JP2002212236A - Thermosetting resin composition, transfer printing material, and method for forming interlayer insulation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in resistance to heat or chemicals, storage stability, and high-temperature reactivity, a transfer printing material using the same, and a method for forming an interlayer insulation film. SOLUTION: This resin composition contains, based on the total solid content, 1 mass%-100 mass% copolymer which is obtained from a monomer mixture containing 5-80 mol% polymerizable monomer represented by the formula I (wherein R1 is H or methyl; and X is a halogen atom, a hydroxyl group, or an optionally substituted alkoxy, aryloxy, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkylsulfonyloxy, or arylsulfonyloxy group) and 5-80 mol% carboxyl-group-containing monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

[0002]

2. Description of the Related Art In recent years, high definition of active matrix liquid crystal display devices has become an issue, and many attempts have been made to improve the aperture ratio of liquid crystal display elements. This is to prevent a decrease in aperture ratio and a decrease in light transmittance, although the pixel size is reduced in accordance with the pursuit of higher definition. In order to increase the aperture ratio, for example, techniques called a so-called high aperture (hereinafter abbreviated as HA) method and a color filter on array (hereinafter abbreviated as COA) method have appeared. The HA method is a method in which a pixel electrode is formed on a transparent interlayer insulating film provided in advance on a signal wiring in order to provide the pixel electrode so as to overlap the signal wiring. By using a photosensitive insulating resin as the transparent interlayer insulating layer, it is possible to manufacture a TFT substrate having high productivity and a high aperture ratio in which capacitive crosstalk is suppressed (Japanese Patent Application Laid-Open No. 6-242433, US Pat. No. 5,780,871). Description) is known.

Japanese Patent Application Laid-Open No. 9-96837 discloses an HA
It discloses that not only the transmittance of the color filter but also the viewing angle is improved by defining the height difference or step on the surface of the TFT substrate, the thickness of the transparent interlayer insulating film, the dielectric constant, and the light transmittance.

An active matrix substrate in a transmission type liquid crystal display device of the HA system will be described with reference to FIG.

FIG. 1 is a sectional view showing a structure of one pixel portion of an active matrix substrate in a transmission type liquid crystal display device. In FIG. 1, a gate electrode 12 is provided on a transparent insulating substrate 11, and a gate insulating film 13 is provided on the gate electrode 12. A semiconductor layer 14 is provided on the gate insulating film 13 so as to overlap with the gate electrode 12, and a channel protection layer 15 (the channel protection film 15 can be simplified depending on a manufacturing process) is provided on a central portion of the semiconductor layer 14. Is provided. An n + Si layer covering both ends of the channel protective layer 15 and the semiconductor layer 14 is provided, and one end of the channel protective layer 15 is
A, the other end side is a drain electrode 16B. A metal layer 17 is provided on an end of the source electrode 16A on the side opposite to the channel protective layer 15 side to serve as a source signal line. Further, a metal layer 21 is provided on an end of the drain electrode 16B opposite to the channel protective layer 15 side. A transparent interlayer insulating film 18 is provided on the protection channel 15, the source electrode 16A, the drain electrode 16B, and the metal layers 17 and 21. This transparent interlayer insulating film 18
A contact hole 20 is formed at a position on the metal layer 21. A pixel electrode 19, which is a transparent conductive film, is provided so as to cover the contact hole 20. The pixel electrode 19 is connected to the drain electrode 16 of the TFT via a metal layer 21.
B.

The COA method (for example, Japanese Patent Application Laid-Open No. 10-20688)
The configuration according to 8) is similar to the configuration in the above-mentioned HA method except that a colored resin is used instead of the transparent insulating film. It is said that the COA method can realize a higher aperture ratio than the HA method because the HA method eliminates the need for setting the alignment error margin between the color filter substrate and the electrode substrate and eliminates the need to set an alignment error margin. I have.
As another method of the COA technique, a method of using a color filter layer 22 and a transparent interlayer insulating film directly on top of each other is also known (FIG. 2).

Liquid photosensitive resins are known as photosensitive insulating resins used in these methods. According to the method of applying the liquid photosensitive resin, it is possible to easily improve the mass productivity and reduce the cost. In addition, this coating method, compared with the sputtering method, reduces the difference in height or level difference of the waviness of the surface of the transparent interlayer insulating film formed when unevenness due to the structure occurs in the lower layer of the transparent interlayer insulating film. By forming a transparent interlayer insulating film using a coating solution having a viscosity of 100 cps or less, the thickness can be reduced to 500 angstrom or less. Further, when a photosensitive material is used, steps such as resist application and stripping can be simplified, and further cost reduction can be achieved. It is also known that when the transparent interlayer insulating film is formed to a thickness of 1.5 μm or more, leak defects and the like can be reduced, reliability can be improved, and the yield can be improved, and the cost can be reduced by improving the yield.

However, in recent years, as liquid crystal display devices have become larger for television applications and the like, large-area substrates (6
In the case of forming an insulating film by a coating method (80 mm × 880 mm or more), the problem caused by uneven coating cannot be ignored. Specifically, when a large number of TFTs are present on a large area substrate, unevenness occurs and the insulation becomes non-uniform,
Malfunction occurs. That is, due to the variation in the film thickness in the application surface, the pulling in of the potential of the pixel capacitance due to the capacitance between the edge of the pixel electrode 19 and the gate signal line 12 is not uniform, and the display quality and the reliability are deteriorated. In addition, there is a problem that the accuracy of the shape of the contact hole is insufficient, and the amount of residual film after development at the bottom of the contact hole varies greatly.

On the other hand, photolithography using a photosensitive resin has a complicated manufacturing process and is expensive, and a simpler manufacturing method is required.

As a simpler manufacturing method, for example, a method for manufacturing a multicolor image such as a color filter using a laser ablation technique is disclosed in Japanese Patent Application Laid-Open No. 9-3188.
11, JP-A-10-8294, JP-A-10-1639
6, JP-A-10-39129, JP-A-10-96812
In each publication. According to these methods, a photomask is not required, and a conventional UV light irradiation device and wet developing equipment are not required.

That is, after securing a uniform film thickness by a transfer method of a thermosetting resin layer applied in advance on a film with high precision, a thermosetting resin is applied as a transparent insulating layer, and a laser ablation method is used. A method of making holes is an effective means for achieving these problems in the insulating layer forming technology.

A transfer material using a thermosetting resin is found in the field of multilayer printed wiring boards.

A typical example of a conventional thermosetting resin composition for an interlayer adhesive film for multilayer printed wiring is disclosed in JP-A-11-87.
927, the resin composition which is solid at room temperature contains (A) an epoxy resin which is liquid at room temperature (
B) 2 in one molecule having a softening point above the lamination temperature
A multifunctional epoxy resin (C) having two or more epoxy groups, and a resin having a latent epoxy curing agent that initiates a reaction at a temperature higher than the lamination temperature as an essential component are described.

Thermosetting resins are also used in the field of liquid crystal displays.
No. 3 describes that a thermosetting resin composition containing (A) an epoxy group-containing compound and (B) a surfactant is used as a protective film for a color filter.

As in these examples, as the thermosetting resin composition, a composition based on an epoxy resin is generally used, and the composition is cured by devising a latent epoxy curing agent for accelerating the curing. Speed and some storage stability have been ensured. However, these thermosetting resin film products require a low-temperature environment of about −5 ° C. for storage, and the storage stability of these thermosetting resin compositions is several μm.
In order to stably thermally laminate a thin insulating layer without bubbles, it is still insufficient, so that it cannot be applied to the liquid crystal display field.

Therefore, in order to manufacture an interlayer insulating film for a liquid crystal display at low cost and with high precision by a laser ablation method, a thermosetting resin composition capable of forming a transparent thin film of a transfer material having excellent thermal stability has been developed. Was sought.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide an active matrix substrate for an HA method liquid crystal display device,
An object of the present invention is to provide a thermosetting resin composition capable of forming a transparent resin insulating layer having a uniform thickness and an excellent contact hole shape formed by a laser ablation method, and a transfer material using the same.

Another object of the present invention is to provide a method for forming a transparent interlayer insulating film on an active matrix substrate for a liquid crystal display device by the HA method or the COA method using the present transfer material.

It is a further object of the present invention to provide a thermosetting resin composition having excellent heat resistance, chemical resistance, storage stability and high-temperature reactivity.

[0020]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above conventional problems can be solved by using a specific crosslinking agent, and have completed the present invention. <1> A copolymer containing 5 to 80 mol% of a polymerizable monomer represented by the following general formula I and 5 to 80 mol% of a carboxylic acid group-containing monomer as a monomer is contained in an amount of 1% by mass to 10% in a total solid content.
A thermosetting resin composition containing 0% by mass.

[0021]

Embedded image

(Where R ¹ represents a hydrogen atom or a methyl group; X represents a halogen atom, a hydroxy group,
12, which may have a substituent, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group,
Represents an arylcarbonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group. <2> The thermosetting resin composition according to <1>, wherein the copolymer is synthesized from the polymerizable monomer of the general formula I, a carboxylic acid group-containing monomer, and an ethylenically unsaturated monomer. <3> (A) 99 to 40% by mass of the total solid content, a resin having a carboxylic acid group in the molecule of 10 to 300 in terms of acid value, and (B) 1 to 60% by mass of the total solid content. A thermosetting resin composition comprising a compound represented by the following general formula II:

[0023]

Embedded image

(Where A represents an organic residue having at least two oxygen atoms at the terminal. X comprises a halogen atom, a hydroxy group, and a carbon number of 1 to 12, and may have a substituent. An alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group,
Represents an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group, and n represents an integer of 2 or more. <4> The thermosetting resin composition according to any one of <1> to <3>, further including a decolorizable colorant. <5> A transfer material comprising, on a support, a layer comprising the thermosetting resin composition according to any one of <1> to <4>. <6> The transfer material according to <5>, wherein a release layer, a layer of the thermosetting resin composition, and a protective film are provided on a support. <7> The transfer material according to <5>, wherein a thermoplastic layer, an intermediate layer, a layer of the thermosetting resin composition, and a protective film are provided on a support. <8> (1) <5> on active matrix substrate
To forming a thermosetting resin composition layer by laminating any of the transfer materials of <1> to <7>, (2) heating and curing the thermosetting resin composition layer, and (3) applying a laser beam. Irradiating the transparent thermosetting resin layer with a laser beam by irradiating the transparent thermosetting resin layer imagewise. <9> The method for forming an interlayer insulating film according to <8>, further comprising a step of forming a multicolored resin film on the active matrix substrate before forming the thermosetting resin composition layer. <10> The method for forming an interlayer insulating film according to <9>, wherein the color of the colored resin layer is four colors of red, blue, green, and black.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin composition of the present invention comprises
A polymer (crosslinking agent (1)) obtained by copolymerization of the polymerizable monomer represented by the general formula I and 5 to 80 mol% of a carboxylic acid group-containing monomer is 1 to 100% by mass in the total solid content. Or (A) 99 to 40% by mass of the total solid content of a carboxylic acid group in the molecule, having an acid value of 10 to 300
Resin (hereinafter, referred to as carboxylic acid group-containing alkali-soluble resin), and (B) 1 to 60% by mass of the total solid content
(Crosslinking agent (2)).

The crosslinking agent (1) contains 5 mol% to 80 mol% of a polymerizable monomer represented by the following general formula I and 5 mol% to 80 mol% of a carboxylic acid group-containing monomer as essential components. Unlike monomers, it is a polymer crosslinker obtained by copolymerization of other ethylenically unsaturated monomers copolymerizable with these monomers.

