in Synthesis Examples 15 to 19 And a polymerizable acrylic monomer or oligomer and an organic solvent, which are further blended as required, in the following blending ratio (parts by weight) to prepare a solution.
Next, the obtained solution was degreased and washed to a thickness of 1.2 mm.
Was applied to a thickness of about 2 μm on a glass plate and dried, and then heated and dried at 200 ° C. for 60 minutes using a hot air drier. The obtained coating film surface was very smooth.

The obtained samples were evaluated for drying property of the coating film, hardness of the coating film, adhesion to the substrate, reduction in film thickness upon curing, heat resistance, and chemical resistance. Table 1 shows the results. Furthermore,
The adhesion to Nesa glass (glass on which ITO was deposited) was similarly evaluated. Table 1 shows the results. This Table 1
As can be seen from the results shown in Examples 1 to 22, all of Examples 1 to 22 showed good results.

Further, the thermosetting resin composition of the present invention can be used to form a cured product having excellent heat resistance, transparency, adhesion, hardness, solvent resistance, alkali resistance, smoothness, etc. on ITO such as Nesa glass. It can be provided, and this shows that it is useful as a spacer material for touch panels. On the other hand, in Comparative Example 1, an epoxy compound was blended in place of the spiroorthoester compound, but it was found that the film thickness decreased more than in the above Examples. Comparative Example 2 containing no C component
It was found that there was a problem in the alkali resistance after heat curing.

Example 1 (m / n = 50/50) Ingredients Ratio (parts by weight) Compound 1 20 Compound 15 4 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 2 (m / n = 50/50) Ingredient ratio (parts by weight) Compound 1 20 Compound 16 4 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 3 (m / n = 50/50) Ingredient Ratio (parts by weight) Compound 1 20 Compound 174 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 4 (m / n = 50/50) Ingredient ratio (parts by weight) Compound 1 20 Compound 18 4 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 5 (m / n = 50/50) Ingredient ratio (parts by weight) Compound 1 20 Compound 194 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 6 (m / n = 80/20) Ingredient Ratio (parts by weight) Compound 2 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 7 (m / n = 50/50) Ingredient ratio (parts by weight) Compound 5 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 8 (m / n = 50/50) Ingredient ratio (parts by weight) Compound 6 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 9 (m / n = 50/50) Ingredient Ratio (parts by weight) Compound 7 20 Compound 15 4 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 10 (m / n = 50/50) Ingredient Ratio (parts by weight) Compound 8 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 11 (m / n = 50/50) Ingredient ratio (parts by weight) Compound 9 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 12 (m / n = 50/50) Component Ratio (parts by weight) Compound 10 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 13 (m / n = 50/50) Component Ratio (parts by weight) Compound 11 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 14 (m / n = 50/50) Ingredients Ratio (parts by weight) Compound 12 20 Compound 154 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 15 (m / n = 50/50) Ingredient ratio (parts by weight) Compound 5 20 Compound 174 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 16 (m / n = 50/50) Component Ratio (parts by weight) Compound 5 20 Compound 18 4 Benzoyl peroxide 0.7 Cellosolve acetate 75.3 Total 100

Example 17 (m / n = 50/50) Component Ratio (parts by weight) Compound 1 20 Dipentaerythritol 8.6 Compound 15 4.4 Benzoyl peroxide 1.4 Cellosolve acetate 65.6 Total 100

Example 18 (m / n = 50/50) Component ratio (parts by weight) Compound 5 16 Compound 15 12 Benzoyl peroxide 0.6 2MA-OK (manufactured by Shikoku Chemicals) 0.1 Cellosolve acetate 71.3 Total 100

Example 19 (m / n = 0.5 / 99.5) Ingredient Ratio (parts by weight) Compound 3 20 Compound 16 8 Benzoyl peroxide 0.7 Cellosolve acetate 70.9 Total 100

