KR20180135886A - A thermosetting resin composition, a cured film, a substrate with a cured film, and an electronic part - Google Patents

Abstract

A thermosetting resin composition capable of forming a cured film having high hardness, high transparency, and adhesion to glass or ITO, and a use thereof. The thermosetting resin composition is preferably a thermosetting resin composition comprising a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton, an epoxy curing agent (C), a solvent (D), silica fine particles having an average particle diameter of 50 nm or less E) and the optical adjusting epoxy resin (F), it is possible to form a cured film having good balance, high hardness, high transparency, and adhesion to glass or ITO.

Description

A thermosetting resin composition, a cured film, a substrate with a cured film, and an electronic part

The present invention relates to a thermosetting resin composition, a cured film, a substrate with a cured film, and electronic parts. More particularly, the present invention relates to a thermosetting resin composition containing a specific compound, a cured film formed from the composition, a substrate with a cured film having the cured film, and electronic parts having the cured film or a substrate with a cured film.

2. Description of the Related Art In recent years, a touch panel type input device in which a liquid crystal display device or an organic electroluminescence (EL) device and a position detection device are combined as an input device has been popular. The touch panel type input device is an input device for detecting the contact position when a finger or a pen tip is brought into contact with the display screen. Various types of detection methods exist in the touch panel type input device, such as a resistance film type and a capacitance type.

For example, in the electrostatic capacitance method, a device having a structure in which X and Y electrodes are arranged in a matrix form on a glass substrate is used to detect a change in capacitance caused by the contact of a hand tip or the like as a current variation Method.

In order to recognize the X and Y positions when forming the electrode, a jumper is formed of ITO (indium tin oxide) or the like on the overlapping portion of the X and Y electrodes, and a transparent An insulating film is provided. The transparent insulating film is required to have high hardness, high transparency, and adhesion to glass or ITO.

In addition, an insulating overcoat may be provided on the capacitive touch panel in order to flatten the X and Y electrodes, for example. In addition to flatness, the overcoat is required to prevent degassing, to achieve high hardness, high transparency, and adhesion to glass or ITO.

Various compositions have been studied for a highly transparent insulating material which can be used for such a transparent insulating film or an overcoat. For example, Patent Documents 1 and 2 disclose a resin composition comprising a polyester amide acid having a specific structure, an epoxy resin, an epoxy curing agent, and the like. However, none of these patent documents have examined the adhesion or hardness of the cured film obtained from the composition to the ITO substrate.

Patent Document 3 discloses a curable composition comprising an epoxy compound having a fluorene skeleton and a curing agent. However, in Patent Document 3, no study has been made on the transparency of the cured film obtained from the composition, the adhesion to glass and ITO, and the hardness thereof.

Japanese Patent Application Laid-Open No. 2005-105264 Japanese Patent Application Laid-Open No. 2008-156546 Japanese Patent Application Laid-Open Publication No. 2012-102228

In manufacturing a touch panel type input device, a resin composition which can be used anywhere of the above-mentioned transparent insulating film and overcoat is considered to be preferable from the viewpoints of simplification of lines and improvement of yield, but such a resin composition is not yet realized have.

The object of the present invention is to provide a thermosetting resin composition capable of forming a cured film having high hardness, high transparency, and adhesion to glass or ITO, and a use thereof.

The present inventors conducted a careful examination to solve the above problems.

For example, when a resin composition specifically disclosed in the above patent literature was examined, the cured film obtained from the composition described above was poor in adhesion and hardness to glass and ITO, especially ITO.

DISCLOSURE OF THE INVENTION The inventors of the present invention have made various studies based on the above findings and have found that the above problems can be solved by a thermosetting resin composition having the following constitution and have completed the present invention. That is, the present invention relates to, for example, the following [1] to [23].

(B), an epoxy curing agent (C), a solvent (D), silica fine particles (E) having an average particle diameter of 50 nm or less, a polyester amide acid (A), a fluorene skeleton or a dicyclopentadiene skeleton, And an optical tunable epoxy resin (F).

[2] The thermosetting resin composition according to [1], wherein the optical control epoxy resin (F) is an alicyclic epoxy compound.

[3] The thermosetting resin composition according to [1] or [2], wherein the cured film having a thickness of 2.2 micrometers obtained from the thermosetting resin composition has a transmittance of 97% or more at a wavelength of 400 nm.

[4] The thermosetting resin composition according to any one of [1] to [3], wherein the epoxy equivalent of the epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton is 150 to 550 g / eq.

[5] The epoxy resin composition according to any one of [1] to [4], which comprises 15 to 400 parts by weight of an epoxy compound (B) having fluorene skeleton or dicyclopentadiene skeleton relative to 100 parts by weight of the polyester amide acid (A) Wherein the thermosetting resin composition is a thermosetting resin composition.

[6] The epoxy resin composition according to [1], wherein the epoxy curing agent (C) is at least one compound selected from the group consisting of an acid anhydride curing agent, a phenol resin curing agent, an amine duct, a polycarboxylic acid curing agent, a polyamine curing agent, Wherein the thermosetting resin composition is a thermosetting resin composition according to any one of [1] to [5].

[7] The thermosetting resin composition according to any one of [1] to [6], wherein the content of the silica fine particles (E) is 140 parts by weight or less based on 100 parts by weight of the polyester amide acid (A).

[8] The epoxy resin composition as described in [1], wherein the epoxy curing agent (C) is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total amount of epoxy compounds containing two or more oxiran rings or oxetane rings in the molecule in the thermosetting resin composition. Wherein the thermosetting resin composition is a thermosetting resin composition according to any one of [1] to [7].

[9] The thermosetting resin composition according to any one of [1] to [8], wherein the polyester amide acid (A) has a weight average molecular weight of 2,000 to 30,000.

[10] The thermosetting resin composition according to any one of [1] to [9], wherein the polyester amide acid (A) is a compound having a structural unit represented by the formula (3) and the formula (4).

(Wherein R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is a divalent organic group having 1 to 20 carbon atoms.)

[11] The compound of [1] to [10], wherein the polyester amide acid (A) is a compound obtained by reacting tetracarboxylic acid dianhydride (a1), diamine (a2) and polyhydric hydroxy compound (a3) Wherein the thermosetting resin composition is a thermosetting resin composition.

The polyester amide acid (A) is a compound obtained by reacting a tetracarboxylic dianhydride (a1), a diamine (a2), a polyhydric hydroxy compound (a3) and a monohydric alcohol (a4) The thermosetting resin composition according to any one of [1] to [11].

(13) A process for producing a polyester amide compound according to any one of (1) to (9), wherein the polyester amide acid (A) The thermosetting resin composition according to any one of [1] to [12], wherein the thermosetting resin composition is a compound which is obtained by reacting the compound of the formula

0.2? Z / Y? 8.0 ... (i)

0.2? (Y + Z) /X? 1.5 ... (ii)

[14] The method according to any one of [1] to [3], wherein the tetracarboxylic dianhydride (a1) is at least one compound selected from the group consisting of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic dianhydride, , At least one compound selected from the group consisting of 2- (bis (3,4-dicarboxyphenyl)) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate). Wherein the thermosetting resin composition is a thermosetting resin composition.

[15] The method according to [11], wherein the diamine (a2) is at least one compound selected from the group consisting of 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) [14] The thermosetting resin composition according to any one of [12] to [14].

The polyhydric hydroxy compound (a3) is at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- [14] The thermosetting resin composition according to any one of [11] to [15], wherein the thermosetting resin composition is at least one compound selected from the group consisting of hexanediol, octanediol,

[17] The method according to any one of [1] to [4], wherein the monohydric alcohol (a4) is selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl- The thermosetting resin composition according to any one of [11] to [16], which is at least one compound selected.

[18] The organic electroluminescent device according to the above [18], wherein the tetracarboxylic dianhydride (a1) is 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, the diamine (a2) is 3,3'-diaminodiphenylsulfone, The thermosetting resin composition according to any one of [11] to [17], wherein the polyhydric hydroxy compound (a3) is 1,4-butanediol and the epoxy curing agent (C) is anhydrous trimellitic acid.

[19] The thermosetting resin composition according to any one of [1] to [18], which is for a touch panel.

[20] A cured film obtained from the thermosetting resin composition according to any one of [1] to [19].

[21] A substrate with a cured film having the cured film according to [20].

[22] An electronic component having the cured film according to [20] or the substrate with a cured film according to [21].

[23] The electronic component according to [22], which is a touch panel.

According to the present invention, it is possible to form a cured film having high hardness, high transparency, adhesion to glass or ITO, resistance to an ITO etchant solution containing oxalic acid, and particularly good balance. Accordingly, the thermosetting resin composition of the present invention is highly practicable, and for example, a transparent insulating film for a touch panel and an overcoat can be produced with good productivity and can be suitably used for such use.

Hereinafter, the thermosetting resin composition of the present invention (hereinafter also referred to as " composition of the present invention "), the method of preparing the composition, the method of forming a cured film, the substrate with a cured film, and electronic components will be described in detail.