[0027]

Embedded image

Here, R ¹ represents a hydrogen atom or a methyl group, X represents a halogen atom, a hydroxy group, and a C ¹ -C 12 group.
Consisting of an optionally substituted alkoxy group,
Aryloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylsulfonyloxy group, represents an arylsulfonyloxy group,
Examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group, and an aryl group.

Examples of the monomer represented by the general formula I include 3-chloro-2-hydroxypropyl (meth) acrylate, 3-bromo-2-hydroxypropyl (meth) acrylate, 3-fluoro-2-hydroxypropyl (Meth) acrylate, 3-iodo-2-hydroxypropyl (meth) acrylate, 3-methoxy-2-hydroxypropyl (meth) acrylate, 3-ethoxy-2-hydroxypropyl (meth) acrylate, 3-
t-butoxy-2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3-acetoxy-2-hydroxypropyl (meth) acrylate, 3-benzoyloxy-
Examples thereof include 2-hydroxypropyl (meth) acrylate and 3-methoxycarbonyloxy-2-hydroxypropyl (meth) acrylate, with 3-chloro-2-hydroxypropyl (meth) acrylate being particularly preferred.

Examples of the carboxylic acid group-containing monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, cinnamic acid, and acrylic acid dimer. An addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride can also be used. Among these, (meth) acrylic acid is particularly preferred.

Examples of other monomers include those of the general formula I
Examples of the monomer and the carboxylic acid group-containing monomer can include an ethylenically unsaturated monomer copolymerizable with,
It is preferable that the monomer does not have chemical reactivity with a group other than the ethylenically unsaturated group contained in the monomer.
Specifically, acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylonitrile, (meth) acrylamides, Styrenes and vinyl ethers are preferred. Examples of such a compound include the following compounds.

Examples of the acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, and acetoxyethyl acrylate. ,
Examples thereof include phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, cyclohexyl acrylate, and benzyl acrylate.

Examples of the methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, te
rt-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, acetoxyethyl methacrylate, phenyl methacrylate, 2-
Hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate,
2- (2-methoxyethoxy) ethyl methacrylate,
Examples include cyclohexyl methacrylate and benzyl methacrylate.

Examples of crotonic esters include butyl crotonate and hexyl crotonate.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate and the like.

The maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate and the like.

The diesters of fumaric acid include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

The acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, t
tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, di # methylacrylamide, diethylacrylamide, phenylacrylamide, benzylacrylamide and the like.

Examples of the methacrylamides include methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, 2-methoxyethyl methacrylamide, di # methyl Examples include methacrylamide, diethyl methacrylamide, phenyl methacrylamide, and benzyl methacrylamide.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like.

The styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene,
Methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate, α-methylstyrene, and the like.

In addition, maleimide, vinylpyridine, vinylpyrrolidone, vinylcarbazole and the like can also be used.

These compounds may be used alone or in combination of two or more. Examples of particularly preferred other monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, benzyl methacrylate, styrene, methylstyrene, α-methylstyrene, chlorostyrene, Bromostyrene, chloromethylstyrene, hydroxystyrene and the like.

Particularly preferred copolymers include a copolymer of 3-chloro-2-hydroxypropyl methacrylate and methacrylic acid, a copolymer of 3-chloro-2-hydroxypropyl methacrylate and cyclohexyl methacrylate and methacrylic acid, Copolymers of chloro-2-hydroxypropyl methacrylate, benzyl methacrylate and methacrylic acid can be mentioned.

Such a copolymer can be obtained by copolymerizing a monomer by a known method. For example, it can be obtained by adding a radical polymerization initiator to a solution in which these monomers are dissolved in an appropriate solvent and polymerizing the monomers in the solution. These monomers dispersed in an aqueous medium may be polymerized by so-called emulsion polymerization.

Examples of suitable solvents can be arbitrarily selected depending on the monomers to be used and the solubility of the copolymer to be formed. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, Acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate,
Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene, and mixtures thereof can be used. As a polymerization initiator, 2,2′-azobis (isobutyronitrile) (AIB
N), an azo-based polymerization initiator such as 2,2'-azobis- (2,4'-dimethylvaleronitrile), a peroxide-based polymerization initiator such as benzoyl peroxide, a persulfate, and the like can be used. .

When the preferred composition ratio of the copolymer contained in the composition of the present invention is represented by mol%, the amount of the monomer (a) of the general formula I is 5 to 80 mol%, and the amount of the monomer having a carboxylic acid group ( b) is preferably from 5 to 80 mol%, the amount of the other monomer (c) is preferably from 0 to 80 mol%, the amount of the monomer of general formula I (a) is from 10 to 70 mol%, and the amount of the monomer having a carboxylic acid group (b) Is more preferably from 10 to 70 mol%, and the amount of the other monomer (c) is more preferably from 0 to 70 mol%.
It is particularly preferable that the monomer amount (a) is 20 to 60 mol%, the monomer amount having a carboxylic acid group (b) is 20 to 60 mol%, and the other monomer amount (c) is 0 to 60 mol%.
(Here, a + b + c = 100 mol%.) When the amount of the monomer (a) of the general formula I is less than 5 mol%, the resistance after curing by baking is insufficient, and when it exceeds 80 mol%, the film after curing is cured. Decreases the chemical resistance. If the amount of the carboxylic acid group-containing monomer (b) is less than 5 mol%, the curability is insufficient, and if it exceeds 80 mol%, the change in film properties due to humidity is large. If the amount of the other monomer (c) exceeds 80 mol%, the resistance after baking hardens.

The molecular weight of the copolymer can be arbitrarily adjusted, but the weight average molecular weight is preferably from 2,000 to 200,000, particularly preferably from 4,000 to 100,000. When the weight average molecular weight is less than 2,000, the strength of the film becomes insufficient. When the weight average molecular weight exceeds 200,000, the film formability during coating is reduced.

Such a monomer containing a hydroxyl group and an X group and a copolymer thereof are known. Monomers are used as reactive diluents in photosensitive resin compositions, paints and adhesives, and copolymers are used as copolymers in pressure-sensitive adhesive compositions. (For example, JP-A-4-29351, 4-145183, 7-13330, 7-1
However, these are those in which these units are introduced as a kind of vinyl monomer, and in the copolymer containing a carboxylic acid group in the same molecule as in the present invention, It is not aimed at the manifestation of a specific effect, and there is no description about the manifestation of a specific effect.

It is also known that these are introduced as one of the halogen-containing resins (Japanese Patent Laid-Open No. Hei 3-8888).
3). However, this is a component of the photocurable adhesive, and is different from the stabilization at room temperature and the thermosetting at a high temperature as in the present invention. There is also known an example in which a function as a low-temperature crosslinking component is imparted to such a unit. (Japanese Patent Laid-Open No. 5-555
26, etc.) In this case, however, the unit having a hydroxyl group and a halogen and the unit having an amine salt are both introduced into the copolymer to impart self-crosslinking properties at a low temperature. However, even in this example, there is no description of the low-temperature stability when a carboxyl group is introduced into the molecule, nor the cross-linking by baking at a high temperature as in the present invention.

The crosslinking agent (1) can also serve as the component (A). In that case, other resins containing carboxylic acid groups in oxidation 10 to 300 can be omitted.

The carboxylic acid group-containing alkali-soluble resin includes
This resin is obtained by copolymerization of a carboxylic acid group-containing monomer and a carboxylic acid group-free monomer, or by a polymer reaction of a hydroxyl group-containing resin such as celluloses and PVA, and is soluble in a weak alkaline aqueous solution. Examples of the resin soluble in the weak alkaline aqueous solution include known polymer binders used for the alkali-soluble photopolymerizable resin. In particular,
Copolymers of (meth) acrylic acid and alkyl (meth) acrylate (alkyl groups such as methyl group, ethyl group, butyl group, etc.), poly (meth) acrylic acid, styrene and maleic anhydride, etc. There are copolymers of a saturated dibasic acid anhydride, a reaction product of the polymer with an alcohol, a reaction product of the polymer with a polybasic acid anhydride of cellulose, and the like. Among the above-mentioned polymers, those preferably used in the present invention include styrene / maleic anhydride copolymer, methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / methacrylic acid described in JP-A-60-258439. Benzyl quaternary copolymer, Tokiko Sho 55
Styrene / maleic acid mono-described in JP-A-38961
n-butyl ester copolymer, JP-B-54-25957
Quaternary copolymer of styrene / methyl methacrylate / ethyl acrylate / methacrylic acid described in JP-A No.
Benzyl methacrylate / methacrylic acid copolymer described in JP-B-99810, acrylonitrile / 2-ethylhexyl methacrylate described in JP-B-58-12577.
Terpolymer of methacrylic acid and JP-B-55-62
No. 10 terpolymer of methyl methacrylate / ethyl acrylate / acrylic acid and styrene / maleic anhydride copolymer partially esterified with isopropanol.

The carboxylic acid group-containing resin used in the present invention is:
Usually, an acid value in the range of 10 to 300 mg KOH / g and 1
It preferably has a weight average molecular weight in the range of 000 to 300,000. When the acid value is less than 10 mg KOH / 1 g, the curability is greatly reduced, and the acid value is less than 300 mg KOH.
If it exceeds / 1 g, it will be difficult to obtain sufficient alkali water resistance. Further, a plurality of carboxylic acid group-containing resins may be used in combination. The preferable addition amount of the carboxylic acid group-containing resin is 10 to 80% by mass of the total solid, and the more preferable addition amount is 20 to 60% by mass. Further, in order to maintain the contact hole shape in a rubbed shape, the mass ratio (A / B) of the component (A) and the component (B) is desirably 0.5 to 0.9.

The component (B) is selected from low-molecular-weight crosslinking agents which are crosslinking agents (2).

The crosslinking agent (2) is at least one low molecular crosslinking agent represented by the following general formula II.

[0057]

Embedded image

Here, A represents an organic residue having at least two oxygen atoms at the terminal. X is a halogen atom, a hydroxy group, having 1 to 12 carbon atoms, which may have a substituent; an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyloxy group, an aryloxy Represents a carbonyloxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group, and the substituent is selected from a halogen atom, a hydroxy group, an alkoxy group, and an aryl group. n
Represents an integer of 2 or more.

Low molecular weight crosslinking agent (2) represented by general formula II
Examples of polyols include poly (3-halo-2-hydroxypropyl) ethers of polyol and poly (3-halo-2-hydroxypropyl) of polyol.
Hydroxy-2-hydroxypropyl) ethers, polyol poly (3-alkoxy-2-hydroxypropyl) ethers, polyol poly (3-aryloxy-2-hydroxypropyl) ethers, polyol poly (3-acyloxy) -2-hydroxypropyl) ethers, polyol poly (3-aryloxycarbonyloxy-2-hydroxypropyl) ethers, polyol poly (3-alkylsulfonyloxy-2-hydroxypropyl) ethers, polyol poly ( 3-arylsulfonyloxy-2-hydroxypropyl) ethers and polyphenol poly (3-
Halo-2-hydroxypropyl) ethers, poly (3-hydroxy-2-hydroxypropyl) ethers of polyphenols, poly (3-alkoxy-2-hydroxypropyl) ethers of polyphenols, poly (3-aryloxy) of polyphenols -2-hydroxypropyl) ethers, polyphenol poly (3-acyloxy-2-hydroxypropyl) ethers, polyphenol poly (3-alkylcarbonyloxy-2-)
Hydroxypropyl) ethers, polyphenol poly (3-arylcarbonyloxy-2-hydroxypropyl) ethers, polyphenol poly (3-alkylsulfonyloxy-2-hydroxypropyl) ethers, polyphenol poly (3-arylsulfonyl) Oxy-2-hydroxypropyl) ethers, poly (3-halo-2-hydroxypropyl) ethers of polyol polyphenols, poly (3-acyloxy-2-hydroxypropyl) ethers of polyol polyphenols, poly (3 -Alkoxy-2-hydroxypropyl) ethers and poly (3-alkoxycarbonyloxy-2-hydroxypropyl) ethers of polyol polyphenols.

