JP2008165222A - Thermosetting composition for protective film, cured product, TFT active matrix substrate, and liquid crystal display device - Google Patents

Abstract

An object of the present invention is to form a coated and dried film having a uniform film thickness, excellent chemical resistance after thermosetting, no coloring during hard baking, and good light transmittance in the visible light region. The present invention provides a thermosetting composition for a protective film that can form a protective layer that does not swell during development and has excellent resolution and adhesion to a substrate.
SOLUTION: (A) an alkali-soluble resin, (B) a compound having an ethylenically unsaturated group, (C) a photopolymerization initiator, and (D) a nonionic surfactant having an HLB value of 0.5 or more and 5 or less. The thermosetting composition for protective films containing this. Component (A) is an alkali-soluble resin containing an alkyl (meth) acrylate, (meth) acrylic acid and a styrene derivative as a copolymerization component, and preferably has an acid value of 80 mg-KOH / g or more. (D) is a silicon atom-containing surfactant and preferably further contains (E) a thermal crosslinking agent.
[Selection figure] None

Description

The present invention relates to a thermosetting composition for a protective film. In particular, the present invention relates to a thermosetting composition for a protective film useful for an overcoat and an organic insulating film, which is used for a liquid crystal panel such as a liquid crystal display.
The present invention also relates to a cured product formed using the thermosetting composition for a protective film, and a TFT active matrix substrate and a liquid crystal display device having the cured product.

  Conventionally, in a TFT active matrix substrate used for a liquid crystal display device, an interlayer insulating film for protecting the TFT array element is formed between the TFT array element and a transparent conductive film forming a pixel electrode. Here, a contact hole for connecting the drain electrode of the TFT array and the wiring formed of the transparent conductive film is usually formed in the interlayer insulating film. Therefore, a photosensitive thermosetting composition is generally used as a material for the interlayer insulating film.

More specifically, as a thermosetting composition used for such applications, a composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound is known as a positive photosensitive composition ( For example, see Patent Document 1). Moreover, a photopolymerizable photosensitive composition is known as a negative thermosetting composition (see, for example, Patent Document 2). In addition, such a photopolymerizable photosensitive composition is also known in which a surfactant is blended for the purpose of improving the film-forming property (see, for example, Patent Document 3).
JP 2004-4733 A JP 2002-131899 A JP 2006-91490 A

  However, in the conventional positive photosensitive composition as described in Patent Document 1, for example, a 1,2-quinonediazide compound is colored by thermal decomposition during hard baking after exposure and development, In some cases, the light transmittance in the visible light region is lowered.

  On the other hand, in the photopolymerizable negative photosensitive composition as described in Patent Document 2, the above-mentioned coloring problem hardly occurs, but an alkali developer resulting from a change in molecular weight due to photopolymerization. Since the image is formed using the change in solubility with respect to water, the swelling is more likely to occur when immersed in an aqueous solution compared to a positive photosensitive composition that forms an image using the change in polarity due to exposure. There was a point.

  In particular, in display substrate applications, it is necessary to form a coating film having a uniform film thickness on a large area of 2 m square or more, so that a surfactant as described in Patent Document 3 is generally added. However, the addition of a surfactant improves the hydrophilicity of the coating film, and it becomes easier to swell at the time of development, resulting in a decrease in resolution and a decrease in adhesion to the substrate.

  Furthermore, in the TFT active matrix substrate application as described above, a cured film (a cured film having chemical resistance) having resistance to various etching solutions when processing the upper transparent conductive film after forming the contact hole is required. However, in a negative photosensitive composition containing a surfactant, the surfactant may aggregate in the cured film during immersion in the etching solution, resulting in a non-uniform film. That is, it was difficult to improve both the chemical resistance and the uniformity of the coating film thickness. Incidentally, the decrease in film uniformity due to the aggregation of the surfactant when immersed in the etching solution is not a problem generally known to those skilled in the art, but has been found for the first time by the present inventors. is there.

The present invention has been made in view of such circumstances.
That is, a main object of the present invention is to provide a thermosetting composition for a protective film that can form a coating and drying film having a uniform film thickness and is excellent in chemical resistance after thermosetting. Another object of the present invention is to provide a thermosetting composition for a protective film which is not colored during hard baking and has a good light transmittance in the visible light region. Furthermore, another object of the present invention is to provide a thermosetting composition for a protective film that can form a protective layer that does not swell at the time of development and has excellent resolution and adhesion to a substrate. is there. Still another object of the present invention is to provide a cured product formed of such a thermosetting composition for a protective film, a TFT active matrix substrate having such a cured product as a protective film, and a liquid crystal display device. It is in.

  As a result of intensive studies on the above problems, the present inventors have found that a specific photosensitive composition can achieve the above object, and have completed the present invention.

That is, the thermosetting composition for a protective film of the present invention contains the following components (A) to (D) (claim 1).
(A) Alkali-soluble resin (B) Compound having ethylenically unsaturated group (C) Photopolymerization initiator (D) Nonionic surfactant having HLB value of 0.5 or more and 5 or less Here, component (A) is , Alkyl (meth) acrylate, (meth) acrylic acid and a styrene derivative as a copolymerization component and an alkali-soluble resin, and preferably has an acid value of 80 mg-KOH / g or more.

  Component (D) is preferably a silicon atom-containing surfactant.

  Furthermore, this thermosetting composition for protective films can contain a component (E) thermal crosslinking agent (Claim 4).