Example 20 (m / n = 100/0) Component ratio (parts by weight) Compound 4 20 Compound 168 Benzoyl peroxide 1.0 2MA-OK (manufactured by Shikoku Chemicals) 0.1 Cellosolve acetate 70.9 Total 100

Example 21 (m / n = 100/0) Component Ratio (parts by weight) Compound 13 20 Compound 158 Benzoyl peroxide 0.7 Cellosolve acetate 71.3 Total 100

Example 22 (m / n = 100/0) Component Ratio (parts by weight) Compound 14 20 Compound 168 Benzoyl peroxide 0.6 2MA-OK (manufactured by Shikoku Chemicals) 0.1 Cellosolve Acetate 71.3 Total 100

Comparative Example 1 Components Ratio (parts by weight) Compound 1 20 Tetramethylbiphenol-type epoxy 3 Benzoyl peroxide 0.6 2MA-OK (manufactured by Shikoku Chemicals) 0.1 Cellosolve acetate 76.3 Total 100

Comparative Example 2 Components Ratio (parts by weight) Compound 1 20 Benzoyl peroxide 0.7 Cellosolve acetate 79.3 Total 100

The data of the various physical properties were measured under the following conditions. (1) Drying property of coating film The drying property of the coating film was evaluated according to JIS-5400.
The ranking of the evaluation is as follows. ：: no tack was observed at all Δ: slight tack was observed ×: marked tack was observed

(2) Coating Film Hardness After the coating film was dried, it was heated at 200 ° C. for 30 minutes, and the hardness of the coating film was measured by applying a load of 1 kg using a pencil hardness tester in accordance with the test method of JIS-K5400. Indicated with the highest hardness that does not scratch the coating film. The pencil used is "Mitsubishi High Uni".

(3) Adhesion to substrate After coating film was dried, it was heated at 200 ° C for 30 minutes.
A cross cut was made so as to form at least 100 base eyes, and then a peeling test was performed using cellophane tape, and the state of peeling of the base eyes was visually evaluated. The ranking of the evaluation is as follows. ：: No peeling was observed at all ×: Peeling was observed at all

(4) Film thickness reduction rate The film thickness reduction rate was defined by the following equation based on the film thickness d after the coating film was dried and the film thickness D after heating at 200 ° C. for 30 minutes. Film thickness reduction rate (%) = 100 {1- (D / d)}

(5) Heat resistance After the coating film was dried, it was heated at 200 ° C. for 30 minutes.
It was placed in an oven at 50 ° C. for 3 hours to evaluate the state of the coating film.
The ranking of the evaluation is as follows. ：: No abnormality in appearance of coating film ×: Appearance of coating film, peeling and coloring.

(6) Chemical resistance After the coating film was dried, the coating film heated at 200 ° C. for 30 minutes was subjected to
It was immersed in the following chemicals under the following conditions, and the appearance and adhesion after immersion were evaluated. Acid resistance: 24 hours in 5% HCl Alkali resistance: 24 hours immersion in 5% NaOH 50 ° C.-10 min. In 4% KOH 80 in 1% NaOH
-5 min. Solvent resistance: 40 ° C. for 10 minutes in NMP. 80 ° C. for 5 minutes in NMP. (NMP: N-methyl-pyrrolidone)

(7) Transparency The same glass plate as the one coated with the coating film was used as a reference, and the transparency was 400 to 8 before and after the heat resistance test and the chemical resistance test.
The absorption spectrum at a wavelength of 00 nm was measured. ：: 95% or more in all regions ×: less than 95%

Example 23 A varnish having the composition shown in Example 17 and a pigment previously dispersed in an organic solvent were mixed and subjected to a dispersion treatment to prepare a color filter ink. The pigments used were CF Color Red EX-274, CF Color Green EX-276,
CF Color Blue EX-275, CF Color Black E
X-277 (manufactured by Okuni Pigment). At this time, the dispersion was performed so that the pigment particle diameter was 0.3 μm for each color. Table 2 shows the weight ratio of the composition of each color.