Specific illustrative compounds are as follows.
Poly (3-halo-2-hydroxypropyl) ethers of polyols include trimethylolpropane tri (3-chloro-2-hydroxypropyl) ether, trimethylolpropane tri (3-bromo-2-hydroxypropyl) ether, Trimethylolethane (3
-Chloro-2-hydroxypropyl) ether, pentaerythritol tetra (3-chloro-2-hydroxypropyl) ether, trimethylolmethanetri (3-chloro-2-hydroxypropyl) ether, dipentaerythritol penta (3-chloro- 2-hydroxypropyl) ether, ethylene glycol di (3-chloro-
2-hydroxypropyl) ether, 1,2-propylene glycol di (3-chloro-2-hydroxypropyl) ether, 1,3-propylene glycol di (3-
Chloro-2-hydroxypropyl) ether, ethylene glycol di (3-chloro-2-hydroxypropyl)
Ether, tetramethylene glycol di (3-chloro-
2-hydroxypropyl) ether, hexanediol di (3-chloro-2-hydroxypropyl) ether,
1,4-cyclohexanediol di (3-chloro-2-
Hydroxypropyl) ether, diethylene glycol di (3-chloro-2-hydroxypropyl) ether,
Polyoxyethylene glycol di (3-chloro-2-hydroxypropyl) ether, tris (4-hydroxycyclohexyl) methane tri (3-chloro-2-hydroxypropyl) ether, poly (3-chloro-2-hydroxypropyl acrylate) oligomer , Poly (3-
Chloro-2-hydroxypropyl methacrylate) oligomers, such as polyol poly (3-acyloxy-2-hydroxypropyl) ethers, polyol poly (3-hydroxy-2-hydroxypropyl) ethers, and polyol poly (3 -Alkoxy-2-hydroxypropyl) ethers and polyol poly (3
-Aryloxy-2-hydroxypropyl) ethers, polyol poly (3-acyloxy-2-hydroxypropyl) ethers, polyol poly (3-alkoxy-2-hydroxypropyl) ethers, polyol poly (3- Alkoxycarbonyloxy-2-
Hydroxy (propyl) ethers, polyol poly (3-aryloxycarbonyloxy-2-hydroxypropyl) ethers, polyol poly (3-alkylsulfonyloxy-2-hydroxypropyl) ethers, polyol poly (3-aryl) Sulfonyloxy-2-hydroxypropyl) ethers include
Trimethylolpropane tri (3-acetoxy-2-hydroxypropyl) ether, pentaerythritol poly (3-acetoxy-2-hydroxypropyl) ether, pentaerythritol poly (3-chloroacetoxy-2-hydroxypropyl) ether, trimethylol Propane tri (3-hydroxy-2-hydroxypropyl) ether, trimethylolpropane tri (3-methoxy-2-hydroxypropyl) ether,
Trimethylolpropane tri (3-phenoxy-2-hydroxypropyl) ether, trimethylolpropane tri (3-methoxycarbonyloxy-2-hydroxypropyl) ether, trimethylolpropane tri (3
-Phenoxycarbonyloxy-2-hydroxypropyl) ether, trimethylolpropanetri (3-methanesulfonyloxy-2-hydroxypropyl) ether, trimethylolpropanetri (3-benzenesulfonyloxy-2-hydroxypropyl) ether Can be.

Examples of poly (3-halo-2-hydroxypropyl) ethers of polyphenol include bisphenol A-di (3-chloro-2-hydroxypropyl) ether and bisphenol A-di (3-bromo-2-hydroxypropyl). ) Ether, bisphenol S-di (3-
Chloro-2-hydroxypropyl) ether, bis (p
-Hydroxyphenyl) methanedi (3-chloro-2-hydroxypropyl) ether, bis (p-hydroxy-
m-methylphenyl) methanedi (3-chloro-2-hydroxypropyl) ether, bis (p-hydroxy-
m, m'-dimethylphenyl) methanedi (3-chloro-
2-hydroxypropyl) ether, bis (o-hydroxyphenyl) methanedi (3-chloro-2-hydroxypropyl) ether, bis (o-hydroxy-m-methylphenyl) methanedi (3-chloro-2-hydroxypropyl) ether , 2,2-bis (p-hydroxy-m
-Methylphenyl) propanedi (3-chloro-2-hydroxypropyl) ether, 2,2-bis (p-hydroxy-m, m'-dimethylphenyl) propanedi (3-
Chloro-2-hydroxypropyl) ether, 2,2-
Bis (p-hydroxy-m-isopropylphenyl) propanedi (3-chloro-2-hydroxypropyl) ether, 2,2-bis (p-hydroxy-m-sec-butylphenyl) propanedi (3-chloro-2-hydroxy Propyl) ether, 2,2-bis (p-hydroxy-m-tert-butylphenyl) propanedi (3-chloro-2-hydroxypropyl) ether, 2,2-bis (p-hydroxy-m-phenylphenyl) propanedi (3-chloro-2-hydroxypropyl) ether,
2,2-bis (p-hydroxy-m-cyclohexylphenyl) propanedi (3-chloro-2-hydroxypropyl) ether, 2,2-bis (p-hydroxyphenyl) butanedi (3-chloro-2-hydroxypropyl)
Ether, 2,2-bis (p-hydroxyphenyl),
4-methylpentanedi (3-chloro-2-hydroxypropyl) ether, 2,2-bis (p-hydroxyphenyl), 2-phenylethane (3-chloro-2-hydroxypropyl) ether, 1,1-bis (P-hydroxyphenyl) cyclohexanedi (3-chloro-2-hydroxypropyl) ether, 1,1-bis (p-hydroxy-m-methylphenyl) cyclohexanedi (3-chloro-2-hydroxypropyl) ether, 1 1,1-bis (p-hydroxy-m-cyclohexylphenyl) cyclohexanedi (3-chloro-2-hydroxypropyl) ether, 1,1-bis (p-hydroxyphenyl) cyclopentanedi (3-chloro-2-hydroxy Propyl) ether, 1,1-bis (p-hydroxy-m
-Methylphenyl) cyclopentanedi (3-chloro-2
-Hydroxypropyl) ether, 1,1-bis (p-
Hydroxy-m-isopropylphenyl) pentanedi (3-chloro-2-hydroxypropyl) ether, tris (p-hydroxyphenyl) methanetri (3-chloro-2-hydroxypropyl) ether, tris (p-
Hydroxyphenyl) methanedi (3-chloro-2-hydroxypropyl) ether, tris (p-hydroxy-
m-methylphenyl) methanetri (3-chloro-2-hydroxypropyl) ether, 2,2-bis (p-hydroxyphenyl) -2 (2-p-hydroxyphenylpropylphenyl) -ethanetri (3-chloro-2- Hydroxypropyl) ether, 2,6-bis (o-hydroxy-m-methylphenylmethyl) -4-cresoltri (3-chloro-2-hydroxypropyl) ether,
4-benzylpyrogallol tri (3-chloro-2-hydroxypropyl) ether, poly (3-chloro-2-hydroxypropyl) ether of cresol novolak resin, poly (3-chloro-2) of phenol novolak resin
-Hydroxypropyl) ether, poly (3-chloro-2-hydroxypropyl) ether of polyhydroxystyrene oligomer, biphenoldi (3-chloro-2-
Hydroxypropyl) ether, such as polyphenol poly (3-acyloxy-2-hydroxypropyl) ethers, polyphenol poly (3-hydroxy-2-hydroxypropyl) ethers, and polyphenol poly (3-alkoxy-2-). (Hydroxypropyl) ethers, polyphenol poly (3-aryloxy-2-hydroxypropyl) ethers, polyphenol poly (3-acyloxy-2-hydroxypropyl) ethers, polyphenol poly (3-alkoxy-2-hydroxy) Propyl) ethers and polyphenol poly (3-alkoxycarbonyloxy-2)
-Hydroxypropyl) ethers, poly (3-aryloxycarbonyloxy-2-hydroxypropyl) ethers of polyphenols, poly (3-alkylsulfonyloxy-2-hydroxypropyl) ethers of polyphenols, poly (3- Examples of arylsulfonyloxy-2-hydroxypropyl) ethers include bisphenol A-di (3-acetoxy-2-hydroxypropyl) ether and poly (3-acetoxy-phenol) of phenol novolak resin, respectively.
2-hydroxypropyl) ether, bisphenol A
-Di (3-hydroxy-2-hydroxypropyl) ether or poly (3-hydroxy-2-hydroxypropyl) ether of phenol novolak resin, bisphenol A-di (3-methoxy-2-hydroxypropyl) ether or phenol novolak resin Poly (3-methoxy-2-hydroxypropyl) ether, bisphenol A-di (3-phenoxy-2-hydroxypropyl)
Poly (3-phenoxy-2-hydroxypropyl) ether of ether or phenol novolak resin, poly (3-methoxycarbonyloxy-2) of bisphenol A-di (3-methoxycarbonyloxy-2-hydroxypropyl) ether or phenol novolak resin -Hydroxypropyl) ether, bisphenol A-di (3-
Phenoxycarbonyloxy-2-hydroxypropyl) ether or phenol novolak resin poly (3-
Phenoxycarbonyloxy-2-hydroxypropyl) ether, bisphenol A-di (3-methanesulfonyloxy-2-hydroxypropyl) ether, poly (3-methanesulfonyloxy-2-hydroxypropyl) ether of phenol novolak resin, bisphenol A -Di (3-benzenesulfonyloxy-2-hydroxypropyl) ether and poly (3-benzenesulfonyloxy-2-hydroxypropyl) ether of phenol novolak resin can be mentioned.

Examples of poly (3-halo-2-hydroxypropyl) ethers of polyol polyphenols include poly (3-chloro-2-hydroxypropyl) ether derived from polyglycidyl ether of phenoxy resin by a hydrochloric acid addition reaction. Is mentioned.

In general, the greater the number of functional groups per molecule in these compounds, the better the efficiency as a crosslinking agent, but if the molecular weight is too large, it is disadvantageous in terms of compatibility with other components. Therefore, the number average molecular weight is generally from 200 to 50,000, preferably from 300 to 10,000.
And more preferably from 350 to 5,000. Among these compounds, the most preferred compounds are bisphenol A-di (3-chloro-2-hydroxypropyl) ether and poly (3-phenol-novolak resin).
Chloro-2-hydroxypropyl) ether, pentaerythritol tetra (3-chloro-2-hydroxypropyl) ether, trimethylolmethanetri (3-chloro-2-hydroxypropyl) ether phenol, bisphenol A-di (3-acetoxy- 2-hydroxypropyl) ether, poly (3-acetoxy-2-hydroxypropyl) ether of phenol novolak resin, pentaerythritol tetra (3-acetoxy-2)
-Hydroxypropyl) ether, pentaerythritol poly (3-chloroacetoxy-2-hydroxypropyl) ether, and trimethylolmethanetri (3-acetoxy-2-hydroxypropyl) ether.