  The cured product of the present invention is formed using such a thermosetting composition for a protective film of the present invention (Claim 5).

  The TFT active matrix substrate of the present invention is provided with such a cured product as a protective film (Claim 6), and the liquid crystal display device of the present invention is provided with such a cured product as a protective film. (Claim 7).

  According to the thermosetting composition for a protective film of the present invention, it is possible to provide a protective film that can form a coated and dried film having a uniform film thickness and is excellent in chemical resistance after thermosetting. Alternatively, it is possible to provide a protective film that is not colored during hard baking and has good light transmittance in the visible light region. Furthermore, it is possible to form a protective film that does not swell during development and has excellent resolution and adhesion to the substrate.

  The cured product formed of such a thermosetting composition for a protective film of the present invention has no coloration during hard baking, and has a high quality with a good light transmittance in the visible light region. A high-quality TFT active matrix substrate and a liquid crystal display device are provided by forming a protective film such as an overcoat or an organic insulating film using a high-quality cured product.

  The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[1] Thermosetting composition for protective film The thermosetting composition for protective film of the present embodiment (hereinafter, sometimes simply referred to as “thermosetting composition”) includes the following (A) to (A) to It is a composition containing each component of (D).
That is, in this embodiment, in order to provide a thermosetting composition for a protective film capable of forming a protective film having a good coating film thickness uniformity and excellent chemical resistance, The HLB value of component (D) contained in the composition is defined within a certain range.
(A) Alkali-soluble resin (B) Compound having ethylenically unsaturated group (C) Photopolymerization initiator (D) Nonionic surfactant having an HLB value of 0.5 to 5

  Here, the component (A) is an alkali-soluble resin containing an alkyl (meth) acrylate, (meth) acrylic acid and a styrene derivative as a copolymerization component, and has an acid value of 80 mg-KOH / g or more. Is preferred.

In addition to the essential components (A) to (D), the thermosetting composition of the present embodiment includes the following components (E) and further components (F) to (H). Can be blended.
(E) Thermal crosslinking agent (F) Other components such as adhesion aid (G) Additives such as ultraviolet absorber (H) Organic solvent

  The “HLB value” and “acid value” according to the present invention are defined as follows.

[HLB value]
The HLB value is a value representing the degree of affinity of the surfactant with water or an organic compound insoluble in water, and the “HLB value” in the present embodiment is a value defined by the Griffin method.
That is, it is defined by HLB value = 20 × [sum of formula weights of hydrophilic part] / [molecular weight].
The closer the HLB value is to 0, the higher the lipophilicity, and the closer to 20, the higher the hydrophilicity.

[Acid value]
The “acid value” in the present embodiment is a value measured according to JIS-K0070 (standard oil and fat test method).

Hereinafter, each structural component of the thermosetting composition for protective films of this invention is demonstrated.
In the present embodiment, “(meth) acryl” means “acryl and / or methacryl”. The same applies to “(meth) acrylo” and “(meth) acrylate”.
The “total solid content” means the total amount of components of the thermosetting composition excluding the solvent.

(A) Alkali-soluble resin The alkali-soluble resin used in the present embodiment is not particularly limited as long as it is a resin soluble in an alkaline developer, but may be a resin containing a carboxyl group and / or a hydroxyl group. Is preferred.

As such an alkali-soluble resin, for example,
Unsaturated group and carboxyl group-containing epoxy resin obtained by adding a carboxylic acid derivative such as (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, vinyl acetate, maleimide, etc. to an epoxy resin;
(Meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc., containing hydroxyl group or carboxyl group, hydroxyl group or carboxyl group Containing vinyl resin;
And
Polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose;
Etc. These may be used alone or in combination of two or more.

  Among these alkali-soluble resins, unsaturated group and carboxyl group-containing epoxy resins and carboxyl group-containing vinyl resins are preferable from the viewpoints of alkali developability and image-forming properties.

  Furthermore, among the carboxyl group-containing vinyl resins, a carboxyl group-containing vinyl resin not containing an unsaturated group is preferably used from the viewpoint of peelability after exposure and development.

  In the present embodiment, the acid value of component (A) is preferably 80 mg-KOH / g or more, more preferably 90 mg-KOH / g or more, and further preferably 100 mg-KOH / g or more. Moreover, as an upper limit, it is 300 mg-KOH / g or less normally, Preferably it is 200 mg-KOH / g or less. When the acid value is small, the tackiness of the coating film formed from the thermosetting composition of the present invention tends to be high. If the coating film is highly tacky, it may contact the mask during exposure and stick to the mask, the mask may become contaminated, or dust may be adsorbed on the coating film, causing defects after image formation. There is a case. If the value of the acid value is large, the solubility in an alkali developer increases, and therefore the residual film ratio after exposure and development tends to be low.

(A-1) Unsaturated group and carboxyl group-containing epoxy resin As the unsaturated group and carboxyl group-containing epoxy resin, for example, an α, β-unsaturated monocarboxylic acid adduct of an epoxy resin, a polyvalent carboxylic acid and An unsaturated group- and carboxyl group-containing epoxy resin to which an anhydride thereof is added is included. That is, (a) ethylenically unsaturated via an ester bond (—COO—) formed by ring-opening addition of (b) a carboxyl group of an α, β-unsaturated monocarboxylic acid to an epoxy group of an epoxy resin. Examples include those in which a bond is added and (c) a carboxyl group of a polyvalent carboxylic acid or an anhydride thereof is added to the hydroxyl group generated at that time.
Hereinafter, the components of the unsaturated group- and carboxyl group-containing epoxy resin will be described.