1. Thermosetting resin composition

The composition of the present invention is a composition comprising a polyester amide acid (A), an epoxy compound (B) having a fluorene or dicyclopentadiene skeleton and an epoxy curing agent (C), a solvent (D), silica fine particles having an average particle diameter of 50 nm or less E) and an optical adjusting epoxy resin (F). In addition to the above components, the composition of the present invention may contain an additive, or may be colored or colorless.

According to the composition of the present invention, it is possible to obtain an excellent cured film having good balance of hardness, high transparency, adhesion to glass or ITO, and resistance to ITO etching solution containing oxalic acid. Thus, it is possible to manufacture a transparent insulating film for a touch panel or an overcoat with good productivity, and can be suitably used for such a use.

The composition of the present invention is a composition comprising a polyester amide acid (A), an epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton, an epoxy curing agent (C), a solvent (D), fine silica particles having an average particle diameter of 50 nm or less (E) and the optical adjusting epoxy resin (F), a cured film excellent in the above effect can be obtained. Particularly, a cured film having a pencil hardness of 3H or more and a transmittance of 97% or more at a wavelength of 400 nm and a transmittance of a cured film having a film thickness of 2.2 micrometers can be obtained, and a cured film excellent in adhesiveness to glass and ITO can be obtained.

In a conventional composition comprising a polyester amide acid, a composition comprising an epoxy compound having a fluorene skeleton and an epoxy curing agent, these substrates have a pencil hardness of 3H or more, a transmittance of 97% or more, A cured film excellent in adhesion could not be obtained.

Therefore, the composition of the present invention is a composition having an effect that can not be expected with a conventional composition, and is a composition comprising an epoxy compound having a polyester amide acid, a fluorene skeleton or dicyclopentadiene, an epoxy curing agent, Is a composition having a synergistic effect by combining silica fine particles of 50 nm or less and an optical control epoxy resin.

1.1. The polyester amide acid (A)

The polyester amide acid (A) to be used in the present invention is not particularly limited, but is preferably a compound having an ester bond, an amide bond and a carboxyl group. Specifically, the polyester amide acid (A) And more preferably a compound having a constituent unit.

By using such a polyester amide acid (A) in combination with a specific epoxy compound and an epoxy curing agent, it is possible to obtain an epoxy resin composition which has excellent hardness, high transparency, resistance to an ITO etchant containing oxalic acid and excellent adhesion to glass or ITO A composition capable of forming a cured film is obtained.

The polyester amide acid (A) may be used alone or as a mixture of two or more thereof.

(R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is a divalent organic group having 1 to 20 carbon atoms.)

From the standpoint of obtaining a compound having good compatibility with other components in the composition and obtaining a highly transparent cured film, it is preferable that R ¹ is independently a tetravalent organic group having 2 to 25 carbon atoms More preferably a tetravalent organic group having 2 to 20 carbon atoms, more preferably a group represented by formula (5).

In the (expression (5), R ⁴ _{is, -O-, -CO-, -SO 2 -} , -C (CF 3) 2 -, -R 5 - or -COO-R ⁵ -OCO- (R ⁵ Is independently an alkyl group having 1 to 4 carbon atoms.)

It is preferable that R ² is a divalent organic group having ² to 35 carbon atoms because a compound having good compatibility with other components in the composition can be obtained and high transparency and a cured film having good adhesion to glass or ITO can be obtained More preferably a divalent organic group having 2 to 30 carbon atoms, and more preferably a group represented by formula (6).

(6), R ⁶ represents -O-, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -R ⁷ - or -O-ph -R ⁸ -ph-O - (wherein ph is a benzene ring and R ⁸ is -O-, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ - or -R ⁷ -) and R ⁷ is independently , And an alkyl group having 1 to 4 carbon atoms.)

R ³ is preferably a divalent organic group having 2 to 15 carbon atoms, and is preferably a group represented by the formula (7), -R ¹⁰ -NR ¹¹ -R ¹² - ( R ¹⁰ and R 12 are independently alkylene having 1 to 8 carbon atoms and R ¹¹ is hydrogen or alkyl having 1 to 8 carbon atoms in which at least one hydrogen may be substituted with hydroxyl) Alkylene or alkylene having 2 to 15 carbon atoms may be substituted with hydroxyl, more preferably a group which may have -O-, and is preferably a divalent alkylene group having 2 to 6 carbon atoms More preferable.

(In the formula (7), R ⁹ is -O-, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -R ⁷ - or -ph-R ⁸ -ph- is a benzene ring, R ⁸ _{is, -O-, -CO-, -SO 2 -} , -C (CF 3) 2 - or -R ⁷ -.. is), and, R ⁷ are, each independently, a carbon number of 1 to 4 < / RTI >

The polyester amide acid (A) is preferably a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2) and polyhydric hydroxy compound (a3) as essential components, and the tetra carboxylic acid dianhydride (a1) (A2), a polyhydric hydroxy compound (a3) and a monohydric alcohol (a4) as essential components.

That is, in the formulas (3) and (4), R ¹ is independently a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyhydric hydroxy compound residue.

In this reaction, a reaction solvent (a5) or the like may also be used.

These (a1) to (a5) may be used alone or in combination of two or more kinds.

When the polyester amide acid (A) has an acid anhydride group at the molecular end, it is preferably a compound obtained by reacting a monohydric alcohol (a4), if necessary. The polyester amide acid (A) obtained by using the monohydric alcohol (a4) tends to be a compound excellent in compatibility with the epoxy compound (B) and the epoxy curing agent (C) There is a tendency.

1.1.1. The tetracarboxylic dianhydride (a1)

The tetracarboxylic dianhydride (a1) is not particularly limited, but specific examples thereof include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride , 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenylsulfone tetra 2,3,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3'- Diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, and 2,3,4 ', 4'- Aromatic tetracarboxylic acid dianhydride such as glycol bis (anhydrotrimellitate) (trade name: TMEG-100, manufactured by Shin-Nippon Rika Co., Ltd.); Alicyclic tetracarboxylic acid dianhydrides such as cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride; And aliphatic tetracarboxylic dianhydrides such as ethane tetracarboxylic acid dianhydride and butane tetracarboxylic dianhydride.

Among these, from the viewpoint of obtaining a compound having good transparency and the like, it is preferable to use a compound having a structure such as 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic acid dianhydride (Trade name: TMEG-100, Shin-Nippon Rika (Shin-Nihon Rika) (available from Shin-Etsu Chemical Co., Ltd.) Ltd.) is preferable, and 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride are particularly preferable.

1.1.2. The diamine (a2)

The diamine (a2) is not particularly limited, but specific examples include 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, bis [4 (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, Phenyl] sulfone and 2,2-bis [(4-aminophenoxy) phenyl] sulfone, 4- (4-aminophenoxy) phenyl] hexafluoropropane.

Of these, 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are preferable from the viewpoint of obtaining a compound having good transparency, Minodiphenyl sulfone is particularly preferred.

1.1.3. The polyhydric hydroxy compound (a3)

The polyhydric hydroxy compound (a3) is not particularly limited as long as it is a compound having two or more hydroxy groups, and specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 1,000 or less, Glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, - pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6- 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2 , 8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonantiol, 1,2-decanediol, Decanediol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, tri Methylol propane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine and triethanolamine.

Of these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol are preferable, , 1,5-pentanediol and 1,6-hexanediol are particularly preferable in view of good solubility in the reaction solvent (a5).

1.1.4. Monohydric alcohol (a4)

The monohydric alcohol (a4) is not particularly limited as long as it is a compound having one hydroxy group, and specific examples thereof include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, Propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl Ether, phenol, borneol, mannitol, linalool, terpineol, dimethylbenzylcarbinol and 3-ethyl-3-hydroxymethyloxetane.

Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are preferable. Taking into account the compatibility of the resulting polyester amide acid (A) with the epoxy compound (B) and the epoxy curing agent (C) and the coating properties of the resulting composition to glass or ITO, the monohydric alcohol (a4) Is more preferable.

1.1.5. The reaction solvent (a5)

Specific examples of the reaction solvent (a5) include, but are not limited to, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl- Acetamide.

Of these, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, methyl 3-methoxypropionate and N-methyl-2-pyrrolidone are preferable in terms of solubility.

Specific examples of the reaction solvent (a5) include, but are not limited to, those solvents in which a solvent other than the above solvent is mixed in a ratio of 30% by weight or less based on the total amount of the solvent used in the reaction Mixed solvents may also be used.

&Quot; Synthesis of polyester amide acid (A) "

The method of synthesizing the polyester amide acid (A) is not particularly limited, but it is preferable that the tetra carboxylic acid dianhydride (a1), the diamine (a2), the polyhydric hydroxy compound (a3) and, if necessary, the monohydric alcohol (a4) , And it is more preferable to carry out the reaction in the reaction solvent (a5).

The order of addition of each component in this reaction is not particularly limited. That is, the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyhydric hydroxy compound (a3) can be simultaneously added to the reaction solvent (a5) and the diamine (a2) and the polyhydric hydroxy compound (a3) The reaction product may be reacted by adding tetracarboxylic dianhydride (a1) after dissolving it in the solvent (a5) or by reacting the tetracarboxylic dianhydride (a1) with the diamine (a2) in advance, The reaction may be carried out by adding the hydroxy compound (a3), either of which can be used.