The amount of the crosslinking agent added is 10 to 100% by mass of the total solid content of the composition, and preferably 15 to 80% by mass.
%, Particularly preferably from 20 to 70% by mass. When the added amount of the crosslinking agent is less than 10% by mass, the cured product required for the insulating layer is insufficient in heat resistance, spatter resistance, chemical resistance, hardness and the like. Further, although the molar equivalent of the carboxylic acid group in the molecule of the component (A) and the molar equivalent of the 3-chloro-2-hydroxypropyl group in the molecule of the component (B) are equal, the resulting cured film has excellent resistance, They do not have to be the same.

Other crosslinking agents can be added to the composition of the present invention as long as storage stability is not deteriorated.

Other suitable crosslinking agents include compounds capable of addition polymerization having at least two ethylenically unsaturated bonds.

The addition-polymerizable compound having at least two ethylenically unsaturated bonds is selected from compounds having two or more terminal ethylenically unsaturated bonds in one molecule. For example, monomers, prepolymers, ie, dimers, trimers and oligomers, mixtures thereof and copolymers thereof. Examples of the monomer include an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with an aliphatic polyhydric alcohol compound, and an unsaturated carboxylic acid and an aliphatic carboxylic acid. Examples include amides with polyvalent amine compounds.

Specific examples of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates, methacrylates, itaconic esters, crotonic esters, isocrotonic esters, maleic esters and the like. .

More specifically, acrylates include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, and neopentyl glycol diacrylate. Acrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol Diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta Risuri tall diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl)
There are isocyanurate, polyester acrylate oligomer and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis [p- (methacryloxyethoxy)
Phenyl] dimethylmethane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4 butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Specific examples of the amide of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylenebis-
Acrylamide, methylenebis-methacrylamide,
1,6-hexamethylenebis-acrylamide, 1,6
-Hexamethylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As another example, see JP-B-48-417.
JP-A-08-0832, a polyisocyanate compound having two or more isocyanate groups in one molecule and a hydroxyl-containing vinyl monomer represented by the following general formula III being added, two or more in one molecule. And vinyl urethane compounds containing a polymerizable vinyl group. General formula III CH ₂ CC (R) COOCH ₂ CH (R ¹ ) OH In the formula, R and R ¹ each independently represent hydrogen or a methyl group.

Further, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490 also have at least two ethylenically unsaturated bonds. It can be mentioned as a compound capable of addition polymerization. Furthermore, the Japan Adhesion Association magazine vol.20, No.
7, pages 300 to 308 (1984) as photocurable monomers and oligomers can also be used. These addition-polymerizable compounds having at least two ethylenically unsaturated bonds can be used alone or in combination of two or more.

The amount of the addition polymerizable compound having at least two ethylenically unsaturated bonds is 50% by mass or less, preferably 30% by mass or less based on the total solid content.

In addition to these essential components, the thermosetting resin composition of the present invention contains, for various purposes, a surfactant, an adhesion promoter,
Various additives such as a thermal polymerization inhibitor, an oxygen polymerization inhibitor, a plasticizer, and a decolorizable colorant can be added.

The surfactant can be used for improving the coating property and the smoothness of the obtained coating film. Specific examples thereof include, for example, BM-1000 (BM Chemie)
Company), MegaFac F142D, F172, F1
73, F183 (above, Dainippon Ink and Chemicals, Inc.)
Co., Ltd.), Florard FC-135, FC-170C, Florard FC-430, FC-431 (all manufactured by Sumitomo 3M Limited), Surflon S-112, S-1
13, S-131, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-19
0, SH-193, SZ-6032, SF-8428,
Examples thereof include a fluorine-based or silicone-based surfactant commercially available under the trade name of DC-57 and DC-190 (both manufactured by Toray Silicone Co., Ltd.). The amount of the surfactant to be used is generally 5% by mass or less, preferably 2% by mass or less, based on the total solid content.

The adhesion promoter is added in order to improve the adhesion between the thermosetting resin composition and the substrate when the layer of the thermosetting resin composition of the present invention is formed on the substrate. As the adhesion promoter, a functional silane coupling agent can be suitably used. In the present specification, the functional silane coupling agent means a silane compound having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group, and specific examples thereof include trimethoxysilylbenzoic acid. , Γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane,
Examples thereof include vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The preferred use amount of the adhesion promoter is 10% by mass or less, particularly preferably 0.05 to 5% by mass, based on the total solid content.

When the thermosetting resin layer is used, it is preferable that the thermosetting resin layer is colored for the purpose of inspecting the properties of the thermosetting resin layer surface after application and coating defects, but the final cured image is substantially It must be colorless and transparent. For this purpose, it is possible to use a coloring agent which is decolored by heating or light irradiation.

As the decolorizable colorant, those which decolorize by decomposition in the course of heat treatment at a temperature of 150 ° C. or more for 10 minutes to 150 minutes, those which fly out of the system, and those which react with other components Those that decompose and decolor can be used.
As such a decolorizable colorant, a triphenylmethane dye that easily transmits light in the UV region and has excellent decoloration properties after heat treatment can be advantageously used. For example, preferred dyes include crystal violet, methyl violet,
Ethyl violet, oil blue # 603, Victoria Pure Blue BOH, malachite green, diamond green and the like.
−97061, Japanese Patent Application Laid-Open No. 10-104827, and
The colorants described in US Pat. The preferred use amount of the decolorizable colorant is 10% by mass or less based on the total solid content, and particularly preferably 0.05 to 5% by mass.

When a polymerizable compound having at least two polymerizable ethylenically unsaturated groups is used as a crosslinking agent, the thermopolymerization inhibitor can be polymerized during the production or storage of the thermosetting resin composition layer. It is used to prevent unnecessary thermal polymerization of a polymerizable compound having at least two ethylenically unsaturated groups. Suitable thermal polymerization inhibitors include haloquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), 2,2'-methylenebis (4-methyl-6-t-butylphenol), phenothiazine, cerium N-nitrosophenylhydroxyamine, and the like. The addition amount of the thermal polymerization inhibitor
About 0.01% to about 5% by weight, based on total solids, is preferred.

In order to improve the physical properties of the cured film, known additives such as an inorganic filler and other plasticizers may be added. As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, etc. % Or less.

The transfer material having a layer of the thermosetting resin composition of the present invention has the following requirements: 1) adhesiveness to a substrate; 2) followability to a step formed by a TFT or a wiring pattern (lamination without bubbles). ), 3) contact hole forming property, 4) heat resistance, 5) stripping solution resistance, 6) insulating property, 7)
Excellent transparency.

As shown in FIG. 5, the transfer material of the present invention comprises the thermosetting resin composition layer 52 on a support 51. If necessary, the transfer material of the present invention may be formed by laminating a protective film 53 on the thermosetting resin composition layer 52 or by releasing a mold between the support 51 and the thermosetting resin composition layer 52. A layer 54 (FIG. 6), an alkali-soluble thermoplastic resin layer 55 and an intermediate layer 56 (FIG. 7) may be provided.

The support preferably has good releasability from the layer formed thereon, is chemically and thermally stable, and is composed of a flexible material. Specifically, Teflon (registered trademark), polyethylene terephthalate,
A thin sheet of polyethylene naphthalate, polyarylate, polycarbonate, polyethylene, polypropylene or the like or a laminate thereof is preferred. In order to obtain good releasability, it is general that no surface treatment such as glow discharge is performed and no undercoat such as gelatin is provided. The thickness of the support is suitably 5 to 300 μm, and 10 μm to 150 μm.
μm is particularly preferred. When the thickness of the support is 5 μm or less, the tensile strength at the time of lamination is insufficient, so that the support is elongated and undesired wrinkles are formed. On the other hand, if the thickness is more than 300 μm, the heat conduction of the thermal lamination is delayed, so that the lamination speed cannot be increased.

The thermosetting resin composition layer comprises the component A,
A solution prepared by uniformly dissolving and mixing the component B and other components contained as necessary in an organic solvent is applied onto a support, and the coating is dried to form a film. Any organic solvent may be used as long as it dissolves component A, component B, and other components contained as necessary, and does not react with these components.

Specific examples of such an organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether and the like. Glycol ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol acetates such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Kill ethers; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Ketones such as ethyl; 2-hydroxypropionate;
Methyl-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2
Esters such as methyl-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate and butyl acetate.

Further, N-methylformamide, N, N
-Dimethylformamide, N-methylformanilide,
N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic acid,
-High-boiling solvents such as -octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. It can also be added to the resin composition.

Among them, glycol alkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, ethyl 2-hydroxypropinate, methyl 3-methoxypropionate, and 3-ethoxypropionic acid Esters such as ethyl and diethylene glycol alkyl ethers such as diethylene glycol dimethyl ether can be suitably used in view of solubility of each component and ease of forming a coating film. These organic solvents can be used alone or in combination of two or more.

The thermosetting resin layer coating solution obtained as described above may be filtered using, for example, a microfiltration filter having a pore size of 0.2 μm before use.

The method for applying the thermosetting resin layer coating solution is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, an extrusion coating method, a curtain coating method, a die coating method, and the like. Various methods such as a wire bar coating method and a knife coating method can be employed.

The heating and drying are usually performed in an oven. The prebaking conditions vary depending on the type of each component, the proportion used, and the like, but are usually at 60 to 110 ° C for 30 seconds to 15 seconds.
About a minute.

The thickness of the thermosetting resin composition layer is from 0.1 to
A range of 10 μm is preferred. If it is less than 0.1 μm, only a cured film having poor resistance can be produced. If it exceeds 10 μm, problems such as a decrease in film thickness accuracy occur. The thickness of the insulating film of the HA or COA method is determined according to the dielectric constant, and the dielectric constant is 3-3.5.
In this case, the thickness is preferably 3 to 5 μm.

The dielectric constant of the layer is 4 or less, preferably 3.5 or less.

When the thermosetting resin layer is transferred to the substrate, the release layer is difficult to peel off the support, or the unevenness of the surface of the support material is caused by the unevenness of the thermosetting resin layer after the transfer. Is provided to prevent a problem in flatness as a result.

The release layer may be any film-forming resin that disperses or dissolves in water or an aqueous alkaline solution, and known resins can be used. For example, polyvinyl ether / maleic anhydride polymers described in JP-A-46-2121 and JP-B-56-40824, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, salts of carboxyalkyl starch, Water salts, polyvinyl alcohol, water-soluble polyvinyl butyral, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like And styrene / maleic acid copolymers, maleate resins, and combinations of two or more of these. Particularly, a combination of polyvinyl alcohol and polyvinyl pyrrolidone and water-soluble polyvinyl butyral are preferable. The polyvinyl alcohol preferably has a saponification rate of 80 mol% or more, and the content of polyvinylpyrrolidone is generally 1 to 75% by mass of the solid of the release layer, preferably 1 to 60% by mass, and 10 to 10% by mass. 50 mass% is more preferable. 1 mass%
If the amount is less than the above, sufficient adhesion to the thermosetting resin layer cannot be obtained, and if it exceeds 75% by mass, the resistance of the thermosetting resin layer to the coating solvent decreases. The thickness of the release layer is very thin, preferably about 0.1 to 5 μm, particularly preferably 0.5 to 2 μm. If it is less than about 0.1 μm, the solvent-blocking ability of the film is too low, and if it exceeds about 5 μm, it takes too much time to remove the release layer.