(A-1-a) Epoxy resin used for unsaturated group and carboxyl group-containing epoxy resin As an epoxy resin used for unsaturated group and carboxyl group-containing epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy Examples thereof include resins, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, trisphenol epoxy resins, and polymerized epoxy resins of phenol and dicyclopentane. Among these, from the viewpoint of high cured film strength, phenol novolac epoxy resin or cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, copolymer of glycidyl (meth) acrylate and alkyl (meth) acrylic ester Etc. are preferred.

(A-1-b) α, β-unsaturated monocarboxylic acid Examples of α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, cinnamic acid, and p-methoxycinnamic acid. , Α-phenylcinnamic acid, 1-cyclohexene-1-carboxylic acid, 2-hexenoic acid, 2-decenoic acid, monomethylmaleic acid, monoethylfumaric acid, 3- (2-furyl) acrylic acid and the like. Among these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

(A-1-c) Polyvalent carboxylic acid or anhydride thereof Examples of the polyvalent carboxylic acid or anhydride thereof include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and These anhydrides are mentioned.

  Among these, from the viewpoint of image reproducibility and developability, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and tetrahydrophthalic anhydride is more preferable.

  In the present embodiment, from the viewpoint of improving the sensitivity, resolution, adhesion to the substrate, etc. as the thermosetting composition, the epoxy resin is a phenol novolac epoxy resin as the unsaturated group and carboxyl group-containing epoxy resin. , Bisphenol epoxy resin, hydroxyfluorene epoxy resin or cresol novolac epoxy resin, α, β-unsaturated monocarboxylic acid is (meth) acrylic acid, polyvalent carboxylic acid or anhydride thereof is tetrahydrophthalic anhydride Some are preferred.

  Moreover, as an unsaturated group and a carboxyl group-containing epoxy resin, what has an acid value of 80-200 mg-KOH / g is preferable, and what is 85-180 mg-KOH / g is more preferable.

  Further, the molecular weight of the unsaturated group and carboxyl group-containing epoxy resin is usually 1,000 or more, preferably 1,500 or more, usually 40,000 or less, preferably 30,000 or less, more preferably 20,000. It is as follows.

Unless otherwise specified, the molecular weight in the present embodiment means a weight average molecular weight (Mw) in terms of polystyrene measured using a gel permeation chromatography method (GPC method). The details of the measuring method are as follows.
[Equipment] HLC-8020 manufactured by Tosoh Corporation
[Column] Tosoh Co., Ltd. GMHXL-N 30 cm × 2 [Mobile phase] 1.0 ml / min
[Column temperature] 40 ° C
[Solvent] Tetrahydrofuran stabilized with about 0.03% butylhydroxytoluene [Standard sample] Polystyrene (PSt) standard sample [Calibration curve] Fifth [Detection] RI (built-in device)
[Injection amount] 0.1 wt% 100 μL (sample is made in advance by GL Science Co., Ltd.
(Filtered with GL Chromatodisc 13P)

  The unsaturated group- and carboxyl group-containing epoxy resin in the present embodiment can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, the α, β-unsaturated monocarboxylic acid is added in the presence of a catalyst and a thermal polymerization inhibitor, and an addition reaction is carried out. A method in which a reaction is continued by adding a substance can be used.

  Here, examples of the organic solvent include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.

  Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, or tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride, and the like. Quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, or stibins such as triphenylstibine.

  Further, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

  The blending amount of the α, β-unsaturated monocarboxylic acid is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents relative to one chemical equivalent of the epoxy group of the epoxy resin. The amount can be. Moreover, as temperature at the time of addition reaction, it is 60-150 degreeC normally, Preferably it can be set as the temperature of 80-120 degreeC. Furthermore, the blending amount of the polyvalent carboxylic acid or its anhydride is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, with respect to 1 chemical equivalent of the hydroxyl group generated in the addition reaction. The amount can be one chemical equivalent.

  About the unsaturated group and carboxyl group-containing epoxy resin mentioned above, the specific example of a structural repeating unit is shown below.

(A-2) Carboxyl group-containing vinyl resin Examples of the carboxyl group-containing vinyl resin according to the present embodiment include a copolymer of an unsaturated carboxylic acid and a vinyl compound.

  Examples of the unsaturated carboxylic acid include one or more of (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and the like.

Moreover, as a vinyl compound,
Styrene derivatives such as styrene, α-methylstyrene, hydroxystyrene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-ethyladamantyl (meta ) Alkyl (meth) acrylates such as acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate;
(Meth) acrylamides such as N- (meth) acryloylmorpholine, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide;
Vinyl compounds such as (meth) acrylonitrile and vinyl acetate;
1 type, or 2 or more types, etc. are mentioned.

  Among these vinyl compounds, alkyl (meth) acrylates such as dicyclopentanyl (meth) acrylate are preferable from the viewpoint of providing a wide latitude with respect to development time and developer deterioration. Examples of such alkyl (meth) acrylates such as dicyclopentanyl (meth) acrylate include compounds exemplified in JP 2001-89533 A, for example, dicyclopentadiene skeleton, dicyclopentanyl skeleton, dicyclopentenyl. Examples thereof include alkyl (meth) acrylates having a skeleton and a dicyclopentenyloxyalkyl skeleton.