The monohydric alcohol (a4) may be added at any point in the reaction.

In order to increase the weight average molecular weight of the obtained polyester amide acid (A) during the reaction, a compound having three or more acid anhydride groups may be added to carry out the synthesis reaction. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer.

The polyester amide thus synthesized contains the structural unit represented by the above-mentioned formula (3) and the formula (4), and the terminal thereof is an acid derived from the tetracarboxylic acid dianhydride, diamine or polyhydric hydroxy compound, An anhydride group, an amino group or a hydroxyl group, or a group derived from a component other than these compounds (for example, a monovalent alcohol residue).

When the amounts of tetracarboxylic dianhydride (a1), diamine (a2) and polyhydric hydroxy compound (a3) used in the above reaction are X mol, Y mol and Z mol, respectively, It is preferable that the relationship of the formula (i) and the formula (ii) is established. By using each component in such an amount, a polyester amide acid (A) having high solubility to the solvent (D) can be obtained, a composition having excellent coatability can be obtained, and a cured film having excellent flatness can be obtained .

0.2? Z / Y? 8.0 ... (i)

0.2? (Y + Z) /X? 1.5 ... (ii)

The relationship of the formula (i) is preferably 0.7? Z / Y? 7.0, more preferably 1.3? Z / Y? 7.0. The relationship of the formula (ii) is preferably 0.5? (Y + Z) / X? 0.9, more preferably 0.7? (Y + Z) /X? 0.8.

When the amount of the monohydric alcohol (a4) used in the reaction is Z'mols, the amount thereof is not particularly limited, but preferably 0.2? ? 0.5.

The reaction solvent (a5) is preferably used in an amount of 100 parts by weight or more based on the total 100 parts by weight of the tetracarboxylic dianhydride (a1), the diamine (a2) and the polyhydric hydroxy compound (a3) .

The reaction is preferably carried out at 40 to 200 DEG C for 0.2 to 20 hours.

&Quot; Property, amount of polyester amide acid (A) "

The weight average molecular weight (in terms of polystyrene) of the polyester amide acid (A) measured by gel permeation chromatography (GPC) can be measured by solubility in the solvent (D) From the viewpoint of obtaining a cured film in which the adhesion to the substrate and the chemical resistance of the substrate can be obtained, and more preferably from 2,000 to 30,000, more preferably from 3,000 to 28,000.

This weight average molecular weight can be measured specifically by the method described in the following examples.

The viscosity of the polyester amide acid (A) is preferably from 5 to 200 at 25 占 폚, from the viewpoint of easy handling of the resulting polyester amide acid (A) and controlling the weight average molecular weight to the above- mPa · s, more preferably 10 to 150 mPa · s, and furthermore preferably 15 to 100 mPa · s.

The content of the polyester amide acid (A) is preferably 100% by weight or more based on 100% by weight of the solid content of the composition of the present invention (the residue excluding the solvent) from the viewpoint of obtaining a cured film which is highly transparent and excellent in chemical resistance, 1 to 60% by weight, more preferably 5 to 55% by weight, and still more preferably 10 to 50% by weight.

1.2. An epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton,

The epoxy compound (B) used in the present invention is not particularly limited as long as it is an epoxy compound having a fluorene skeleton or a dicyclopentadiene skeleton. Since such an epoxy compound (B) has a high decomposition temperature and excellent heat stability, a cured film having these effects can be obtained in addition to the above effects such as high transparency. The epoxy compound (B) may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy compound (B) is preferably from 150 to 550 g / eq, more preferably from 150 to 490 g / eq, from the viewpoint of obtaining a cured film excellent in chemical resistance, Is 160 to 480 g / eq.

The epoxy equivalent of the epoxy compound (B) can be measured, for example, by the method described in JIS K7236.

The refractive index of the epoxy compound (B) is preferably from 1.40 to 1.75, more preferably from 1.45 to 1.73, and further preferably from 1.48 to 1.71 from the viewpoint of obtaining a cured film excellent in transparency.

The refractive index of the epoxy compound (B) can be measured, for example, by the method described in JIS K7105 or JIS K7142.

The epoxy compound (B) may be synthesized or may be a commercial product.

Examples of commercial products of the epoxy compound (B) include OGSOL PG-100 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.64, epoxy equivalent 259 g / eq), OGSOL CG- OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.62, epoxy equivalent 292 g / eq), OGSOL EG-250 (trade name, manufactured by Osaka Gas Chemical Co., (Refractive index 1.58, epoxy equivalent 417 g / eq), OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.56, epoxy equivalent 467 g / eq), OGSOL CG- (Refractive index 1.50, epoxy equivalent 540 g / eq), EP-4088S (trade name, manufactured by ADEKA, refractive index 1.50, epoxy equivalent 170 g / Epoxy equivalent of 165 g / eq).

When a compound having a refractive index of 1.60 or more and an epoxy equivalent of less than 280 g / eq such as OGSOL PG-100 is used as the epoxy compound (B), the epoxy compound (B) (B) having a refractive index of 1.70 or less and an epoxy equivalent of more than 280 g / eq are preferably used. In this case, the total epoxy compound (B) contained in the composition of the present invention preferably has a refractive index of 1.60 or more And the content of the compound having an epoxy equivalent of less than 280 g / eq is preferably 70% by weight or less, more preferably 65% by weight or less, and still more preferably 60% by weight or less.

When a compound having a refractive index of 1.68 or more and an epoxy equivalent of 400 g / eq or less, for example, OGSOL CG-500 is used as the epoxy compound (B), the cured film obtained from the composition of the present invention has particularly high hardness. On the other hand, when the epoxy compound (B) having a refractive index of less than 1.68 and an epoxy equivalent of 200 g / eq or more is used in combination, an excellent cured film having a good balance of hardness and transparency can be obtained. In this case, the content of the compound having a refractive index of 1.68 or more and an epoxy equivalent of 400 g / eq or less is preferably 90% by weight or less, more preferably 80% by weight or less, of the entire epoxy compound (B) , And more preferably 70 wt% or less.

When a compound having a refractive index of less than 1.60 and an epoxy equivalent of 300 g / eq or more, for example, OGSOL EG-280 is used as the epoxy compound (B), the cured film obtained from the composition of the present invention is excellent in adhesion and transparency . On the other hand, resistance to acids such as oxalic acid aqueous solution tends to be lowered. Therefore, by using the epoxy compound (B) having a refractive index of 1.60 or more and an epoxy equivalent of less than 400 in combination, it is possible to improve adhesion, transparency to glass or ITO, It is possible to obtain an excellent cured film having a good balance of resistance to chemicals. In this case, the compounding amount of the compound having a refractive index of less than 1.60 and an epoxy equivalent of 300 g / eq or more in the total epoxy compound (B) contained in the resin composition of the present invention is preferably 70% by weight or less, , And more preferably 50 wt% or less.

The content of the epoxy compound (B) is preferably 100% by weight or less, more preferably 100% by weight or less, more preferably 100% by weight or less, more preferably 100% by weight or less, Is preferably 3 to 60% by weight, more preferably 5 to 50% by weight, and still more preferably 7 to 50% by weight based on 100% by weight of the polyester amide acid (A) More preferably 20 to 300 parts by weight, still more preferably 20 to 250 parts by weight.

1.3. Epoxy curing agent (C)

The composition of the present invention is blended with an epoxy curing agent (C), whereby a cured film excellent in heat resistance and chemical resistance can be obtained.

Examples of the epoxy curing agent (C) include compounds different from the polyester amide acid (A), specifically, an acid anhydride type curing agent, a polyamine type curing agent, a polyphenol type curing agent and a catalyst type curing agent. And an acid anhydride-based curing agent in terms of heat resistance and the like.

The epoxy curing agent (C) may be used alone or as a mixture of two or more thereof.

Specific examples of the acid anhydride-based curing agent include aliphatic di (meth) acrylates such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid- Carboxylic anhydride; Aromatic polycarboxylic anhydride compounds such as phthalic anhydride and trimellitic anhydride; Styrene-maleic anhydride copolymer. Of these, trimellitic anhydride is particularly preferable because a compound having excellent solubility in solvent (D) can be obtained and a cured film excellent in heat resistance can be obtained.

The content of the epoxy curing agent (C) is preferably such that the solid content of the composition of the present invention (the composition of the present invention More preferably 2 to 17% by weight, and still more preferably 3 to 15% by weight, based on 100% by weight of the epoxy compound (B) Is preferably 5 to 30 parts by weight, more preferably 7 to 29 parts by weight, and still more preferably 7 to 28 parts by weight, based on 100 parts by weight of the whole epoxy resin.

The proportion of the epoxy compound (B) to be used and the epoxy curing agent (C) is preferably such that the amount of the epoxy curing agent (C) The amount of groups capable of reacting with an epoxy group such as an acid anhydride group or a carboxyl group in the resin is preferably 0.2 to 2 times, more preferably 0.5 to 1.5 times, more preferably because the chemical resistance of the obtained cured film is further improved . In this case, for example, when one equivalent of a compound having one epoxy group is used as the epoxy compound (B) and one equivalent of a compound having one acid anhydride group is used as the epoxy curing agent (C) The amount of the epoxy curing agent (C) relative to the compound (B) is assumed to be two times the amount.