The alkali-soluble thermoplastic resin layer and the intermediate layer 7
3 is disclosed in Japanese Patent No. 2794242 and Japanese Patent Application Laid-Open No. 10-97061.
As described in Japanese Patent Application Laid-Open No. H10-97061, provided to cope with the problem that bubbles are generated during high-speed lamination between the substrate and the photosensitive layer during transfer due to the unevenness of the base. It can be formed by a method similar to that described.

The alkali-soluble thermoplastic resin layer functions as an auxiliary layer for preventing air bubbles during lamination, and the resin constituting this layer preferably has a substantial softening point of 80 ° C. or less. Examples of the alkali-soluble thermoplastic resin having a softening point of 80 ° C. or lower include a saponified product of ethylene and an acrylate copolymer, a saponified product of styrene and a (meth) acrylate copolymer, and vinyltoluene and (meth) acrylic. Saponified acid ester copolymers, poly (meth) acrylates, and saponified products such as (meth) acrylate copolymers such as butyl (meth) acrylate and vinyl acetate, and the like. Plastic Performance Handbook "(edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, 19
Organic polymers having a softening point of about 80 ° C. or lower, which is soluble in an alkaline aqueous solution, can be used. Alternatively, various plastics compatible with the polymer substance may be added to the organic polymer substance having a softening point of 80 ° C. or higher to lower the substantial softening point to 80 ° C. or lower.

In order to control the adhesive strength between these organic polymer substances and the support, various polymers, supercooled substances, adhesion improvers, interface improvers, etc. are used within a range where the substantial softening point does not exceed 80 ° C. Activators, release agents and the like can be added.

Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.

The thickness of the alkali-soluble thermoplastic resin layer is 6
μm or more is preferred. If the thickness of the thermoplastic resin layer is less than 6 μm, it is difficult to completely absorb the unevenness of the underlayer of 1 μm or more. The upper limit is generally about 100 μm or less in view of film thickness accuracy and manufacturing suitability, and is about 50 μm
The following is preferred.

The intermediate layer is provided for the purpose of preventing undesired mixing between the alkali-soluble thermoplastic resin layer and the thermosetting resin layer. The intermediate layer may be any film-forming resin that disperses or dissolves in water or an aqueous alkali solution, and a known resin can be used. For example, polyvinyl ether / maleic anhydride polymers described in JP-A-46-2121 and JP-B-56-40824, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, salts of carboxyalkyl starch, Water salts, polyvinyl alcohol, water-soluble polyvinyl butyral, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like And styrene / maleic acid copolymers, maleate resins, and combinations of two or more of these. Particularly, a combination of polyvinyl alcohol and polyvinyl pyrrolidone and water-soluble polyvinyl butyral are preferable. The polyvinyl alcohol preferably has a saponification ratio of 80 mol% or more, and the content of polyvinylpyrrolidone is generally 1 to 75% by mass of the solid matter in the intermediate layer, preferably 1 to 60% by mass, particularly preferably 10 to 60% by mass. 50% by mass. If it is less than 1% by mass, sufficient adhesiveness to the thermosetting resin layer cannot be obtained, and if it exceeds 75% by mass, the resistance of the thermosetting resin layer to a coating solvent decreases. The thickness of the intermediate layer is very thin, about 0.1-5 μm
m, particularly preferably 0.5 to 2 μm. If it is less than about 0.1 μm, the solvent-blocking ability of the film is too low, and if it exceeds about 5 μm, it takes too much time to remove the intermediate layer.

The protective film is used in order to avoid attachment of impurities and damage during storage. The protective film may be made of the same or similar material as the support, but must be easily separated from the thermosetting resin layer. Also, the smoothness of the surface to be laminated on the thermosetting resin layer is important.
The presence of such protrusions causes a problem because the thermosetting resin layer is damaged. As such a material, for example, a silicone paper, a polyolefin or a polytetrafluoroethylene sheet is preferable. Particularly preferred is a polypropylene film or a polyethylene film. The thickness of the protective film is preferably about 5 to 100 μm.
Particularly preferably, it is 7 μm to 15 μm.

The method for forming an interlayer insulating film according to the present invention comprises: (1) a step of laminating the above-mentioned transfer material on an active matrix substrate to form a thermosetting resin composition layer; and (2) a step of forming the thermosetting resin composition. A step of heating and curing the layer; and (3) a step of irradiating a laser beam imagewise to remove a laser beam irradiated portion of the thermosetting resin composition layer.

Examples of the transparent insulating substrate of the active matrix substrate include a known glass plate such as a soda glass plate, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, and a plastic film. Also,
A wiring pattern of a silicon oxide film or a metal film is provided on the transparent insulating substrate. The wiring pattern is formed by forming a metal or nonmetal thin film by sputtering or CVD of a semiconductor, a resistor or a conductor, and performing photolithography. Substrate, TFT array and wiring are introduced to Liquid Crystal Display Engineering (Yuji Suzuki, pp. 28-36)
Page, published by Nikkan Kogyo Shimbun, 1998).

If necessary, a known silane coupling treatment step can be performed for the purpose of improving the adhesion between the substrate and the layer thereon. Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrisilane. Methoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. As the silane coupling treatment method for the substrate, the substrate is dipped in an aqueous solution of a silane coupling agent having a concentration of 0.1 to 10% by mass at room temperature to 50 ° C. for several seconds to several minutes, washed with water, and dried. Under preferred processing conditions, the concentration is between 1 and
At 5%, the temperature is between room temperature and 30 ° C., the time is several minutes.

Before forming the thermosetting resin composition layer, a multicolored colored resin film may be formed on the active matrix substrate.

In the step of forming the thermosetting resin composition layer, after the protective film is peeled off from the transfer material of the present invention,
The thermosetting resin layer is transferred onto the active matrix substrate by laminating under heat and pressure. Advantageously, the temperature of the heat-press roll during transfer is 50 ° C. to 150 ° C., and the linear pressure during press-bond is 5 kg / cm to 25 kg / cm.
The lamination speed is 0.2m / min to 4m in transport speed.
/ Min is preferred. Particularly preferable conditions are that the temperature of the heat-pressing roll is 130 ° C. to 140 ° C. and the linear pressure at the time of pressing is 10 ° C.
Kg / cm-15Kg / cm, transport speed 1m / min-3
m / min.

Before the heat curing treatment, the support is removed.
When the transfer material has an alkali-soluble thermoplastic resin layer and an intermediate layer, after the support is removed and before the heat-curing treatment, the alkali-soluble thermoplastic resin layer and the intermediate layer are removed by a weak alkaline water treatment, and dried. Do.

As the liquid for removing the alkali-soluble thermoplastic resin layer and the intermediate layer, a dilute aqueous solution of an alkaline substance is used, and a liquid to which a small amount of an organic solvent miscible with water may be added. Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate) , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), ammonia, ethylamine, n-propylamine, diethylamine , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, diethanolamine, monoethanolamine,
Morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), pyrrole, piperidine, 1,8-diazabicyclo [5,4,
0] -7-undecene, 1,5-diazabicyclo [4,
3,0] -5-nonane or trisodium phosphate. The concentration of the alkaline substance is generally 0.01% by mass to 30% by mass, and the pH is preferably 8 to 14. The thermosetting resin composition layer of the present invention is made of HA or CO
When used as a transparent interlayer insulating film for A, it is needless to say that it is desirable to use a metal ion-free removing solution in order to prevent malfunction of the semiconductor, and an organic amine aqueous solution is preferred.

The removing liquid can be used as a bath liquid or a spray liquid. Further, as a removing method, a liquid filling method, a dipping method, a rocking immersion method, a spray method, or the like can be used.

The temperature of the removing solution is usually from around room temperature to 40 ° C.
Is preferable. A water washing step may be added after the removal treatment.

After the removal treatment, the thermosetting resin composition layer is subjected to, for example, a rinsing treatment by washing with running water, and further, the layer is baked by a heating device such as a hot plate or an oven to thereby form the layer. Is performed.
The firing temperature in this curing treatment is, for example, 150 to 2
The temperature is 50 ° C, preferably 160 to 250 ° C. The firing time is, for example, 5 to 90 minutes (5 to 30 minutes when firing on a hot plate, 30 to 90 minutes when firing in an oven). In this way,
A thin film having excellent solvent resistance and transparency can be formed on the surface of the substrate.

Subsequently, the thermosetting resin composition layer is removed by ablation by laser beam irradiation. Ablation means irradiating the object with laser light to decompose or evaporate the laser light irradiating part to a desired depth.

In the present invention, gas lasers such as a carbon dioxide gas laser and an argon ion laser, a Nd: YAG laser, a Y
Solid-state lasers such as LF (LiYF4) and excimer lasers are available.

As a method for irradiating the thermosetting resin composition layer with laser light in a pattern, the laser light is narrowed down using an optical component such as a lens, and the narrowed laser light is subjected to CA.
Examples include a direct drawing method in which the thermosetting resin composition layer is irradiated in a pattern based on D data and the like, and a method in which a laser beam is passed through a mask to form a pattern and the thermosetting resin composition layer is irradiated. Can be.

Irradiation of laser beam on thermosetting resin composition layer
Depends on the thickness of the thermosetting resin composition layer.
Normally, the energy density of one pulse is 100-5000mJ
/ Cm ^TwoIrradiate about 1 to 100 pulses of pulse laser
This can be suitably performed.

The application of the transfer material of the present invention to a transparent interlayer insulating film used in the HA or COA technique will be described with reference to FIGS. FIG. 3 shows a process of producing an active matrix panel of HA, and FIG. 4 shows a process of producing an active matrix panel of COA (switching elements are omitted in the drawing). The transparent interlayer insulating film is
It may be a single layer or multiple layers of the same or different materials.

In FIGS. 3A and 4A, a thin film of metal or nonmetal is formed on a transparent insulating substrate 31 by sputtering or CVD of a semiconductor, a resistor, or a conductor, and photolithography is performed. Thereby, a TFT array and a drain signal line pattern 32 for connecting them are formed in the liquid crystal display. FIG. 4 (A)
In this embodiment, a color filter 37 including a red (R), blue (G), green (B) pixel region and a black matrix is provided.

Subsequently, as shown in FIGS. 3B and 4B, a thermosetting resin layer 33 is formed on the pattern by lamination using the transfer material of the present invention.

Subsequently, if there is a release layer, an alkali-soluble thermoplastic resin layer or an intermediate layer, they are removed and only the thermosetting resin layer is left on the substrate. A dilute alkaline aqueous solution can be used for removing the release layer, the alkali-soluble thermoplastic resin layer and the intermediate layer. If an alkaline aqueous solution is used, wash with water and dry. Thereafter, a heat treatment is performed using an oven or the like at a temperature of 150 ° C. or more for 5 to 90 minutes to cure the thermosetting resin layer.

Next, as shown in FIGS. 3 (C) and 4 (C), laser light is applied to form an interlayer connection hole called a contact hole at an appropriate position on the drain signal line pattern to be connected. Irradiate. A contact hole is formed at the irradiation site (FIG. 3D).

Next, as shown in FIGS. 3 (E) and 4 (D), heating is performed at 200 ° C. to 250 ° C. for 10 minutes to 120 minutes to form a mortar shape. This is to prevent the disconnection of ITO described later.