  Among the carboxyl group-containing vinyl resins made of a copolymer of the above unsaturated carboxylic acid and vinyl compound, (meth) acrylic acid and styrene derivatives are copolymerized components from the viewpoint of image shape, sensitivity, and cured film strength. A copolymer containing an alkyl (meth) acrylate- (meth) acrylic acid-styrene derivative as a copolymerization component is particularly preferable. Among them, a copolymer composed of 1 to 60 mol% of alkyl (meth) acrylate, 20 to 70 mol% of (meth) acrylic acid, and 5 to 80 mol% of styrene derivative is more preferable. In particular, a copolymer comprising 30 to 55 mol% of alkyl (meth) acrylate, 25 to 50 mol% of (meth) acrylic acid, and 8 to 50 mol% of a styrene derivative is preferable.

  As the alkyl (meth) acrylate, alicyclic alkyl (meth) acrylate such as isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-ethyladamantyl (meth) acrylate and the like. ) Acrylates are preferred.

  In the case of using a (meth) acrylate- (meth) acrylic acid copolymer containing an alicyclic alkyl (meth) acrylate as a copolymerization component as the alkali-soluble resin of the component (A), the alicyclic alkyl (meth) acrylate The content is preferably 5 mol% or more, more preferably 10 mol% or more, preferably 60 mol% or less, and more preferably 50 mol% or less.

  In addition, the acid value of these carboxyl group-containing vinyl resins is usually 80 to 250 mg-KOH / g, preferably 80 to 200 mg-KOH / g, and more preferably 90 to 150 mg-KOH / g.

  Further, the molecular weight of these carboxyl group-containing vinyl resins is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more, and usually 100,000 or less, preferably 50,000 or less, More preferably, it is 30,000 or less, Most preferably, it is 20,000 or less. The use of a carboxyl group-containing vinyl resin having a molecular weight in the above range is preferable because the peelability after development is good.

  As the alkali-soluble resin in the present embodiment, those that do not contain an aromatic ring, or those that contain an unsubstituted or phenyl group having a substituent at the p (para) position are suitable. In this case, discoloration (red coloring) due to the heat treatment of the protective film is suppressed, and cracking due to heat tends to be suppressed.

  As such an alkali-soluble resin, for example, a copolymer of styrene or dicyclopentanyl (meth) acrylate; a bisphenol A type epoxy compound or an epoxy resin, or an epoxy having a fluorene skeleton which may have a substituent An adduct compound obtained by adding an α, β-unsaturated monocarboxylic acid to a compound or an epoxy resin; a compound obtained by further adding a polyvalent carboxylic acid and an anhydride thereof to the adduct compound. .

  In addition, the alkali-soluble resin in the present embodiment is preferably a component that does not contain any ethylenically unsaturated group or epoxy group because it requires releasability after exposure and development.

  Furthermore, the alkali-soluble resin should satisfy the following relational expression from the viewpoint of suppressing generated gas when the thermosetting composition of the present embodiment is heated, or from the viewpoint of improving heat resistance. preferable.

[Relational expression]
V2 / V3 ≧ 1.3
(V2: Weight of alkali-soluble resin having a molecular weight (M2) 10 ^1/2 times the molecular weight (M1) corresponding to the maximum peak value when a differential molecular weight distribution curve is obtained by the GPC method using polystyrene as a standard substance Content rate.
V3: Weight of alkali-soluble resin having a molecular weight (M3) ^{10-1 / 2} times the molecular weight (M1) corresponding to the maximum peak value when a differential molecular weight distribution curve is obtained by GPC method using polystyrene as a standard substance Content rate. )

  The differential molecular weight distribution curve means the weight content of the alkali-soluble resin corresponding to the molecular weight for each molecular weight contained in the alkali-soluble resin. Further, such a differential molecular weight distribution curve is measured by the GPC method using polystyrene as a standard substance, similarly to the molecular weight measuring method described above.

  The V2 / V3 value is usually 1.3 or more, preferably 1.5 or more, more preferably 1.8 or more, and is usually 1,000 or less, preferably 500 or less, and more preferably 200 or less. By using an alkali-soluble resin having a low molecular weight component and a low molecular weight distribution in this way, image forming properties are improved, the protective film strength is improved, and the generation of crack defects in the ITO film on the protective layer is suppressed. Can do.

  The above-mentioned alkali-soluble resin having a specific molecular weight distribution is, for example, a resin solution obtained by dissolving a normally obtained alkali-soluble resin in (H) an organic solvent (isopropylene glycol monomethyl ether acetate or the like) described later. The resin can be precipitated by mixing with a poor solvent of an alkali-soluble resin such as methanol, followed by filtration of the precipitated resin, for example, by air drying at 40 ° C. for 12 hours under reduced pressure.

  The content of the alkali-soluble resin in the thermosetting composition of the present embodiment is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight, based on the total solid content. Hereinafter, it is preferably 70% by weight or less. If the amount of the alkali-soluble resin is excessively small, the reproducibility of the image cross-sectional shape may be deteriorated and the heat resistance may be decreased. If the amount is excessively large, the sensitivity may be decreased and the development dissolution rate may be decreased.

(B) Compound having an ethylenically unsaturated group A compound having an ethylenically unsaturated group used in the thermosetting composition of the present embodiment (hereinafter sometimes abbreviated as “ethylenically unsaturated compound”). .) Means a compound having at least one ethylenically unsaturated bond in the molecule. And it is preferable that the thermosetting composition of this Embodiment contains the compound which has 2 or more of ethylenically unsaturated groups as an ethylenically unsaturated compound.