1.4. The solvent (D)

The composition of the present invention can be obtained by, for example, dissolving a polyester amide acid (A), an epoxy compound (B) and an epoxy curing agent (C) in a solvent (D). Therefore, the solvent (D) is preferably a solvent capable of dissolving the polyester amide acid (A), the epoxy compound (B) and the epoxy curing agent (C). It is also possible that a solvent which does not dissolve the polyester amide acid (A), the epoxy compound (B) and the epoxy curing agent (C) alone can be used as the solvent (D) have.

The solvent (D) may be used alone, or a mixture of two or more solvents may be used, or the reaction solvent (a5) may be used as it is.

Examples of the solvent (D) include ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, Propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Glycol isopropyl methyl ether, dipropylene glycol monomethyl ether Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether acetate, triethylene glycol divinyl ether, triethylene glycol butyl methyl ether, tripropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, diethylene glycol dibutyl ether, But are not limited to, monomethyl ether, tetramethylene glycol monovinyl ether, tetraethylene glycol dimethyl ether, 2-methoxyethanol, 2-ethoxyethanol, methyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone Pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide , N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-epsilon-caprolactam, 1,3-dimethyl-2-imidazolidinone, -butyrolactone,? -caprolactone,? -hexanolactone,? -hexanolactone, methylethylsulfoxide, dimethylsulfoxide, and an equamide produced by Idemitsu Kosan Co., ).

Among them, in view of the solubility in polyester amide acid (A), epoxy compound (B) and epoxy curing agent (C), the composition of the present invention is preferably selected from ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Glycol monoethyl ether acetate, diethylene glycol monoethyl butyrate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, Diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate,? -Butyrolactone, dimethyl sulfoxide and manufactured by Idemitsu Kosan Co., Ltd. At least one compound selected from the group consisting of It is preferable to include one species as the solvent (D).

 1.5 Silica fine particles (E)

The fine silica particles (E) to be used in the present invention are not particularly limited as long as the average particle diameter is 50 nm or less, more preferably 40 nm or less, and further preferably 25 nm or less. By containing such fine silica particles (E), a cured film excellent in heat resistance, high transparency, and high hardness can be obtained.

The silica fine particles (E) may be used alone or in combination of two or more.

The mean particle diameter of the above-mentioned silica means a diameter equivalent to a sphere evaluated by a dynamic light scattering method.

The content of the fine silica particles (E) in the composition is preferably 35 parts by weight or more, more preferably 50 parts by weight or more based on 100 parts by weight of the polyester amide acid (A) from the viewpoint of obtaining a cured film having a high hardness More preferably 70 parts by weight or more. It is preferably 150 parts by mass or less, more preferably 145 parts by mass or less, and most preferably 140 parts by mass or less based on 100 parts by mass of the polyester amide acid (A) from the viewpoint of obtaining a cured film having good adhesion to ITO Is more preferable.

The silica fine particles (E) may be added to the composition as an epoxy resin containing silica dispersed in the optical adjustment epoxy resin (F). Specific examples of the silica-containing epoxy resin (E) include NANOPOX C450, NANOPOX C460, NANOPOX C620, NANOPOX F400, NANOPOX E500, NANOPOX E601, NANOPOX F631, NANOPOX F640 (trade name, manufactured by EVONIK), COMPOCERAN E203 , Compozera E205, Compozera E206 (trade name, manufactured by Arakawa Chemical Industries, Ltd.). Of these, NANOPOX C620 is particularly preferable in that an excellent cured film having high transparency and high hardness can be obtained.

1.6. Optical adjustment epoxy resin (F)

The optical adjusting epoxy resin (F) used in the present invention is an epoxy resin different from the above-mentioned epoxy resin (B), which is blended to adjust the optical properties of the cured film of the composition. Unlike the fine silica particles (E), the optical adjustment epoxy resin (F) can be added to the composition or used as a dispersion medium for dispersing the fine silica particles (E) in advance. The dispersion state of the fine silica particles (E) can be improved by previously dispersing the silica fine particles (E) in the optical adjusting epoxy resin (F) and then adding them to the composition.

Examples of the optically tuned epoxy resin (F) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, polymers of monomers having an oxirane ring, monomers having an oxirane ring, And copolymers of other monomers. Of these, a cured film having a high transmittance and excellent optical and transparent properties and having good adhesiveness to glass and ITO can be obtained. Therefore, it is preferable to use 3 ', 4'-epoxycyclohexylethyl 3,4-epoxycyclohexanecarboxylate Alicyclic epoxy compounds are preferable.

By using an alicyclic epoxy compound as the optical adjusting epoxy resin (F), a cured film having high transparency can be obtained. For example, when the film thickness is set to 2.2 탆, a cured film having a transmittance of 97% or more with a wavelength of 400 nm and a high transparency can be obtained. Further, by adjusting the blending amount of the composition, a cured film having a transmittance of 98% or more and a cured film having a transmittance of 99% or more can be obtained.

1.7. additive

The composition of the present invention may contain additives other than the polyester amide acid (A), the epoxy compound (B), the epoxy curing agent (C), the silica fine particle (E) and the optical adjusting epoxy resin (F) . As the additive, for example, other epoxy resin (f), polyimide resin, oxetane resin, polymerizable monomer, antistatic agent, coupling agent (g), pH adjuster, rust preventive, preservative, antifungal agent, (H), a surfactant (i), an epoxy resin curing accelerator (j), a reducing agent, an evaporation accelerator, a chelating agent and a water-soluble polymer. It may also contain pigments or dyes depending on the intended use. Only one kind of additives may be used, or two or more kinds of additives may be used in combination.

1.7.1. Other epoxy resin (f)

In the present invention, a compound having at least one oxirane ring or oxetane ring is referred to as an epoxy compound. In the present invention, the other epoxy resin (f) refers to an epoxy resin other than the epoxy compound (B) having the fluorene skeleton or the dicyclopentadiene skeleton and the optical adjusting epoxy resin (F). As the other epoxy resin (f), a compound having two or more oxirane rings is preferably used, and the other epoxy resin (f) may be used alone or in combination of two or more.

Examples of other epoxy resins (f) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, polymers of monomers having oxirane rings, ≪ / RTI > and other monomers.

Examples of the monomer having an oxirane ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, .

In the formula (1), R is a group independently selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl and arylalkyl; In the alkyl having 1 to 45 carbon atoms, any hydrogen may be substituted with fluorine, and any non-adjacent -CH ₂ - may be replaced with -O- or -CH = CH-; For alkylenes in arylalkyl, the number of carbon atoms is from 1 to 10, and any non-adjacent -CH ₂ - may be replaced by -O-; R ¹ and R ² are independently selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl; And X ¹ is a group having any one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl and oxetanylene.

In the present invention, (meth) acrylate refers to acrylate and / or methacrylate, and (meth) acryl refers to acrylic and / or methacryl.

Examples of other monomers copolymerizable with the oxirane ring-containing monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (Meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

Preferable specific examples of the polymer of the monomer having an oxirane ring and the copolymer of the monomer having an oxirane ring and other monomers include polyglycidyl methacrylate, a copolymer of methyl methacrylate and glycidyl methacrylate, benzyl Copolymers of methacrylate and glycidyl methacrylate, copolymers of n-butyl methacrylate and glycidyl methacrylate, copolymers of 2-hydroxyethyl methacrylate and glycidyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and glycidyl methacrylate, and copolymers of styrene and glycidyl methacrylate. When the composition of the present invention contains these epoxy resins, the heat resistance of the cured film formed from the composition is preferably improved.

Specific examples of the other epoxy resin (f) include "jER806", "jER807", "jER815", "jER825", "jER827", "jER828", "jER871", "jER872", "jER190P", "jER191P" JER1004 "," jER1004AF "," jER1007 "," jER1010 "," jER1256 "," jER157S70 "," jER1032H60 "(available from Mitsubishi Chemical Corporation)," araldite CY177 " "Cellid 2021P", "Celllock 3000", "Celllock 8000", "EHPE-3150" and "EHPE-3150CE" (trade names, trade names, manufactured by BASF), "Araldite CY184" (Trade name, manufactured by DICEL CHEMICAL INDUSTRIES, LTD.), "TECHMORE VG3101L" (trade name, manufactured by PRINTECH Co., Ltd.), "HP7200, HP7200H, HP7200HH EPHP-501H, EPPN-501H, EOCN-102S, EOCN-103S, EOCN-104S, EPPN-501H, EPPN- -201-L " (trade name, manufactured by Nippon Kayaku Co., Ltd.) "MA-DGIC", "Me-DGIC", "TG-G" (trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.) FLEP-10 "," FLEP-50 "," FLEP-60 "(trade name, manufactured by Nissan Chemical Industries, Ltd.))," TEPIC- N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N'- Diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane. Among these, a composition comprising a trade name "Araldite CY184", a trade name "Celloxide 2021P", a trade name "TECHMORE VG3101L" and an epoxy resin "jER828" is preferable because a cured film having particularly excellent flatness can be obtained.