Subsequently, as shown in FIGS. 3 (F) and 4 (E), the IT is normally kept at a temperature of 180 to 250 ° C.
An O film 35 is provided by a sputtering method. The thickness of the ITO film is usually from 1500 to 2500 angstroms (0.15
０．２0.25 μm).

Subsequently, as shown in FIG.
For the patterning step, a photoresist 36 for ITO etching is coated on the entire surface, dried, and irradiated with UV light through a pattern mask 34 of ITO. The thickness of the photoresist after coating and drying is about 1 μm to about 3 μm.

Next, after the development of the resist image shown in FIG. 3H, the ITO in the portion not covered by the resist is dissolved by an ordinary acidic etching solution such as a mixed solution of iron chloride / hydrochloric acid and an aqueous solution of hydrobromic acid. You.

Next, as shown in FIGS. 3 (I) and 4 (F), the photoresist is removed by a resist stripper. The resist stripping solution is described in JP-A-51-72503, JP-A-57-84456, U.S. Pat. No. 4,165,294, European Patent Application No. 0119337, and JP-A-6-222573. As a typical stripping solution, a mixed solution of monoethanolamine and dimethyl sulfoxide in a ratio of 7: 3 (mass ratio) can be given. Peeling process is usually 50 ° C
This is performed by immersing the substrate in the stripping solution at a temperature of 〜80 ° C. for 2 to 10 minutes.

[0131]

EXAMPLES (Synthesis Example 1) 40.3 parts by mass of methacrylic acid
3-chloro-2-hydroxypropyl methacrylate 1
19.7 parts by mass, cyclohexyl methacrylate
0 parts by mass (composition ratio: 28:40:32) was dissolved in 500 parts by mass of methoxypropyl acetate. This solution is
The mixture was stirred while heating under a nitrogen stream at 0 ° C., and 2.75 parts by mass of 2,2′-azobis- (2,4′-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added. The mixture was heated and stirred at ℃ for 4 hours. The mixture was further heated at 80 ° C. for 1 hour to obtain a methoxypropyl acetate solution of the copolymer. This solution was poured into 1,000 parts by mass of n-hexane with stirring to precipitate a copolymer (acid value 79), and the obtained solid polymer was collected by filtration and air-dried.

(Synthesis Example 2) 100 parts by mass of chloroform
168.8 parts by mass of hydrochloric acid was stirred in a flask at room temperature, and pentaerythritol polyglycidyl ether (Denacol EX-411, manufactured by Nagase Kasei Kogyo Co., Ltd.)
6.0 parts by weight were added little by little. The mixture was further stirred at room temperature for 1 hour. The reaction solution (two-layer system) was neutralized with an aqueous sodium hydrogen carbonate solution, the product was extracted into an organic layer, and the organic layer was separated. The organic layer was further washed with saturated saline, dehydrated with magnesium sulfate, and concentrated to dryness to obtain 40 parts by mass of a pale yellow liquid of pentaerythritol poly (3-chloro-2-hydroxypropyl) ether.

(Synthesis Example 3) 100 parts by mass of chloroform
79.4 parts by mass of hydrochloric acid was stirred in a flask at room temperature, and 33.7 parts by mass of a phenol novolak-type epoxy resin (DEN438, manufactured by Dow Chemical Co., Ltd.) was added little by little. The mixture was further stirred at room temperature for 1 hour. This reaction solution (2
Layer) was neutralized with an aqueous solution of sodium hydrogen carbonate, the product was extracted into an organic layer, and the organic layer was separated. Further, the organic layer is washed with a saturated saline solution, dehydrated with magnesium sulfate, and concentrated to dryness to obtain a phenol novolak resin poly (3).
As a result, 37.5 parts by mass of a light yellow solid of -chloro-2-hydroxypropyl) ether was obtained.

(Synthesis Example 4) 100 parts by mass of chloroform,
67.6 parts by mass of hydrochloric acid was stirred in a flask at room temperature, and 34.2 parts by mass of cresol novolak type epoxy resin (Epiclon N-695, manufactured by Dainippon Ink Co., Ltd.) was added little by little. The mixture was further stirred at room temperature for 1 hour. The reaction solution (two-layer system) was neutralized with an aqueous sodium hydrogen carbonate solution, the product was extracted into an organic layer, and the organic layer was separated. Further, the organic layer is washed with a saturated saline solution, dehydrated with magnesium sulfate,
By concentrating and drying, 43.4 parts by mass of a pale yellow solid of poly (3-chloro-2-hydroxypropyl) ether of cresol novolak resin was obtained.

(Synthesis Example 5) 100 parts by mass of chloroform
126.6 parts by mass of hydrochloric acid was stirred at room temperature in a flask, and trimethylolpropane polyglycidyl ether (Denacol EX-321, manufactured by Nagase Kasei Kogyo Co., Ltd.) was added thereto.
30.2 parts by weight were added in small portions. The mixture was further stirred at room temperature for 1 hour. The reaction solution (two-layer system) was neutralized with an aqueous sodium hydrogen carbonate solution, the product was extracted into an organic layer, and the organic layer was separated. The organic layer was further washed with saturated saline, dehydrated with magnesium sulfate, and concentrated to dryness to obtain 40.8 parts by mass of a pale yellow liquid of trimethylolpropane poly (3-chloro-2-hydroxypropyl) ether. Was.

(Synthesis Example 6) 100 parts by mass of chloroform,
54 parts by mass of hydrochloric acid were stirred at room temperature in a flask, and bisphenol A described in Example 1 of JP-A-5-5020 was added thereto.
Resin 1 in which all of the alcohol hydroxyl groups are epoxidized by the dehydrochlorination reaction product of epoxy resin and epichlorohydrin
19 parts by weight were added in small portions. The mixture was further stirred at room temperature for 1 hour. The reaction solution (two-layer system) was neutralized with an aqueous sodium hydrogen carbonate solution, the product was extracted into an organic layer, and the organic layer was separated. The organic layer was further washed with saturated saline, dehydrated with magnesium sulfate, and concentrated to dryness to obtain 270 parts by mass of a pale yellow solid of poly (3-chloro-2-hydroxypropyl) ether having a phenoxy resin as a skeleton. Was.

(Synthesis Example 7) Dimethylformamide 200
In parts by mass, pentaerythritol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-41)
1) 36.0 parts by mass, 45.4 parts by mass of chloroacetic acid and 1.82 parts by mass of butyltriethylammonium chloride were added, and the mixture was stirred at 100 ° C. for 8 hours. The reaction solution was poured into a large amount of water, ethyl acetate was added, the product was extracted into an organic layer, and the organic layer was separated. The organic layer is washed with an 8% aqueous sodium carbonate solution, further washed with water and saturated saline, dehydrated with magnesium sulfate, and concentrated to dryness to give pentaerythritol poly (3-hydroxy-2-chloroacetoxypropyl) ether. 60.3 parts by mass of a dark brown liquid was obtained.

(Synthesis Example 8) Dimethylformamide 200
In parts by mass, pentaerythritol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-41)
1) 36.0 parts by mass, 26.6 parts by mass of acetic acid and 1.82 parts by mass of butyltriethylammonium chloride were added, and the mixture was stirred at 100 ° C. for 8 hours. The reaction solution was poured into a large amount of water, ethyl acetate was added, the product was extracted into an organic layer, and the organic layer was separated. The organic layer was washed with an 8% aqueous sodium carbonate solution, further washed with water and saturated saline, dehydrated with magnesium sulfate, and concentrated to dryness to give pentaerythritol poly (3-chloroacetoxy-2-hydroxypropyl) ether. 36 parts by mass of a pale yellow liquid was obtained.

Example 1 21 parts by weight of the copolymer of Synthesis Example 1 was dissolved in a mixed solution of 30 parts by weight of propylene glycol monomethyl ether acetate and 13 parts by weight of methyl ethyl ketone, 10 parts by weight of a plasticizer BDP, and Victoria Pure Blue dye. -BOH (Hodogaya Chemical) 0.02
25 parts by mass and 0.03 parts by mass of a fluorine-based surfactant F176PF (manufactured by Dainippon Ink) were dissolved to obtain a thermosetting resin solution C1. This solution was continuously applied on a 5 mm thick polyethylene terephthalate film roll having a width of 890 mm as a support by a slit coat type coating machine,
The coating was dried in a drying oven at 100 ° C. for 2 minutes,
An m-thick thermosetting resin composition layer was obtained. The distribution of the coating film thickness was within ± 0.05 μm. A 12 μm thick polypropylene protective film was continuously laminated on the thermosetting resin composition layer to obtain a transfer material. A glass substrate provided with a TFT array and an aluminum drain wiring (thickness: 0.1 mm).
7 mm), after removing the protective film from the transfer material, a thermosetting resin layer surface is laminated using a laminator,
Both were laminated while heating at a roll speed of 3 m / min and a roll temperature of 130 ° C.

After the support was removed, four pulses of 1200 mJ of energy density were irradiated by a krypton-fluorine gas excimer laser apparatus through a contact hole mask to decompose the thermosetting resin composition layer of the irradiated part. Removed. Thereafter, the layer was heated at 200 ° C. for 20 minutes.

The thickness of the thermosetting resin composition layer was 4 μm.
The dielectric constant was 2.8 (1 kHz), and a scratch test with a pencil showed that the scratched pencil had a hardness of 5H. The uniformity of the thickness was as good as ± 0.05 μm, and the shape of the contact hole portion was a mortar shape with a bottom diameter of 10 μm and an inclination angle of 25 degrees, which was good. The layer was substantially colorless and transparent, and had a transmittance of 97% with respect to light having a wavelength of 350 nm.

Then, ITO was sputtered from above,
A transparent conductive layer having a thickness of 2 μm was formed. On top of this, a photoresist is applied and dried, and a mask having a pattern of a transparent electrode is overlaid and exposed.
After etching the TO part with hydrobromic acid etchant,
When the photoresist was peeled off by immersing the substrate in a mixed solution of monoethanolamine and dimethyl sulfoxide (mass ratio 7: 3) at 80 ° C. for 10 minutes, the photoresist was peeled off, and the thermosetting resin composition layer ITO
And no damage such as wrinkles due to swelling was observed. Transfer material used at 40 ° C / 70% R
After being left for 5 days in a H thermotester, lamination was performed on the substrate. As a result, lamination could be performed without any problem as before the thermotest. The subsequent process was carried out without any problem, and a transparent interlayer insulating film having a contact hole was obtained.

Example 2 Benzyl methacrylate 73
Of methacrylic acid and an acid value of 10
21 mg by mass of 1 mg KOH / 1 g, mass average molecular weight of about 100,000) was dissolved in a mixed solution of 30 parts by mass of propylene glycol monomethyl ether acetate and methyl ethyl ketone 13, and 12.6 parts by mass of the compound of Synthesis Example 2 was obtained. BOH (Hodogaya Chemical) 0.
0225 parts by mass, and a fluorine-based surfactant F176PF
0.03 parts by mass (manufactured by Dainippon Ink) was dissolved to obtain a thermosetting resin solution C2. This solution was continuously coated on a 890 mm-wide 5 μm-thick polyethylene terephthalate film roll as a support by a slit coat type coating machine, and the coating film was dried in a drying oven at 100 ° C. for 2 minutes.
A 5 μm thick thermosetting resin composition layer was obtained. The distribution of the coating film thickness was within ± 0.05 μm. A 12 μm-thick polypropylene protective film was continuously laminated on this thermosetting resin composition layer to obtain a transfer material.