  Examples of the compound having one ethylenically unsaturated group include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof, (meth) Examples include acrylonitrile, (meth) acrylamide, and styrene.

The compound having two or more ethylenically unsaturated bonds in the molecule may be abbreviated as, for example, esters of unsaturated carboxylic acid and polyhydroxy compound (hereinafter referred to as “unsaturated carboxylic acid esters”). ), (Meth) acryloyloxy group-containing phosphates, urethane (meth) acrylates of hydroxy (meth) acrylate compounds and polyisocyanate compounds (hereinafter sometimes abbreviated as “urethane (meth) acrylates”). And (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound epoxy (meth) acrylates (hereinafter sometimes abbreviated as “epoxy (meth) acrylates”) and the like. .
These can be used alone or in combination of two or more.

(B-1) Esters of unsaturated carboxylic acid and polyhydroxy compound Specific examples of esters of unsaturated carboxylic acid and polyhydroxy compound include the following compounds.
In the following, the “unsaturated carboxylic acid” means (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, etc., shown as a compound having one ethylenically unsaturated group. Or one or more of the unsaturated carboxylic acids.

  Reaction product of unsaturated carboxylic acid and sugar alcohol: Examples of sugar alcohol include ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples thereof include one or more of tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and the like.

  Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol: Examples of sugar alcohol are the same as described above. As an alkylene oxide adduct, 1 type (s) or 2 or more types, such as an ethylene oxide adduct or a propylene oxide adduct, are mentioned, for example.

  Reaction product of unsaturated carboxylic acid and alcoholamine: Examples of alcoholamines include one or more of diethanolamine and triethanolamine.

More specific examples of unsaturated carboxylic acid esters include the following compounds.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

  Other unsaturated carboxylic acid esters include the above unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, and 9,9'-bis (4-hydroxyphenyl) fluorene. Or a reaction product thereof with an ethylene oxide adduct. Specifically, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate] and the like.

  Further, examples of the unsaturated carboxylic acid esters include a reaction product of the unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate. Specific examples include tris (2-hydroxyethyl) isocyanurate di (meth) acrylate and tri (meth) acrylate.

  Further, examples of the unsaturated carboxylic acid esters include a reaction product of the unsaturated carboxylic acid, a polyvalent carboxylic acid, and a polyhydroxy compound. Specifically, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol, condensation of (meth) acrylic acid, terephthalic acid and pentaerythritol And a condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

A commercially available thing can be used as unsaturated carboxylic acid ester in this Embodiment.
Specifically, product names “1G”, “2G”, “3G”, “4G”, “9G”, “14G”, “23G”, “BG”, “BD”, “HD-N”, “NOD”, “IND” manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3PG, 9PG, A-200, A-400, A-600, A-1000, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, A-BPE- 30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A-B1206PE, A-HD-N, A-NOD -N "" APG-100 "" APG-200 "" APG-400 "" APG-700 ", Kyoeisha Chemical Co., Ltd. trade names" Light Ester EG "," Light Ester 2EG "," Light Ester 1.4BG "," Light Ester 1.6 " HX, Light ester 1.9ND, Light ester 1.10DC, Light ester TMP, Light ester G-101P, Light ester G-201P, Light ester BP-2EM, Light ester BP-4EM, Light ester BP-6EM "Tell 3EG""Light ester 4EG""Light ester 9EG""Light ester 14EG""Light ester NP""Light acrylate 3EG-A""Light acrylate 4EG-A""Light acrylate 9EG-A""Light acrylate 14EG-A""Light acrylate NP-A""Light acrylate MPD-A""Light acrylate 1.6HX-A""Light acrylate BEPG-A""Light acrylate 1.9ND-A""Light acrylate MOD-A""Light acrylate DCP-" A, Light acrylate BP-4EA, Light acrylate BP-10EA, Light acrylate TMP-A, Light acrylate TMP-6EO-3A, Light acrylate PE-3A, Light acrylate PE-4A, Light acrylate DPE -6A "," light acrylate BA-134 "," light ester G-201P "," light acrylate HPP-A "," light acrylate PTMGA-250 "," light " Acrylic TMP-3EO-A ”, Toagosei's product names“ Aronix M-113 ”“ Aronix M-210 ”“ Aronix M-220 ”“ Aronix M-305 ”“ Aronix M-309 ”“ Aronix M-350 ” "Aronix M-402", "Aronix M-408", Nippon Kayaku Co., Ltd. trade names "KAYARAD R-526""KAYARADNPGDA""KAYARADPEG400DA""KAYARADMANDA""KAYARADR-167""KAYARADHX-220" KAYARAD HX-620, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-3, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA- 320, KAYARAD TPA-330, KAYARAD PET-30, KAYARAD T-1420, KAYARAD RP-1040, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD And D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and KAYARAD DN-0075.

(B-2) (Meth) acryloyloxy group-containing phosphates (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing (meth) acryloyloxy groups. Those represented by (Ia) to (Ic) are preferred.