The concentration of the other epoxy resin (f) in the composition of the present invention is not particularly limited, but from the viewpoint of obtaining a cured film excellent in heat resistance and good balance between adhesion to glass and ITO, Preferably from 0 to 40% by weight, more preferably from 0 to 30% by weight, based on the total weight of the composition.

1.7.2. Oxetane resin

The optical adjustment epoxy resin (F) includes an oxetane resin as an embodiment thereof. Specific examples of the oxetane resin include "OXT-101", "OXT-121", "OXT-212" and "OXT-221" (trade name, manufactured by Toa Gosei Co., Ltd.). Among them, the composition containing the trade name " OXT-101 " is preferable because a cured film having high transparency can be obtained. The concentration of the oxetane resin in the composition of the present invention is not particularly limited, but from the standpoint of obtaining a cured film having more excellent heat resistance and transparency, it is preferable that the concentration of the oxetane resin in the composition of the present invention By weight, more preferably 0 to 30% by weight.

The "epoxy compound containing two or more oxirane rings or oxetanyl rings in the molecule in the thermosetting resin composition" mentioned in [8] in the section of the solution of the above-mentioned problems is included in the thermosetting resin composition of the present invention (Epoxy compound (B) having a fluorene skeleton or dicyclopentadiene skeleton), an optically tuned epoxy resin (F), and other epoxy resins (f).

1.7.3. Polyimide resin

The polyimide resin is not particularly limited as long as it has an imide group. The polyimide resin may be used alone or as a mixture of two or more thereof.

The polyimide resin is obtained, for example, by imidizing an amide acid obtained by reacting an acid anhydride with a diamine. As the acid anhydride, there is, for example, a tetracarboxylic acid dianhydride (a1) which can be used for the synthesis of the polyester amide acid (A). As the diamine, there is, for example, a diamine (a2) which can be used for the synthesis of the polyester amide acid (A).

When the composition of the present invention comprises a polyimide resin, the concentration of the polyimide resin in the composition of the present invention is not particularly limited, but from the standpoint of obtaining a cured film having better heat resistance and chemical resistance, 0.1 to 20 wt% , More preferably from 0.1 to 10 wt%.

1.7.4. Polymerizable monomer

Examples of the polymerizable monomer include monofunctional polymerizable monomers, bifunctional (meth) acrylates, and trifunctional or more polyfunctional (meth) acrylates. The polymerizable monomers may be used alone or in combination of two or more.

When the composition of the present invention contains a polymerizable monomer, the concentration of the polymerizable monomer in the composition of the present invention is not particularly limited, but from the viewpoint of obtaining a cured film having better chemical resistance and surface hardness, Is preferably contained in an amount of 0.1 to 40% by weight, more preferably 1 to 30% by weight, based on 100% by weight of the composition.

Examples of the monofunctional polymerizable monomer include monofunctional monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl [5.2.1.0 ^2,6 ] decane (meth) acrylate, glycerol mono (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, ethylene oxide adduct of lauryl alcohol Methacrylate, (Meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3 Ethyl-3- (meth) acryloxyethyloxetane, p-vinylphenyl-3-ethyloxetane, (Meth) acryloyloxymethyloxetane, 4-trifluoromethyl-2- ((meth) (Meth) acryloxymethyloxetane, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, vinyltoluene, N-cyclohexylmaleimide, (Meth) acrylamide, N-acryloylmorpholine, polystyrene macromonomer, polymethylmethacrylate macromonomer, (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, (Meth) acrylic acid mono [2- (meth) acryloyloxyethyl] maleic acid mono [2- (meth) acrylate] monocaprylic acid mono Cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl].

Examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and dipentaerythritol di (meth) acrylate.

Examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) (Meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) Acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa Oxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and urethane (meth) acrylate.

1.7.5. Antistatic agent

The antistatic agent can be used to prevent the charging of the composition of the present invention. When the composition of the present invention contains an antistatic agent, it is preferably used in an amount of 0.01 to 1% by weight in the composition of the present invention.

As the antistatic agent, a known antistatic agent can be used. Specifically, metal oxides such as tin oxide, tin oxide-antimony oxide complex oxide, and tin oxide-indium oxide composite oxide; Quaternary ammonium salts.

The antistatic agent may be used alone or in combination of two or more.

1.7.6. Coupling agent (g)

The coupling agent (g) is not particularly limited, and a known coupling agent such as a silane coupling agent can be used for the purpose of improving adhesion with glass or ITO. When the composition of the present invention contains the coupling agent (g), the coupling agent (g) is added in an amount of 10% by weight or less based on 100% by weight of the solid content of the composition of the present invention Is preferably used.

The coupling agent (g) may be used alone or in admixture of two or more.

The silane coupling agent includes, for example, trialkoxysilane compounds and dialkoxysilane compounds. Preferable examples include gamma -vinylpropyltrimethoxysilane, gamma -vinylpropyltriethoxysilane, gamma -acryloylpropylmethyldimethoxysilane, gamma -acryloylpropyltrimethoxysilane, gamma -propyltrimethoxysilane, gamma- Acryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloylpropyltrimethoxysilane,? -Methacryloyl Methyldiethoxysilane,? -Methacryloylpropyltriethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane ,? -glycidoxypropyltriethoxysilane,? -aminopropylmethyldimethoxysilane,? -aminopropyltrimethoxysilane,? -aminopropylmethyldiethoxysilane,? -aminopropyltriethoxysilane, N- Aminoethyl-gamma-iminopropylmethyldimethoxysilane, N- Aminoethyl-gamma -aminopropyltriethoxysilane, N-phenyl- gamma -aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltriethoxy silane, N-phenyl- Silane, N-phenyl- gamma -aminopropylmethyldimethoxysilane, N-phenyl- gamma -aminopropylmethyldiethoxysilane, gamma -mercaptopropylmethyldimethoxysilane, gamma -mercaptopropylmethyldiethoxysilane, gamma- Mercaptopropyltriethoxysilane,? -Isocyanatepropylmethyldiethoxysilane, and? -Isocyanatepropyltriethoxysilane.

Of these, preferred are γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatepropyl Particularly preferred is triethoxysilane.

1.7.7. Antioxidant (h)

By containing the antioxidant (h), the composition of the present invention can prevent the cured film obtained from the composition from being deteriorated when exposed to high temperature or light. When the composition of the present invention contains the antioxidant (h), the antioxidant (h) may be used in an amount of 0.1 to 100 parts by weight, based on 100 parts by weight of the solid content of the composition excluding the antioxidant (h) 3 parts by weight is preferably added.

The antioxidant (h) may be used alone or in combination of two or more.

Examples of the antioxidant (h) include hindered amine compounds, hindered phenyl compounds, and the like. Specific examples thereof include IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 and IRGANOX 1520L (all trade names, manufactured by BASF), adecastab AO-20, adecastab AO- AO-50, adecastab AO-60, adecastab AO-80, and adecastab AO-330 (trade names, manufactured by ADEKA Corporation).

1.7.8. Surfactants (i)

When the composition of the present invention contains the surfactant (i), it is possible to obtain a composition having improved wettability to the substrate, leveling property and applicability, and when the composition of the present invention contains the surfactant (i) (i) is preferably used in an amount of 0.01 to 1% by weight based on 100% by weight of the composition of the present invention.

The surfactant (i) may be used alone or in combination of two or more.

As the surfactant (i), for example, trade names "BYK-300", "BYK-306", "BYK-335", "BYK-310 KP-341 "," BYK-344 "and" BYK-370 "(trade names, manufactured by Big Chemie Japan KK)," KP-112 " (All manufactured by Shin-Etsu Chemical Co., Ltd.); Acrylic surfactants such as BYK-354, BYK-358 and BYK-361 (trade name, manufactured by BICKEMI Japan Co., Ltd.); "Megaface F-444", "Megapack F-477", "Megapack 251" (trade names, manufactured by Neos), "Megafac F- Pack RS-72-K "(trade name, manufactured by DIC Corporation).

1.7.9. Epoxy resin curing accelerator (j)

DBU "," DBN "," U-CAT "," U-CAT "," U-CAT ", and the like can be used as the epoxy resin curing accelerator (j) from the viewpoint of lowering the curing temperature of the composition of the present invention, U-CAT SA1, U-CAT SA102, U-CAT SA506, U-CAT SA603, U- CAT SA810, U- CAT 5002, U- CAT 5003, U-CAT SA881 "," U-CAT 891 "(trade name, manufactured by SANA PRO)," CP-001 "and" NV-203-R4 " (Trade name, manufactured by Osaka Gas Chemical Co., Ltd.), "Karenz MT PE1", "Car lens MT BD1", "Car lens MT NR1" (trade name, Showa Denko Co., ), And the like.

Each of the epoxy resin curing accelerators (j) may be used alone, or two or more epoxy resin curing accelerators may be used in combination.

The content of the epoxy resin curing accelerator (j) is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, still more preferably 30 to 150 parts by weight, per 100 parts by weight of the epoxy curing agent (C) to be.