After removing the protective film from the transfer material on a glass substrate (thickness 0.7 mm) provided with a TFT array and an aluminum drain wiring, the surface of the thermosetting resin layer was laminated using a laminator. And roll speed 3
The layers were laminated while heating at a roll temperature of 130 ° C. for m / min.

After the support was removed, the thermosetting resin composition layer was cured by heating in an oven at 170 ° C. for 30 minutes. After cooling, a krypton-fluorine gas excimer laser was used to form an insulating film to be a contact hole. The part was irradiated.
After that, the layer was heat-treated at 200 ° C. for 20 minutes.

The thickness of the thermosetting resin composition layer was 4 μm.
The dielectric constant was 2.7 (1 kHz), and a scratch test with a pencil showed that the scratched pencil had a hardness of 5H. The uniformity of the thickness was as good as ± 0.05 μm, and the shape of the contact hole portion was a mortar shape with a bottom diameter of 10 μm and an inclination angle of 25 degrees, which was good. The layer was substantially colorless and transparent, and had a transmittance of 98% with respect to light having a wavelength of 350 nm.

Then, ITO was sputtered from above,
A transparent conductive layer having a thickness of 2 μm was formed. A photoresist is coated on this, dried, a mask having a pattern of a transparent electrode is overlaid and exposed, and after development, an ITO portion not covered with the resist is etched with a hydrobromic acid etchant. The photoresist was removed by immersing the substrate in a mixed solution of sulfoxide (mass ratio 7: 3) at 80 ° C. for 10 minutes.
The photoresist was stripped, the insulating layer was not stripped of ITO, and no damage such as wrinkles due to swelling was observed. After leaving the above-mentioned transfer material in a thermo tester at 40 ° C./70% RH for 5 days, it was laminated on a substrate.
Lamination was possible without any problem as before the thermotest. The subsequent process was carried out without any problem, and a transparent interlayer insulating film having a contact hole was obtained.

(Examples 3 to 8) In place of the compound of Synthesis Example 2 in Example 2, a compound of Synthesis Examples 3 to 8 was used to form a transparent interlayer insulating layer in the same manner as in Example 2. Scratch test, measurement of transmittance of light having a wavelength of 350 nm, 40
After standing for 5 days in a thermo tester at a temperature of 70 ° C./70% RH, an interlayer insulating film was formed. Table 1 shows the results.

[0149]

[Table 1]

Comparative Example 1 Using the composition of Example 1 of JP-A-11-87927, an interlayer insulating film was formed in the same manner as in Example 1 of the present invention.

That is, as the component (A), 30 parts by mass of a liquid bisphenol A type epoxy resin (epoxy equivalent: 185, Epicoat 828EL manufactured by Yuka Shell Epoxy Co., Ltd.) (hereinafter, all the compounding amounts are represented by parts by mass), (B) ) Component bisphenol A type epoxy resin (epoxy equivalent 20
00, softening point 124 ° C, 20 parts by mass of Epicron 7051 manufactured by Dainippon Ink and Chemicals, Inc., and a brominated bisphenol A type epoxy resin (epoxy equivalent 499, softening point 7)
5 ° C, bromine content 21% by mass, YDB manufactured by Toto Kasei Co., Ltd.
-500) and 40 parts by mass of methyl ethyl ketone (hereinafter, referred to as methyl ethyl ketone).
MEK), and heated and dissolved therein with stirring. As an epoxy curing agent, 2,4 diamino-6- (2-methyl-1-imidazolylethyl) -1,3,5-triazine / isocyanuric acid adduct 4 parts by mass, 2 parts by mass of crushed silica and 4 parts by mass of antimony trioxide were added to prepare a thermosetting resin composition coating solution.

This coating solution was continuously applied to a 5 μm-thick polyethylene terephthalate film roll support by a slit coat type coating machine so that the thickness after drying was 4 μm, and the coating solution was placed in a drying oven at 100 ° C. The coating film was dried for 2 minutes to obtain a thermosetting resin composition layer having a thickness of 5 μm. The thickness distribution of this layer was within ± 0.05μ.
A 12 μm thick polypropylene protective film was continuously laminated on the thermosetting resin composition layer to obtain a transfer material.

On a glass substrate (0.7 mm thick) provided with a TFT array and an aluminum drain wiring,
After removing the protective film from the transfer material, the surface of the thermosetting resin composition layer was superposed using a laminator, and was heated and laminated at a roll speed of 3 m / min and a roll temperature of 130 ° C.

After the support was removed, the thermosetting resin composition layer was cured by heating at 160 ° C. for 30 minutes and cooled to room temperature. Energy density of one pulse 12 through a contact hole mask with a krypton-fluorine gas excimer laser device
A pulse of 00 mJ was irradiated for 4 pulses, and the thermosetting resin composition layer in the irradiated portion was decomposed into a hole shape and removed. Thereafter, the thermosetting resin composition layer was heat-treated at 200 ° C. for 20 minutes.

The thickness of the thermosetting resin composition layer was 4 μm.
The permittivity was 4.1 (1 kHz), and a scratch test with a pencil was performed. As a result, the hardness of the scratched pencil was 5H. The uniformity of the thickness was as good as ± 0.05 μm, and the shape of the contact hole portion was a mortar shape with a bottom diameter of 10 μm and an inclination angle of 25 degrees, which was good. The layer was substantially colorless and transparent, and the transmittance was 90% for light having a wavelength of 350 nm.

Then, ITO was sputtered from above,
A transparent conductive layer having a thickness of 2 μm was formed. A photoresist is coated on this, dried, a mask having a pattern of a transparent electrode is overlaid and exposed, and after development, an ITO portion not covered with the resist is etched with a hydrobromic acid etchant. The photoresist was removed by immersing the substrate in a mixed solution of sulfoxide (mass ratio 7: 3) at 80 ° C. for 10 minutes.
The photoresist was stripped, the insulating layer was not stripped of ITO, and no damage such as wrinkles due to swelling was observed. The above thermosetting resin transfer material roll was heated at 40 ° C./70
After standing for 5 days in a thermo tester at% RH, the laminate was laminated on a substrate, and the thermal adhesion was lost. It was difficult to laminate under the initial lamination conditions (lamination roll temperature, lamination speed).

Example 9 Preparation of Transfer Material and Formation of HA Type Transparent Interlayer Insulating Film on Substrate Copolymer of 73 mol of benzyl methacrylate and 27 mol of methacrylic acid (acid value: 101 mg KOH / 1 g, mass average molecular weight: about 10 1) 21 parts by mass were dissolved in a mixed solution of 30 parts by mass of propylene glycol monomethyl ether acetate and methyl ethyl ketone 13 to obtain pentaerythritol tetra (2-hydroxy-3-chloropropyl) ether, which is a crosslinking agent compound of Synthesis Example 2. 6 parts by mass,
0.0225 parts by mass of Dye Victoria Pure Blue-BOH (manufactured by Hodogaya Chemical) and fluorinated surfactant F176
0.03 parts by mass of PF (manufactured by Dainippon Ink) was dissolved to obtain a thermosetting resin solution C3. The film was continuously coated on a 890 mm-wide 5 μm-thick polyethylene terephthalate film web as a support with a slit coat type coating machine, and the coating film was dried in a drying oven at 100 ° C. for 2 minutes and dried at 5 μm
A thick thermosetting resin composition layer was obtained. The coating thickness distribution is ±
It was within 0.05μ. A polypropylene protective film having a width of 880 mm and a thickness of 12 μm was continuously laminated on the thermosetting resin composition layer and wound around a paper tube to obtain a transfer material.

A glass substrate provided with a TFT array and an aluminum drain wiring (having a thickness of 0.7 mm:
After removing the protective film from the transfer material on 880 mm × 680 mm), the surface of the thermosetting resin composition layer was laminated using a laminator, and the roll speed was 3 m / min and the roll temperature was 1
Heat lamination was performed at 30 ° C.

After removing the support, the composition layer was heated at 170 ° C. for 3 hours.
The composition was heated and cured in an oven for 0 minutes, and irradiation with a krypton-fluorine gas excimer laser was performed on a portion of the composition layer that was to be a contact hole. Thereafter, the thermosetting composition layer was heated at 200 ° C. for 20 minutes.

The thickness of the thermosetting resin composition layer was 4 μm.
The dielectric constant was 2.8 (1 kHz), and a scratch test with a pencil showed that the scratched pencil had a hardness of 5H. The uniformity of the thickness was as good as ± 0.05 μm, and the shape of the contact hole portion was a mortar shape with a bottom diameter of 10 μm and an inclination angle of 25 degrees, which was good. The layer was substantially colorless and transparent, and had a transmittance of 97% with respect to light having a wavelength of 350 nm.

Then, ITO was sputtered from above,
A transparent conductive layer having a thickness of 2 μm was formed. A photoresist is coated on this, dried, a mask having a pattern of a transparent electrode is overlaid and exposed, and after development, an ITO portion not covered with the resist is etched with a hydrobromic acid etchant. The photoresist was removed by immersing the substrate in a mixed solution of sulfoxide (mass ratio 7: 3) at 80 ° C. for 10 minutes.
The photoresist was stripped, the insulating layer was not stripped of ITO, and no damage such as wrinkles due to swelling was observed. Further, when the above-mentioned transfer material was left in a thermotester at 40 ° C./70% RH for 5 days and then laminated on a base, lamination could be performed without any problem as before the thermotest. The subsequent process was carried out without any problem, and a transparent interlayer insulating film having a contact hole was obtained.

Example 10 Method for Producing HA from Multilayer Material The following composition H1 was formed on a support which was a roll of polyethylene terephthalate film having a width of 890 mm and a thickness of 70 μm.
Is applied and dried to a dry film thickness of 15 μm
Was provided. <Composition H1 of coating liquid for forming thermoplastic resin layer> Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (molar ratio of each monomer = 55 / 11.7 / 4.5 / 28.8, Weight average molecular weight = 80000) 15.0 parts by mass Polyfunctional acrylate (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) 7.0 parts by mass Fluorinated surfactant (F177P, manufactured by Dainippon Ink Co., Ltd.) 3 parts by weight Methanol 30.0 parts by weight Methyl ethyl ketone 19.0 parts by weight 10.0 parts by weight of 1-methoxy-2-propanol Next, an intermediate layer coating solution having the following composition B1 is applied on the thermoplastic resin layer and dried. An intermediate layer having a dry film thickness of 1.6 μm was provided. <Composition B1 of coating solution for forming intermediate layer> Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd., saponification degree: 80 mol%) 130 parts by mass Polyvinylpyrrolidone (PVP, K-30, manufactured by GAF Corporation) 60 parts by mass Distillation 2110 parts by mass of water 1750 parts by mass of methanol 1750 parts by mass of C for the thermosetting resin composition layer of Example 1 on the intermediate layer
(1) A coating solution is applied, and the coating film is dried to form a thermosetting resin composition layer having a dry film thickness of 5 μm. Further, on this thermosetting resin composition layer, protection of polypropylene (thickness: 12 μm) is performed. The film was pressed to form a three-layer transfer material.

After removing the protective film from the transfer material on a glass substrate (thickness 0.7 mm) provided with a TFT array and an aluminum drain wiring, the surface of the thermosetting resin composition layer was coated with a laminator. The sheets were stacked and heated and laminated at a roll speed of 3 m / min and a roll temperature of 130 ° C.

After removing the support, the thermoplastic resin layer and the intermediate layer were removed using a 1% by mass aqueous solution of triethanolamine, and the thermosetting resin composition layer was washed with water and dried. At this time, the thermosetting resin composition layer was not substantially affected by the aqueous triethanolamine solution, and, for example, did not become thin.