Next, a glass substrate washed with a neutral detergent, water, and isopropyl alcohol / fluorocarbon was used as a transparent substrate, and each ink was applied onto the substrate by a spin coater.
After drying at 80 ° C., a heat drying treatment was performed at 200 ° C. for 30 minutes using a hot air drier. At this time, the film thickness of each of R, G, B and black matrix was 2 ± 0.1 μm.
Met.

Comparative Example 3 A photosensitive dye base comprising 6 parts by weight of polyvinyl alcohol (EG-30, manufactured by Nippon Gosei), 0.5 parts by weight of ammonium bichromate, 0.3 parts by weight of chrome alum and 93.2 parts by weight of water 24P, green 1P, blue 5
Using C, staining was performed under the conditions shown in Table 3. Pre-bake is 60
C., 10 minutes, and the application sequence was RGB. At this time, the thickness of each pixel is 1.5 ± 0.2 μm for each of R, G, and B.
m.

The color filters of Example 23 and Comparative Example 3 were subjected to a light resistance test using a xenon fade meter, and ΔE (color difference) due to _Lab after 1,000 hours was examined. Table 4 shows the results. Example 23 compared to Comparative Example 3
It was clear that ΔE was smaller and the reliability of light resistance was superior.

Comparative Example 4 A color filter was produced in the same manner as in Comparative Example 3 using a color mosaic (R, G, B manufactured by Fuji Hunt). The pre-baking was performed at 90 ° C. for 5 minutes, and the developing was performed using a designated developing solution. The thickness of each pixel was 2 ± 0.1 μm for each of R, G, and B.

The color filters of Example 23 and Comparative Example 4 were subjected to a heat resistance test (280 ° C., 1 hour) to examine the reduction in the peak value of the spectral transmittance and the reduction rate of the film thickness. Table 5 shows the results.

Example 24 Using the resin compositions prepared in Examples 1 to 22, suitability for a color filter substrate was examined. The test method is as follows. A car filter substrate was prepared in the same manner as in Comparative Example 4, the resin composition was applied on the substrate by spin coating, dried at 80 ° C. for 10 minutes, and then heated at 200 ° C. using a hot air drier. A heat drying treatment was performed for 30 minutes. The obtained coating film surface was very smooth.

Indium tin oxide (ITO) was vapor-deposited on the thus-prepared color filter with a protective film by an ordinary method, and then patterned by photolithography. When the color filter having the ITO pattern was observed in detail with an optical microscope, no wrinkles or cracks were observed in the color filter or the protective film, and the adhesion and adhesion between the color filter and the protective film were good. Was.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

[0127]

[Table 4]

[0128]

[Table 5]

From the above results, the thermosetting resin composition of the present invention provides cured products, coatings and color filters which are excellent in heat resistance, transparency, adhesion, hardness, solvent resistance, alkali resistance, smoothness and the like. You can see that

[0130]

When the thermosetting resin composition of the present invention is used, the coating film becomes tack-free after drying the solvent, and
Since the curing shrinkage is relatively small, the coating has excellent dimensional stability during curing, and also has excellent adhesion, transparency, heat resistance, acid resistance, alkali resistance, solvent resistance, flatness, surface hardness, etc. Gives a film, cured product. Therefore, it is suitable for forming a transparent electrode such as ITO thereon as a surface protective layer. Moreover, since it is extremely smooth and excellent in transparency, a clear image is obtained when used as a material for a color filter. be able to.