1.7.10. Pigment or dye

Examples of the pigment include at least one compound selected from the group consisting of boron nitride, aluminum nitride, silicon carbide, alumina, magnesia, silica, rutile titanium oxide, zinc oxide, lower titanium oxide and graphite. The rutile-type titanium oxide refers to a white titanium oxide represented by TiO ₂ . The lower titanium oxide refers to black titanium oxide such as Ti ₃ O ₅ , Ti ₂ O ₃ and TiO ₂ . Examples of the low-order titanium oxide (black) known as titanium black include Tiac D (trade name) manufactured by Ako Kasei Kogyo Co., Ltd., 12S, 13M, 13M- C, SC-13M (trade name), and Marco 2004 Black (trade name) manufactured by Tokushiki. Examples of the graphite include Marco 2003, Black Marco 2011 Black, Marco 2020 Black and Marco 2021 Black (trade name) manufactured by Tokushiki Co., Ltd.

Examples of the dyes include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes. Examples of the azo dye include "VALIFAST BLACK 3810", "VALIFAST BLACK 3820", "VALIFAST RED 3304", "VALIFAST RED 3320" and "OIL BLACK 860" (trade names, manufactured by Orient Chemical Industries Ltd.).

Each of the pigment and the dye may be used alone or in combination of two or more.

2. Method for preparing thermosetting resin composition

The composition of the present invention is a composition comprising an epoxy compound having a polyester amide acid (A), a fluorene skeleton or a dicyclopentadiene skeleton, and an epoxy curing agent (C), a solvent (D), silica fine particles (E) F) or other additives.

The composition of the present invention can also be obtained by directly mixing the reaction liquid or mixture obtained in the synthesis of the polyester amide acid (A) with an epoxy compound (B), an epoxy curing agent (C), a solvent (D) Fine particles (E), an optical adjusting epoxy resin (F), other additives, and the like.

3. Method of forming a cured film

The cured film of the present invention is not particularly limited as long as it is a film obtained from the composition of the present invention. The cured film of the present invention can be obtained, for example, by applying the composition of the present invention onto a substrate and heating it.

Hereinafter, the coating method and the curing method will be described with respect to the composition of the present invention.

3.1. Method of applying thermosetting resin composition

The application of the composition of the present invention onto a substrate can be carried out by a known method such as spray coating method, spin coating method, roll coating method, dipping method, slit coating method, bar coating method, gravure printing method, flexo printing method, A dispenser method, a screen printing method, and an inkjet printing method.

For example, when a transparent insulating film is formed from the composition of the present invention so that the X and Y electrodes are not in contact with each other, gravure printing, flexographic printing, offset printing, A printing method such as a screen printing method and an inkjet printing method is preferable.

For example, in the case of forming the overcoat from the composition of the present invention, the overcoat is preferably applied by a spin coating method, a slit coating method, a gravure printing method, a flexographic printing method, an offset printing method, a dispenser method , A screen printing method and the like are preferable.

The substrate is not particularly limited and a known substrate can be used. For example, a glass epoxy substrate, glass composite material suitable for various standards such as FR-1, FR-3, FR-4, CEM- Substrate, paper phenol substrate, paper epoxy substrate, green epoxy substrate, BT (bismaleimide triazine) resin substrate; A substrate made of a metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium or stainless steel; (Zirconium), magnesium oxide (magnesia), aluminum titanate, barium titanate, lead titanate (PT), zirconium titanate (zirconium oxide), zirconium oxide (PZT), zirconate titanate zirconate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllium), silicon oxide (silica), silicon carbide (silicon carbide) A substrate made of an inorganic material such as silicon nitride, boron nitride (boron nitride), zinc oxide, mullite, ferrite, stearate, forsterite, spinel or spougemene being); (Polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylenedimethylene terephthalate), PPS (polyphenylene sulfide), polycarbonate, polyacetal, poly A substrate made of resin such as phenylene ether, polyamide, polyarylate, polysulfone, polyether sulfone, polyether imide, polyamideimide, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer or liquid crystal polymer (Which may be a substrate having on its surface a layer containing these resins); A semiconductor substrate such as silicon, germanium or gallium arsenide; A glass substrate; A substrate on which an electrode material (wiring) such as tin oxide, zinc oxide, ITO or ATO (antimony tin oxide) is formed; gel sheets such as? GEL (alpha gel),? GEL (beta gel),? GEL (theta gel) or? GEL (gamma gel) (registered trademark of Tyaka).

The composition of the present invention is preferably applied to a glass substrate, an ITO substrate or a resin film substrate.

3.2. Curing method of thermosetting resin composition

After the composition of the present invention is applied, the cured film can be obtained by heating the applied composition on the substrate. As a method of forming the cured film in this way, the composition of the present invention is preferably applied, followed by heating in a hot plate or an oven to remove the solvent by vaporization or the like (drying treatment) A method of further heating (curing treatment) is used.

Usually, the heating temperature is 70 to 120 占 폚 and the heating time is 5 to 15 minutes for an oven, 1 for a hot plate if the oven is used, ~ 10 minutes. By such a drying process, it is possible to form a coating film on the substrate to such an extent that the shape can be maintained.

After the coating film is formed, curing treatment is usually carried out at 100 to 300 占 폚, preferably 100 to 250 占 폚. In this case, when the oven is used, the cured film can be obtained by heating for 10 to 120 minutes in general, and for 5 to 30 minutes in the case of using a hot plate.

The curing treatment is not limited to the heat treatment, and may be a treatment such as irradiation with ultraviolet rays, ion beams, electron beams, or gamma rays.

4. The cured film-

The substrate with a cured film of the present invention is not particularly limited as long as it has the cured film of the present invention, but it is preferable that the above-mentioned cured film-attached substrate is provided on at least one kind of substrate selected from the group consisting of the substrate, It is preferable to have a cured film.

Such a cured film-attached substrate can be obtained by applying the composition of the present invention onto a substrate such as glass, ITO, PET, PEN or the like by the coating method or the like in the whole surface or a predetermined pattern (line type) , And thereafter, by the drying treatment and the curing treatment as described above.

5. Electronic parts

The electronic component of the present invention is an electronic component having the aforementioned cured film or substrate with a cured film. Examples of such electronic parts include various optical materials such as a color filter, an LED light emitting element and a light receiving element, and a touch panel.

The touch panel can be manufactured, for example, by combining a liquid crystal display device or an organic electroluminescence device with a position detecting device.

Here, as the position detecting device, for example, a cured film (transparent insulating film) of the present invention is formed so as to cover the wiring with a wiring (X electrode) made of a conductive material such as ITO formed thereon, There is an apparatus in which a wiring (Y electrode) made of a conductive material such as ITO is formed so as to be orthogonal to the electrode, and then an overcoat is formed with the cured film of the present invention so as to cover the entire surface of the substrate.

By using the composition of the present invention in the production of such an apparatus, the cured film (transparent insulating film), which is usually formed in a pattern by a printing method or the like, and the overcoat formed on the entire surface by a coating method, It may be formed of one kind of composition. Thus, by using the composition of the present invention, it is possible to simplify the line and improve the yield in the production of electronic parts.

[Example]

Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited to these examples. (A1), diamine (a2), polyhydric hydroxy compound (a3), monohydric alcohol (a4), reaction solvent (a5), fluorene skeleton or dicyclopentane (B), an epoxy curing agent (C), a solvent (D), a silica fine particle (E), an optical adjusting epoxy resin (F), a coupling agent (g), an antioxidant (h) i), the name of the epoxy curing accelerator (j) and its abbreviation. These abbreviations are used in the following descriptions.

≪ Tetracarboxylic acid dianhydride (a1) >

ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride

≪ Diamine (a2) >

DDS: 3,3'-diaminodiphenyl sulfone

<Polyhydric hydroxy compound (a3)>

BDOH: 1,4-butanediol

<1 is alcohol (a4)>

BzOH: benzyl alcohol

&Lt; Reaction solvent (a5) >

MPM: methyl 3-methoxypropionate

PGMEA: Propylene glycol monomethyl ether acetate

EDM: diethylene glycol methyl ethyl ether

&Lt; Styrene-maleic anhydride copolymer &

SMA1000: styrene component / maleic anhydride component: 50/50, weight average molecular weight: 5,500 (trade name, manufactured by Satoruma Co., Ltd.)

<Epoxy compound (B) having fluorene skeleton or dicyclopentadiene skeleton>

EG-200: OGSOL EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)

EG-280: OGSOL EG-280 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.)