（式（Ｉａ）、（Ｉｂ）及び（Ｉｃ）中、Ｒ¹⁰は水素原子又はメチル基を示し、ｐ及びｐ´は各々独立に１〜２５の整数、ｑは１、２、又は３である。）
ここで、ｐ及びｐ´は、それぞれ１〜１０、特に１〜４であることが好ましい。

(In the formulas (Ia), (Ib) and (Ic), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are each independently an integer of 1 to 25, and q is 1, 2 or 3. .)
Here, it is preferable that p and p 'are 1-10, respectively, especially 1-4.

  Specific examples of such compounds include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and these are used alone. Or may be used as a mixture.

  As the (meth) acryloyloxy group-containing phosphates in the present embodiment, commercially available products can be used. Specifically, product names “KAYARAD PM-2” and “KAYARAD PM-21” manufactured by Nippon Kayaku Co., Ltd., product names “Light Ester P-1M”, “Light Ester P-2M”, “Light Acrylate P- 1A "," light acrylate P-2A "and the like.

(B-3) Urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound As hydroxy (meth) acrylate compounds constituting urethane (meth) acrylates, for example, hydroxymethyl (meth) acrylate, Examples include hydroxy (meth) acrylate compounds such as hydroxyethyl (meth) acrylate and tetramethylolethane tri (meth) acrylate.

Moreover, as a polyisocyanate compound, for example,
Aliphatic polyisocyanates such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane;
Cycloaliphatic polyisocyanates such as cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate; aromatics such as 4,4-diphenylmethane diisocyanate, tris (isocyanatephenyl) thiophosphate Polyisocyanate;
Heterocyclic polyisocyanates such as isocyanurates;
Allophanate-modified polyisocyanurate produced by the method described in JP-A-2001-26626;
And polyisocyanate compounds such as

  Among the urethane (meth) acrylates, urethane (meth) acrylates containing the allophanate-modified polyisocyanurate are preferable. Urethane (meth) acrylates containing allophanate-modified polyisocyanurate have low viscosity, excellent solubility in solvents, and are effective in improving adhesion to the substrate and film strength by photocuring and / or thermal curing. This is preferable in terms of points.

  As urethane (meth) acrylates in the present embodiment, commercially available products can be used. Specifically, Shin-Nakamura Chemical Co., Ltd. product names “U-4HA”, “UA-306A”, “U6LPA”, Nippon Kayaku Co., Ltd. product names “UX-2201”, “UX-3204”, “UX-4101”, “UX6” -101 "," UX-7101 "," UX-8101 "," UX-5000 "," UX-5001T "," UX-5002D "," UX5003D "," UXE1000 "," DPHA-40H ", Negami Kogyo brand name" UN-9000H " `` UN-9000PEP '' `` UN-9200A '' `` UN-7600 '' `` UN-333 '' `` UN-1255 '' `` UN-3320HA '' `` UN-3320HC '' `` UN-3320HS '' `` UN-6060P '' `` UN-5500 "SH-500B", "AGROR4060" which is a compound having an allophanate skeleton manufactured by Bayer Japan.

  As urethane (meth) acrylates in the present embodiment, from the viewpoint of sensitivity, 4 or more (preferably 6 or more, more preferably 8 or more) urethane bonds [—NH—CO—O per molecule]. -] And a compound having 4 or more (preferably 6 or more, more preferably 8 or more) (meth) acryloyloxy groups. Such a compound can be obtained, for example, by reacting the following compound (i) with the following compound (ii).

(I) a compound having 4 or more urethane bonds in one molecule, for example,
A compound obtained by reacting a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerin with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate (i -1);
Or
For compounds having two or more hydroxyl groups in one molecule such as ethylene glycol, "Duranate 24A-100", "Duranate 22A-75PX", "Duranate 21S-75E", "Duranate 21S-75E", and "Duranate 18H-" manufactured by Asahi Kasei Kogyo Co., Ltd. 70B "and other biuret types," Duranate P-301-75E "," Duranate E-402-90T "," Duranate E-405-80T "and other adduct types. Compound (i-2) obtained by reacting a compound having an isocyanate group;
Or
Compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate and the like;
Is mentioned.

  A commercial item can be used as such a compound, for example, "Duranate ME20-100" by Asahi Kasei Kogyo Co., Ltd. is mentioned.

(Ii) Compound having 4 or more (meth) acryloyloxy groups in one molecule, for example, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta Examples thereof include compounds having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as erythritol penta (meth) acrylate and dipentaerythritol hexaacrylate.

Here, the molecular weight of the compound (i) is preferably 500 to 200,000, particularly preferably 1,000 to 150,000.
Moreover, as molecular weight of urethane (meth) acrylates, it is preferable that it is 600-150,000.

  In addition, such urethane (meth) acrylates include, for example, the compound (i) and the compound (ii) in an organic solvent such as toluene and ethyl acetate at 10 to 150 ° C. for 5 minutes to It can be produced by a method of reacting for about 3 hours. In this case, the molar ratio of the former isocyanate group to the latter hydroxyl group is preferably set to a ratio of 1/10 to 10/1, and a catalyst such as n-butyltin dilaurate is preferably used as necessary.

(B-4) Epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound As polyepoxy compounds constituting epoxy (meth) acrylates, for example,
(Poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly ) Aliphatic polyepoxy compounds such as hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether;
Aromatic polyepoxy compounds such as phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds;
Heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate;
And polyepoxy compounds.

  As epoxy (meth) acrylates which are a reaction product of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound, such a polyepoxy compound and (meth) acrylic acid or the above hydroxy ( A reaction product with a (meth) acrylate compound (what was illustrated as a hydroxy (meth) acrylate compound which comprises urethane (meth) acrylates), etc. are mentioned.