Next, the thermosetting resin composition layer was baked in an oven at 180 ° C. for 1 hour to cure the layer.

Using a krypton-fluorine gas excimer laser device, one pulse of 1200 mJ in energy density was irradiated for four pulses through a mask having a contact hole pattern to decompose the irradiated part of the thermosetting resin composition layer. , Removed. Thereafter, the thermosetting resin composition layer was heat-treated at 200 ° C. for 20 minutes.

The thermosetting resin composition layer on the TFT substrate thus obtained had a thickness of 4 μm and a dielectric constant of 2.8 (1 k
Hz), a scratch test with a pencil showed that the scratched pencil had a hardness of 5H. Thickness uniformity is ±
The shape of the contact hole portion was as good as 0.05 μm, and was good in a mortar shape with a bottom diameter of 10 μm and an inclination angle of 25 °. The layer is substantially colorless and transparent,
The transmittance was 97% for light having a wavelength of 350 nm.

Then, ITO was sputtered from above,
A transparent conductive layer having a thickness of 2 μm was formed. A photoresist is coated on this, dried, a mask having a pattern of a transparent electrode is overlaid and exposed, and after development, an ITO portion not covered with the resist is etched with a hydrobromic acid etchant. The photoresist was removed by immersing the substrate in a mixed solution of sulfoxide (mass ratio 7: 3) at 80 ° C. for 10 minutes.
The photoresist was stripped, the insulating layer was not stripped of ITO, and no damage such as wrinkles due to swelling was observed. When the above transfer material was left in a thermotester at 40 ° C./70% RH for 5 days and then laminated on a substrate, it could be laminated without any problem as before the thermotest. The subsequent process was carried out without any problem, and a transparent interlayer insulating film having a contact hole was obtained.

Example 11 Method for Producing a Two-Layer COA (Preparation of Transfer Material and Formation of Insulating Layer on Color Filter) A coating solution having the following composition H2 was formed on a 100 μm-thick polyethylene terephthalate film support. Apply,
After drying, a thermoplastic resin layer having a dry film thickness of 12 μm was provided. <Composition H2 of coating liquid for forming thermoplastic resin layer> Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (molar ratio of each monomer = 55 / 11.7 / 4.5 / 28.8, Weight average molecular weight = 80000) 15.0 parts by mass Polyfunctional acrylate (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) 7.0 parts by mass Fluorinated surfactant (F177P, manufactured by Dainippon Ink Co., Ltd.) 3 parts by weight methanol 30.0 parts by weight methyl ethyl ketone 19.0 parts by weight 10.0 parts by weight of 1-methoxy-2-propanol Next, a coating solution having the following composition B2 was applied on the thermoplastic resin layer and dried. An intermediate layer having a dry film thickness of 1.6 μm was provided. <Composition B2 of coating solution for forming intermediate layer> Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd., degree of saponification: 80 mol%) 130 parts by mass Polyvinylpyrrolidone (PVP, K-30, manufactured by GAF Corporation) 60 parts by mass Distillation 2110 parts by mass of water 1750 parts by mass of methanol 1750 parts by mass of a thermosetting resin composition coating solution having the following composition C3 is applied and dried on the intermediate layer to form a thermosetting resin composition layer having a dry film thickness of 4 µm. A protective film of polypropylene (12 μm in thickness) was pressed on the thermosetting resin composition layer to form a multilayer transfer material. <Composition C3 of coating liquid for forming thermosetting resin layer> Benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, mass average molecular weight = 30,000) 21.0 parts by mass propylene glycol monomethyl ether acetate 30.0 Parts by mass Compound of Synthesis Example 2 10.0 parts by mass Fluorinated surfactant (F176PF, manufactured by Dainippon Ink) 0.25 parts by mass Victoria Pure Blue BOH 0.0225 parts by mass methyl ethyl ketone 13.0 parts by mass Coating of the above transfer material A transfer material for R (red), G (green), B (blue), and K (black) was obtained by using each coating solution of each coating composition for forming a photosensitive layer shown in Table 2 in place of the solution C3. (Each having a dry film thickness of 2 μm). The numerical values in Table 2 are parts by mass.

[0170]

[Table 2]

On a glass substrate (thickness 0.7 mm) on which a wiring composed of a TFT array and a lower ITO was formed, using these R, G, B, and K transfer materials, a lower ITO substrate was formed. The photosensitive layer was transferred, subjected to pattern exposure, developed, and baked to form a black matrix having a thickness of 1.8 μm and a pixel having a diameter of 20 μm and a tilt angle of 3 μm for each pixel.
R, G, and B pixels having a 0-degree contact hole were formed to form a color filter.

After the protective film was removed from the transfer material of the present example on the black matrix and the color filter having R, G, and B pixels, the surface of the thermosetting resin composition layer was coated with a laminator. The support was removed.

The thermoplastic resin layer and the intermediate layer were removed using a 1% by mass aqueous solution of triethanolamine. On this occasion,
The thermosetting resin composition layer was not substantially affected by the aqueous triethanolamine solution, and, for example, did not become thin.

The thermosetting resin composition layer was heated and cured in an oven at 170 ° C. for 30 minutes, and passed through a contact hole mask using a krypton-fluorine gas excimer laser apparatus to obtain a layer.
Irradiate four pulses of 1200 mJ pulse energy density to decompose the irradiated part of the thermosetting resin composition layer,
Removed. Thereafter, the thermosetting resin composition layer was heated at 200 ° C. for 2 hours.
Heat treatment was performed for 0 minutes.

The thickness of the thermosetting resin composition layer was 3.3 μm.
The dielectric constant was 2.7 (1 kHz), and a scratch test was performed with a pencil. As a result, the hardness of the scratched pencil was 8H. The thickness uniformity is as good as ± 0.05 μm,
The shape of the contact hole portion was a good mortar shape with a bottom diameter of 10 μm and an inclination angle of 25 °. The layer was substantially colorless and transparent, and had a transmittance of 95% with respect to light having a wavelength of 350 nm. ITO was sputtered from above to form a 0.2 μm thick transparent conductive layer. A photoresist is coated thereon and dried, and a mask having a pattern of a transparent electrode is overlaid and exposed. After development, an ITO portion not covered with the resist is etched with an acidic etchant, and then dimethyl sulfoxide and monoethanolamine (mass ratio 3) : The substrate was added to the mixed solution of 7) at 80 ° C 10
When the photoresist was peeled off by immersion for minutes, the photoresist was peeled off, the ITO did not peel off in the insulating layer, and no damage such as wrinkles due to swelling was observed.

The above transfer material was left in a thermo tester at 40 ° C./70% RH for 5 days and then laminated on a substrate. As a result, it was possible to laminate without any problem as before the thermo test. The subsequent process was carried out without any problem, and a transparent interlayer insulating film having a contact hole was obtained.

[0177]

According to the present invention, since a specific crosslinking agent is used, a thermosetting resin composition excellent in heat resistance, chemical resistance, storage stability, and high-temperature reactivity, and a transfer material using the same. ,
In addition, a method for forming an interlayer insulating film can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view of a high aperture type active matrix substrate.

FIG. 2 is a cross-sectional view of a color filter on array (with a transparent interlayer insulating film) type active matrix substrate.

FIG. 3 is a cross-sectional view illustrating a manufacturing process of the HA type active matrix substrate.

FIG. 4 is a cross-sectional view illustrating a manufacturing process of a COA active matrix substrate with a transparent interlayer insulating film.

FIG. 5 is a cross-sectional view of the transfer material of the present invention.

FIG. 6 is a cross-sectional view of another transfer material of the present invention.

FIG. 7 is a sectional view of still another transfer material of the present invention.

[Explanation of symbols]

 Reference Signs List 11 transparent insulating substrate 18 transparent interlayer insulating film 22 color filter 31 transparent insulating substrate 33 thermosetting resin layer 51 support 52 thermosetting resin composition layer 53 protective film 54 release layer 55 alkali-soluble thermoplastic resin layer 56 Middle class

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tanki 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H090 HA03 HA04 HB13X HC01 HD03 HD05 HD08 JB02 LA04 LA15 2H092 HA04 HA06 JA24 JA46 JB57 JB58 KB04 KB25 MA01 MA05 MA10 MA15 MA18 NA07 NA11 NA17 NA18 NA19 NA29 PA08 4J002 BG011 BG071 BH011 ED017 ED027 ED047 FD096 GQ01 4J100 AB02R AB03R AB04R AB07Q AB07R AB08R AB09R AE02R AE03R AE09R AG02R AG04R AG08R AJ01Q AJ02Q AJ03Q AJ08Q AJ09Q AK31Q AK32Q AL03R AL04R AL08P AL08R AL09R AL14R AL34R AL44R AM15R AM17R AM19R AM21R AM43R AQ08R AQ12R AQ26R BA03P BA04P BA04R BA05P BA05R BA06P BA06R BA15P BA16Q BA20P BA20R BA31R BB01P BB03P BB05P BB10P BC04CA04BCBC43P BC43P

Claims (10)

[Claims] 1. A copolymer comprising 5-80 mol% of a polymerizable monomer represented by the following general formula I and 5-80 mol% of a carboxylic acid group-containing monomer as a monomer in an amount of 1% by mass based on the total solid content.
A thermosetting resin composition, characterized in that the composition contains about 100% by mass. Embedded image (Where R ¹ represents a hydrogen atom or a methyl group, and X is
An alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, which comprises a halogen atom, a hydroxy group and a carbon number of 1 to 12 and may have a substituent; Represents an alkylsulfonyloxy group or an arylsulfonyloxy group. ) 2. The thermosetting resin composition according to claim 1, wherein the copolymer is synthesized from the polymerizable monomer of the general formula I, a carboxylic acid group-containing monomer and an ethylenically unsaturated monomer. 3. (A) 99 to 40% by mass of the total solid content
Characterized in that it contains a resin having a carboxylic acid group in the molecule of 10 to 300 in terms of acid value, and (B) 1 to 60% by mass of the total solid content of a compound represented by the following general formula II. Thermosetting resin composition. Embedded image (Where A represents an organic residue having at least two oxygen atoms at the terminal. X represents a halogen atom, a hydroxy group,
Consisting of 1 to 12 carbon atoms, and may have a substituent;
Represents an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group, and n represents an integer of 2 or more. ) 4. The thermosetting resin composition according to claim 1, further comprising a decolorizable colorant. 5. A transfer material comprising a layer comprising the thermosetting resin composition according to claim 1 on a support. 6. The transfer material according to claim 5, wherein a release layer, a layer of the thermosetting resin composition, and a protective film are provided on a support. 7. The transfer material according to claim 5, wherein a thermoplastic layer, an intermediate layer, a layer of the thermosetting resin composition, and a protective film are provided on a support. 8. A step of (1) laminating the transfer material according to claim 5 on an active matrix substrate to form a thermosetting resin composition layer, and (2) the thermosetting resin. A method of forming an interlayer insulating film, comprising: a step of heating and curing a composition layer; and (3) a step of irradiating a laser beam imagewise to remove a laser beam irradiated portion of the transparent thermosetting resin layer. 9. Before forming the thermosetting resin composition layer,
9. The method for forming an interlayer insulating film according to claim 8, further comprising a step of forming a multicolored resin film on the active matrix substrate. 10. The method according to claim 9, wherein the color of the colored resin layer is four colors of red, blue, green and black.