4088S: EP-4088S (trade name, manufactured by ADEKA Corporation)

&Lt; Epoxy curing agent (C) >

TMA: Anhydrous trimellitic acid

&Lt; Solvent (D) >

EDM: diethylene glycol methyl ethyl ether

DB: Diethylene glycol monobutyl ether

MTEM: tetraethylene glycol dimethyl ether

Eca: diethylene glycol monoethyl ether

EDGAC: diethylene glycol monoethyl ether acetate

PGME: Propylene glycol monomethyl ether

DEGBEA: Diethylene glycol monobutyl ether acetate

MTM: triethylene glycol dimethyl ether

&Lt; Silica fine particles (E) >

C450: NANOPOX C450 (trade name, manufactured by EVONIK), average particle diameter: 20 nm

C460: NANOPOX C460 (trade name, manufactured by EVONIK), average particle diameter: 20 nm

C620: NANOPOX C620 (trade name, manufactured by EVONIK), average particle diameter: 20 nm

C680: NANOPOX C680 (trade name, manufactured by EVONIK), average particle diameter: 20 nm

&Lt; Optical Adjusting Epoxy Resin (F) >

BPA: bisphenol A type epoxy resin (C450 dispersion medium)

BPF: bisphenol F type phenol resin (C460 dispersion medium)

OXT-101 (manufactured by Daicel Chemical Industries, Ltd.), 3 ', 4'-epoxycyclohexylethyl 3,4-epoxycyclohexanecarboxylate (dispersant of C620) (Trade name, manufactured by TOA Corporation), oxetane resin (dispersion medium of C680)

&Lt; Other epoxy resin (f) >

EHPE3150: EHPE3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.), 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl)

SQ: A compound represented by the formula (1-1) synthesized by the method described in Japanese Patent Laid-Open No. 2009-167390

&Lt; Coupling agent (g) >

GMS:? -Glycidoxypropyltrimethoxysilane

&Lt; Antioxidant (h) >

I1010: IRGANOX 1010 (trade name, manufactured by BASF)

&Lt; Surfactant (i) >

BYK344: BYK-344 (trade name, manufactured by Big Chem Japan Co., Ltd.)

&Lt; Epoxy resin curing accelerator (j) >

PE1: Karenz MT PE1 (trade name, manufactured by Showa Denko K.K.)

SA506: U-CAT SA506 (trade name, manufactured by San A Pro Co., Ltd.)

First, a polyester amide acid solution was synthesized as shown below (Synthesis Examples 1 and 2). Table 1 summarizes Synthesis Examples 1 and 2.

[Synthesis Example 1]

446.6 g of dehydrated and purified MPM, 31.93 g of BDOH, 25.54 g of BzOH and 183.20 g of ODPA were charged into a 1000 ml separable flask equipped with a thermometer, a stirrer, a feed inlet and a nitrogen gas inlet, Lt; / RTI &gt; for 3 hours. Thereafter, the reaction solution was cooled to 25 deg. C, 29.33 g of DDS and 183.4 g of MPM were added, stirred at 20 to 30 DEG C for 2 hours and then at 115 DEG C for 1 hour. Thereafter, the solution was cooled to 30 DEG C or lower to obtain a 30 wt% solution of light yellow transparent polyester amide acid.

The spinning viscosity of this solution was 28.1 mPa · s. Here, the rotational viscosity is a viscosity measured at 25 캜 using an E-type viscometer (trade name: VISCONIC END, manufactured by TOKYO INSTRUMENTS CO., LTD.) (The same applies hereinafter).

The weight average molecular weight of the resulting polyester amide acid was 4,200. The weight average molecular weight of the polyester amide acid was measured in the following manner.

The obtained polyester amide acid was diluted with N, N-dimethylformamide (DMF) so that the concentration of the polyester amide acid became about 1% by weight. The polyester amide acid was measured by GPC apparatus: Chrom Nav (Japan Spectroscopy) (Differential refractivity meter RI-2031 Plus), the diluent was measured by GPC method using the diluent as a developing agent, and the value was converted by polystyrene conversion. The columns were obtained by connecting three columns of GF-1G7B, GF-510HQ and GF-310HQ manufactured by Showa Denko KK in this order and measuring them under conditions of a column temperature of 40 ° C and a flow rate of 0.5 ml / min (Hereinafter the same).

[Synthesis Example 2]

A 500 ml flask equipped with a thermometer and a stirrer was purged with nitrogen, and 179.2 g of dehydrated and purified PGMEA, 16.96 g of ODPA, 51.6 g of SMA1000, 19.7 g of BzOH, 3.28 g of BDOH and EDM 34.2 were charged and dried And the mixture was stirred at 125 DEG C for 2 hours in a stream of nitrogen. Thereafter, the reaction solution was cooled to 25 deg. C, 4.52 g of DDS and 10.6 g of EDM were added thereto, followed by stirring at 20 to 30 DEG C for 2 hours and then at 120 DEG C for 1 hour. Thereafter, the solution was cooled to 30 占 폚 or lower to obtain a 30 wt% solution of light yellow transparent polyester amide acid (A).

The rotational viscosity of this solution was 35.3 mPa · s. The weight average molecular weight measured by GPC was 24,000 (in terms of polystyrene).

[Table 1]

[Example 1]

Necked flask equipped with a stirrer was purged with nitrogen. To the flask, 4.8 g of the polyester amide acid solution obtained in Synthesis Example 1, 1.44 g of EG-200, 1.44 g of C620, 0.43 g of TMA, 0.2 g of GMS, 0.02 g of I1010 and 11.6 g of dehydrated and purified MTM were added and stirred at room temperature for 1 hour to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to obtain a filtrate (thermosetting resin composition).

[Examples 2 to 25]

In Examples 2 to 25, thermosetting resin compositions were prepared in the same manner as in Example 1, except that the kind and amount of each component were changed as shown in Tables 2 and 3.

As described in Example 1, the fine silica particles (E) were added as an epoxy resin containing silica dispersed in an optical adjustment epoxy resin (F). Therefore, in Tables 2 and 3, the amount of each component is described by dividing the fine silica particles (E) constituting the epoxy resin containing dispersed silica and the optical control epoxy resin (F). The type and amount of epoxy resin (NANOPOX) containing dispersed silica containing silica fine particles (E) and optical adjusted epoxy resin (F) are shown in Table 5.

[Example 26]

A 100 ml three-necked flask equipped with a stirring wing was purged with nitrogen. To the flask, 4.79 g of the polyester amide acid solution obtained in Synthesis Example 1, 0.72 g of EG-200, 1.44 g of C620, 0.72 g of EHPE3150, 0.43 g of TMA, 0.23 g of GMS, 0.02 g of I1010 and 11.6 g of dehydrated and purified MTM were added and stirred at room temperature for 1 hour to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to obtain a filtrate (thermosetting resin composition).

[Examples 27 to 28]

In Examples 27 to 28, a thermosetting resin composition was prepared in the same manner as in Example 26 except that the kind and amount of each component were changed as shown in Table 3.

[Example 29]

Necked flask equipped with a stirrer was purged with nitrogen. To the flask, 4.8 g of the polyester amide acid solution obtained in Synthesis Example 1, 1.44 g of EG-200, 1.44 g of C620, 0.35 g of TMA, 0.22 g of GMS, 0.02 g of I1010, 0.16 g of SA506 and 11.3 g of dehydrated and purified MTM were added and stirred at room temperature for 1 hour to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to obtain a filtrate (thermosetting resin composition).

[Examples 30 to 32]

In Examples 30 to 32, thermosetting resin compositions were prepared in the same manner as in Example 29 except that the kind and amount of each component were changed as shown in Table 3.

[Comparative Example 1]

A 100 ml three-necked flask equipped with a stirring wing was purged with nitrogen. To the flask, 4.80 g of the polyester amide acid solution obtained in Synthesis Example 1, 2.88 g of C 620, 0.43 g of TMA, 0.23 g of GMS, And 11.6 g of dehydrated and purified MTM were added and stirred at room temperature for 1 hour to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to obtain a filtrate (thermosetting resin composition).

[Comparative Example 2]

A thermosetting resin composition was prepared in the same manner as in Comparative Example 1 except that the kind and amount of each component were changed as shown in Table 4.

[Comparative Example 3]

Necked flask equipped with a stirrer was purged with nitrogen. To the flask, 4.79 g of the polyester amide acid solution obtained in Synthesis Example 1, 2.88 g of EG-200, 0.43 g of TMA, 0.23 g of GMS, 0.010 g of I1010 and 11.6 g of dehydrated and purified MTM were added and stirred at room temperature for 1 hour to dissolve each component uniformly. Next, 0.05 g of BYK344 was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to obtain a filtrate (thermosetting resin composition).

[Comparative Examples 4 to 5]

Comparative Examples 4 to 5 were prepared in the same manner as in Comparative Example 3 except that the kind and amount of each component were changed as shown in Table 4 to prepare a thermosetting resin composition.

[Table 2]

[Table 3]

[Table 4]

[Table 5]

The thermosetting resin composition obtained by the above-mentioned adjustment method was spin-coated on a glass substrate and an ITO substrate such that the thickness of the obtained cured film was as shown in Table 6, and then dried on a hot plate at 80 DEG C for 5 minutes To form a coating film. Thereafter, for Examples 1 to 28 and Comparative Examples 1 to 5, a cured film was obtained by heating at 150 DEG C for 30 minutes using an oven. For Examples 29 to 32, a cured film was obtained by heating at 120 DEG C for 30 minutes using an oven. The cured films thus obtained were evaluated for transparency, adhesion, surface hardness and chemical resistance. The evaluation results are shown in Table 3.

[Assessment Methods]

(i) transparency

Using the obtained glass substrate with a cured film, the transmittance of the cured film was measured at a wavelength of 400 nm by a spectrophotometer V-670 (manufactured by Nippon Bunko K.K.).