  Commercially available products can be used as the epoxy (meth) acrylates in the present embodiment. Specifically, product names “KAYARAD PCR-1069”, “KAYARAD K-48C”, “KAYARAD CCR-1105”, “KAYARAD CCR-1115”, “KAYARAD TCR-1025”, “KAYARAD TCR-1064”, “KAYARAD” manufactured by Nippon Kayaku Co., Ltd. TCR-1286, KAYARAD ZFR-1122, KAYARAD ZFR-1124, KAYARAD ZFR-1185, Kyoeisha Chemical Co., Ltd. trade names "Epoxy ester 40EM", "Epoxy ester 70PA", "Epoxy ester 200PA", "Epoxy ester 80MFA" Examples include epoxy ester 3002M, epoxy ester 3002A, epoxy ester 3000M, and epoxy ester 3000A.

(B-5) Other ethylenically unsaturated compounds Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, and allyl esters such as diallyl phthalate. And vinyl group-containing compounds such as divinyl phthalate, and thioether bond-containing compounds whose crosslinking rate has been improved by sulfidizing the ether bond of an ether bond-containing ethylenically unsaturated compound with phosphorus pentasulfide to change it to a thioether bond. It is done.

  Further, for example, polyfunctional (meth) acrylate compounds described in JP-A-5-287215 and JP-A-9-100111 and silica sols having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (Nissan Chemical Co., Ltd.) "IPA-ST"), methyl ethyl ketone-dispersed organosilica sol ("MEK-ST" manufactured by Nissan Chemical Co., Ltd.), methyl isobutyl ketone-dispersed organosilica sol ("MIBK-ST" manufactured by Nissan Chemical Co., Ltd.)), Examples thereof include compounds bonded using a group-containing silane coupling agent.

  These compounds are compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding silica sol to an ethylenically unsaturated compound via a silane coupling agent.

  As other ethylenically unsaturated compounds, known compounds described in JP-A No. 2005-165294 can also be used. They may be used alone or in combination of two or more.

  In the present embodiment, the (B) ethylenically unsaturated compound preferably includes a compound having two or more ethylenically unsaturated groups in the molecule from the viewpoints of polymerizability and crosslinkability. Among them, (B-1) unsaturated carboxylic acid esters, (B-2) (meth) acryloyloxy group-containing phosphates, or (B-3) urethane (meth) acrylates, (B-4) epoxy ( (Meth) acrylates are preferred, (B-1) unsaturated carboxylic acid esters, and (B-4) epoxy (meth) acrylates are more preferred. Among the (B-1) unsaturated carboxylic acid esters, fragrances such as bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc. A group polyhydroxy compound or a reaction product thereof with an ethylene oxide adduct is particularly preferable. Among the (B-4) epoxy (meth) acrylates, (meth) acrylic acid or hydroxy (meth) acrylate compound and aroma Particularly preferred are reactants with group polyepoxy compounds.

  In addition, in the (B) ethylenically unsaturated compound according to the present embodiment, those that do not contain an aromatic ring, or those that contain an unsubstituted or phenyl group having a substituent at the p (para) position are protected. This is preferable because discoloration (red coloring) due to heat treatment of the film can be suppressed. Examples of such ethylenically unsaturated compounds include aliphatic polyfunctional (meth) acrylates and polyhydric alcohol (meth) acrylate compounds having a bisphenol A or fluorene skeleton.

  The content of the (B) ethylenically unsaturated compound in the thermosetting composition of the present embodiment is usually 20% by weight or more, preferably 30% by weight or more, based on the total solid content, Usually, it is 80% by weight or less, preferably 70% by weight or less. If the amount of the compound having an ethylenically unsaturated group is excessively small, the sensitivity and the development dissolution rate are likely to decrease. If excessively large, the reproducibility of the cross-sectional shape of the image is decreased, and the resist film is liable to be thin. .

  When component (B) in the present embodiment contains a compound having two ethylenically unsaturated groups, the compound having two ethylenically unsaturated groups is the total of component (A) and component (B). The proportion in the weight is usually 10% by weight or more, preferably 20% by weight or more, and the upper limit is usually 70% by weight or less, preferably 60% by weight or less. If the content of the compound having two ethylenically unsaturated groups is excessively large, the chemical resistance may be lowered. On the other hand, if the content is excessively small, the peelability may be lowered.

  Moreover, as a component (B) in this Embodiment, when using the compound which has 3 or more of ethylenically unsaturated groups for at least one part, as content of the compound which has 3 or more of the said ethylenically unsaturated groups, The amount is usually 100 parts by weight or less, preferably 60 parts by weight or less, and more preferably 55 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin of component (A).

  Furthermore, the content of the compound having 3 or more ethylenically unsaturated groups in the component (B) is usually 80 parts by weight or less and 60 parts by weight or less with respect to 100 parts by weight of the total weight of the component (B). It is preferable that it is 55 parts by weight or less.

  Furthermore, the proportion of the compound having three or more ethylenically unsaturated groups in the total weight of the component (A) and the component (B) is usually 60% by weight or less, preferably 50% by weight or less, more Preferably, it is 45% by weight or less, and the lower limit is usually 5% by weight or more.

  If the content of the compound having 3 or more ethylenically unsaturated groups is excessively large, the peelability after exposure is likely to be lowered.