When the present thermosetting resin composition is used as a spacer material for a touch panel, a decrease in the film thickness and pattern width during heat treatment is small, and the spacer has excellent surface hardness and transparency. In addition, there are advantages in that the basic key matrix can be made smaller, pen input can be performed, the number and arrangement of keys on the touch panel can be obtained flexibly, and various input information can be handled. Further, since the formed film is excellent in adhesion to the substrate and chemical resistance, the present invention can be applied to a wide range of fields such as interlayer insulating materials related to printed wiring boards, optical members, adhesives, paints, and inks for screen printing. Even when a resin composition or a cured product thereof is used, high reliability can be obtained.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/038 503 G03F 7/038 503 G06F 3/033 360 G06F 3/033 360 (72) Inventor Masaya Furukawa 1618 Ida, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Address, Nippon Steel Corporation Advanced Technology Research Institute (72) Inventor Takeo Teramoto 1618 Ida, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Nippon Steel Corporation Advanced Technology Research Laboratory (56) References JP-A-2-116851 (JP, a) JP flat 5-70528 (JP, a) JP flat 4-355450 (JP, a) JP Akira 56-167717 (JP, a) (58 ) investigated the field (Int.Cl. ⁷ , DB name) G03F 7/004

Claims (11)

(57) [Claims] 1. A method according to claim 1, wherein (A) 100 parts by weight of a thermopolymerizable compound having an ethylenically unsaturated double bond and a carboxyl group,
(B) a polymerization initiator which generates a radical by heat is 0.1
And (C) the following general formula (1): (Where p is an integer of 3 to 5), and 5 to 100 parts by weight of a spiroorthoester compound having two or more spiroorthoester groups in one molecule. Low curing shrinkable thermosetting resin composition. 2. The thermopolymerizable compound according to claim 1, wherein the thermopolymerizable compound is a product obtained by further reacting a reaction product of an epoxy compound and (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof. Curable resin composition. 3. The thermopolymerizable compound is represented by the following general formulas (2) and (3): [However, in the general formulas (2) and (3), R ₁ and R
₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, R ₃ is a hydrogen atom or a methyl group, and X is —CO—, —SO ₂ —, —C (CF ₃ )
_{2 -, - Si (CH 3} ) 2 -, - CH 2 -, - C (CH
₃ ) _2- , -O-, embedded image Y represents an acid anhydride residue, Z represents
Represents a residue of an acid dianhydride, and the structural unit m: n is a compound having a unit structure represented by a molar ratio of 0/100 to 100/0). .5g
Is dissolved in 100 ml of N-methylpyrrolidone.
0.1 d inherent viscosity (η _inh ) measured at 0 ° C
The thermosetting resin composition according to claim 1, which is 1 / g or more. 4. A spiroorthoester compound represented by the following general formula (4): [Where A is the following formula: (Wherein, R ₁ and R ₂ represent the same as those in formulas (2) and (3)), q is 0 or an integer of 1 to 10, and p is the same as in formula (1). The thermosetting resin composition according to any one of claims 1 to 3, which is a fluorene group-containing orthospiroester compound represented by the following formula: (A) an ethylenically unsaturated double bond and carbohydrate
Per 100 parts by weight of the thermopolymerizable compound having a xyl group, (B) a polymerization initiator which generates a radical by heat 0.1 to 0.1
10 parts by weight, and (C) a spiroorthoester group represented by the general formula (1)
Compound having two or more in a molecule thereof
From 5 to 100 parts by weight, giving a transparent cured resin
A low-hardening shrinkable thermosetting material according to any one of claims 1 to 4.
Curable resin composition. 6. A cured product obtained by curing the thermosetting resin composition according to any one of claims 1 to 5. 7. A material for a color filter, wherein the thermosetting resin composition according to claim 1 is used. 8. (A) per 100 parts by weight of a thermopolymerizable compound having an ethylenically unsaturated double bond and a carboxyl group,
(B) a polymerization initiator which generates a radical by heat is 0.1
(C) 5 to 100 parts by weight of a spiroorthoester compound having two or more spiroorthoester groups represented by the general formula (1) in one molecule; Total of compound and spiroorthoester compound 1
A color filter ink comprising 10 to 200 parts by weight of a pigment dispersed in 00 parts by weight. 9. A color filter using the cured product according to claim 7 and / or 8. 10. A spacer material for a touch panel, wherein the thermosetting resin composition according to claim 1 is used. 11. A touch panel obtained by curing the spacer material according to claim 10.