(ii) Adhesion

The resulting glass substrate with a cured film and ITO substrate with a cured film were immersed in ultrapure water at 60 DEG C for 60 minutes and subjected to a crosscut test (JIS-K-5400) by tape peeling, The adhesion between the substrate and the cured film was evaluated by counting. 100 pieces of 1 mm x 1 mm grid were formed on the cured film at intervals of 1 mm using a cutter knife, and # 600 manufactured by 3M Company was used as a tape for peeling after adhering to the grid. The case where the number of cured films formed on the substrate and the number (remaining number / 100) remaining on the substrate after peeling the tape out of 100 grids was 100/100 was evaluated as 0, and the case where it was evaluated as x was 99/100 or less.

 (iii) Surface hardness

Using the obtained glass substrate with a cured film, the hardness of the surface of the cured film was measured with a pencil hardness meter according to JIS-K-5400.

(iv) Chemical resistance

The obtained glass substrate with a cured film and the ITO substrate with a cured film were immersed in a 3.5% oxalic acid aqueous solution at 40 占 폚 for 6 minutes. The change in the film thickness of the cured film before and after the immersion was measured using a contact-type film subassystem XP-200 (manufactured by AMBIOS TECHNOLOGY). The film thickness change was evaluated as?, When the film thickness variation was less than 3% did. The transmittance before and after the immersion was observed in the same manner as in (i), and the case where the change of the transmittance was less than ± 1% was rated "O", and the case where the transmittance was ± 1% or more was evaluated as "

[Table 6]

Comparing Examples 1 to 32 and Comparative Examples 3 to 5, it was found that a cured film having a high hardness can be obtained by blending the fine silica particles (E) with the thermosetting resin composition.

As is clear from the results shown in Table 6, the cured films formed from the thermosetting resin compositions obtained in Examples 1 to 16 and 26 to 32 are excellent in adhesion to glass and ITO, and have a transmittance at 400 nm of not less than 97% The transparency was high, and the surface hardness was as high as 3H or more. In addition, resistance to oxalic acid aqueous solution was good, and high transparency, high hardness, adhesion to glass and ITO, and resistance to oxalic acid aqueous solution were balanced.

On the other hand, the cured films formed from the thermosetting resin compositions obtained in Examples 17 to 23 had a low transparency with a transmittance of 95% or less at 400 nm, and the cured films of Examples 24 to 25 and Comparative Examples 1 and 2 had poor adhesion to ITO And the cured films of Comparative Examples 3 to 5 had low surface hardness of H or less.

Examples 1 to 16 and 24 to 32 containing the 3 ', 4'-epoxycyclohexylethyl 3,4-epoxycyclohexanecarboxylate, which is an alicyclic epoxy compound, as the optical adjustment epoxy resin (F) Had a high transparency at a transmittance of 400 nm or more of 97% or more. On the other hand, the cured films formed of the thermosetting resin compositions of Comparative Examples 1 and 2 did not have sufficient adhesion to ITO. As a result, it is found that the epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton is required for the thermosetting resin composition in order to form a cured film having good adhesion to ITO. From the results of Examples 4 and 5, it can be said that the content of the epoxy compound (B) is effective for forming a cured film having high adhesion to ITO if it is 25 parts by weight or more based on 100 parts by weight of the polyester amide acid (A) .

As described above, since Synthesis Examples 1 and 2 are 30 wt% solutions of the polyester amide acid (A), the amount of the polyester amide acid (A) contained in the thermosetting composition is as shown in Tables 2 to 4 30% by weight of the blending amounts of Synthesis Examples 1 and 2.

In order to form a cured film having high adhesion to the ITO substrate, it is preferable that the content of the fine silica particles (E) relative to the polyester amide acid (A) is not excessively increased. From the results of Examples 24 and 25, the content of the fine silica particles (E) is preferably 140 parts by weight or less, more preferably 130 parts by weight or less, based on 100 parts by weight of the polyester amide acid (A).

As described above, only a cured film obtained from a composition comprising an epoxy resin having a polyester amide acid, a fluorene skeleton or a dicyclopentadiene skeleton, silica fine particles, an optical adjusting epoxy resin and an epoxy curing agent satisfies all the desired characteristics I could.

[Industrial applicability]

The composition of the present invention is useful for forming a protective film for various optical materials such as a color filter, a LED light emitting element and a light receiving element from the viewpoint of being able to form a cured film having excellent characteristics as an optical material such as adhesion and transparency, (For forming a transparent electrode insulating film or an overcoat film for use in a touch panel).

Claims (23)

(B), an epoxy curing agent (C), a solvent (D), fine silica particles (E) having an average particle diameter of 50 nm or less, and an optically anisotropic layer (B) having a fluorene skeleton or a dicyclopentadiene skeleton. And an adjustable epoxy resin (F). The method according to claim 1,
Wherein the optically tuned epoxy resin (F) is an alicyclic epoxy compound. 3. The method according to claim 1 or 2,
Wherein the cured film having a thickness of 2.2 micrometers obtained from the thermosetting resin composition has a transmittance of 97% or more at a wavelength of 400 nm. 4. The method according to any one of claims 1 to 3,
Wherein the epoxy equivalent of the epoxy compound (B) having the fluorene skeleton or dicyclopentadiene skeleton is 150 to 550 g / eq. 5. The method according to any one of claims 1 to 4,
And 15 to 400 parts by weight of an epoxy compound (B) having a fluorene skeleton or a dicyclopentadiene skeleton relative to 100 parts by weight of the polyester amide acid (A). 6. The method according to any one of claims 1 to 5,
Wherein the epoxy curing agent (C) is at least one compound selected from the group consisting of an acid anhydride type curing agent, a phenol resin type curing agent, an amine adduct, a polycarboxylic acid type curing agent, a polyamine type curing agent and a catalyst type curing agent Resin composition. 7. The method according to any one of claims 1 to 6,
Wherein the content of the silica fine particles (E) is 140 parts by weight or less based on 100 parts by weight of the polyester amide acid (A). 8. The method according to any one of claims 1 to 7,
Wherein the epoxy curing agent (C) is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total of 100 parts by weight of an epoxy compound containing two or more oxiran rings or oxetane rings in the molecule in the thermosetting resin composition. 9. The method according to any one of claims 1 to 8,
Wherein the polyester amide acid (A) has a weight average molecular weight of 2,000 to 30,000. 10. The method according to any one of claims 1 to 9,
Wherein the polyester amide acid (A) is a compound having a constituent unit represented by the following formula (3) and (4):

(In the formulas (3) and (4), R ¹ is independently a tetravalent organic group having 1 to 30 carbon atoms, R ² is a divalent organic group having 1 to 40 carbon atoms, and R ³ is a divalent organic group having 1 to 20 carbon atoms Of the divalent organic group. 11. The method according to any one of claims 1 to 10,
Wherein the polyester amide acid (A) is a compound obtained by reacting tetracarboxylic dianhydride (a1), diamine (a2) and polyhydric hydroxy compound (a3) as essential components. 12. The method according to any one of claims 1 to 11,
Wherein the polyester amide acid (A) is a compound obtained by reacting a tetracarboxylic dianhydride (a1), a diamine (a2), a polyhydric hydroxy compound (a3) and a monohydric alcohol (a4) . 13. The method according to any one of claims 1 to 12,
Wherein the polyester amide acid (A) is at least one compound selected from the group consisting of X mol of tetracarboxylic dianhydride (a1), Y mol of diamine (a2) and Z mol of polyhydric hydroxy compound (a3) In a ratio that establishes the relationship between the thermosetting resin composition and the thermosetting resin composition:
0.2? Z / Y? (i)
0.2? (Y + Z) /X? 1.5 ... (ii). 14. The method according to any one of claims 11 to 13,
Wherein the tetracarboxylic dianhydride (a1) is at least one compound selected from the group consisting of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic dianhydride, 2,2- And at least one compound selected from the group consisting of bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate). 15. The method according to any one of claims 11 to 14,
Wherein the diamine (a2) is at least one compound selected from the group consisting of 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. 16. The method according to any one of claims 11 to 15,
Wherein the polyhydric hydroxy compound (a3) is at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8- Wherein the thermosetting resin composition is a thermosetting resin composition. 17. The method according to any one of claims 11 to 16,
Wherein the monohydric alcohol (a4) is at least one selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl- Or more of a thermosetting resin composition. 18. The method according to any one of claims 11 to 17,
Wherein the tetracarboxylic dianhydride (a1) is 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, the diamine (a2) is 3,3'-diaminodiphenylsulfone, the polyhydric hydroxy Wherein the compound (a3) is 1,4-butanediol, and the epoxy curing agent (C) is anhydrous trimellitic acid. 19. The method according to any one of claims 1 to 18,
A thermosetting resin composition for a touch panel. A cured film obtained from the thermosetting resin composition according to any one of claims 1 to 19. A cured film-attached substrate comprising the cured film according to claim 20. An electronic part comprising the cured film according to claim 20 or the cured film-attached substrate according to claim 21. 23. The method of claim 22,
Touch panel, electronic parts.