  The compounding ratio of the component (B) to the component (A) is usually 150 parts by weight or less, preferably 130 parts by weight or less, more preferably 120 parts by weight as the compounding amount of the component (B) with respect to 100 parts by weight of the component (A). Part or less, usually 50 parts by weight or more, preferably 70 parts by weight or more, and more preferably 80 parts by weight or more.

(C) Photopolymerization initiator Any known photopolymerization initiator used in the thermosetting composition of the present embodiment can be used, and an ethylenically unsaturated group is polymerized from ultraviolet to visible light. And a compound capable of generating a radical to be generated.

Specific examples of the polymerization initiator that can be used in the present embodiment are listed below.
(1) 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 Halomethylated triazines such as-(4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine Derivative.
(2) Halomethylated oxadiazole derivative, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole 2 2-mer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methylphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)- Imidazole derivatives such as 4,5-diphenylimidazole dimer.
(3) Benzoin and benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.
(4) Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone.
(5) Benzanthrone derivatives.
(6) Benzophenone derivatives such as benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone.
(7) 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- ( p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloro Acetophenone derivatives such as methyl- (p-butylphenyl) ketone.
(8) Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.
(9) Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
(10) Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine.
(11) Phenazine derivatives such as 9,10-dimethylbenzphenazine.
(12) Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6- Pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-difluoropheny 1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6- Di-fluoropheny-1 Yl, di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl.
(13) 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropio Such as phenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. α-aminoalkylphenone compounds.
(14) Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
(15) 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl]-, 1- (O-acetyloxime)
(16) JP 2000-80068, JP 2001-233842, JP 2001-235858, JP 2005-182004, JP 2006-36750, WO 02/00903, And oxime derivatives represented by the compounds described in Japanese Patent Application No. 2005-305074.
Specific examples of the oxime derivatives include the compounds exemplified below.

  These photopolymerization initiators are used alone or in combination. Examples of combinations are described in, for example, JP-B 53-12802, JP-A-1-279903, JP-A-2-48664, JP-A-4-164902, or JP-A-6-75373. And a combination of photopolymerization initiators.

  The content of the photopolymerization initiator in the thermosetting composition of the present embodiment is usually 0.1% by weight or more, preferably 0.5% by weight or more, based on the total solid content, Usually, it is 40% by weight or less, preferably 30% by weight or less. If the amount of the photopolymerization initiator is excessively small, the sensitivity is likely to decrease, and if excessively large, the background stain (development solubility) is likely to decrease.

  Moreover, as a compounding ratio of the component (C) with respect to the component (B), the compounding amount of the component (C) with respect to 100 parts by weight of the component (B) is usually 20 parts by weight or less, preferably 10 parts by weight or less. 0.1 parts by weight or more, preferably 0.5 parts by weight or more.

(D) Nonionic surfactant In the thermosetting composition of the present embodiment, the nonionic surfactant having an HLB value of 0.5 or more and 5 or less is 0.5 as defined by the Griffin method described above. However, the lower limit of the HLB value is preferably 0.7 or more, more preferably 0.8 or more, and the upper limit is preferably 4.7 or less, more preferably 4 or less, particularly Preferably it is 3 or less.

  If the HLB value is lower than this range, the oleophilicity is increased, so that the wettability with respect to the developing solution tends to be poor and development failure tends to occur. It tends to absorb moisture when the coating solvent is dried, and uneven coating tends to occur.

As such a nonionic surfactant,
Fatty acid ester surfactants such as sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene pentaerythritol fatty acid ester;
Fatty acid amide surfactants such as fatty acid alkanolamides;
Polyether surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether;
And so on.

  In addition, silicon-containing surfactants such as fluorine-based surfactants in which some of the hydrogen atoms of these surfactants are substituted with fluorine atoms, silicone-based surfactants substituted with alkylpolysiloxane groups, and the like are also used. Can do.

  Among these, polyether surfactants, fluorine surfactants, and silicone surfactants are preferable, and polyether-modified silicone surfactants in which alkylpolysiloxane groups are introduced into a part of the polyether surfactant are used. Particularly preferred.

Specific examples of such nonionic surfactants include fatty acid ester surfactants manufactured by Lion Corporation, trade names Kadenax GS-90 (HLB: 4.3), Kadenax SO-80C (HLB: 5.3);
Polyether-modified silicone surfactants manufactured by Toray Dow Corning, trade names FZ-2110 (HLB: 1), FZ-2166 (HLB: 5), FZ-2191 (HLB: 5), SS-2805 (HLB: 5 );
Polyether-modified silicone surfactants manufactured by Shin-Etsu Silicon Co., Ltd., trade names KF-6015 (HLB: 4.5), KF-6016 (HLB: 4.5), KF-6017 (HLB: 4.5), KF-6017P (HLB: 4.5) , KF-6028 (HLB: 4.0), KF-6028P (HLB: 4.0), KF-6038 (HLB: 3.0)
And so on.

  The content of the nonionic surfactant in the thermosetting composition of the present embodiment includes (A) an alkali-soluble resin, (B) a compound having an ethylenic double bond, and (C) a photopolymerization initiator. Is usually 0.001 part by weight or more and 10 parts by weight or less, preferably 0.01 part by weight or more and 5 parts by weight or less, and more preferably 0.05 part by weight or more. Less than parts by weight. If the amount of the nonionic surfactant is less than this range, the coating property tends to be poor, and if it is large, the swelling during development tends to occur, the resolution is lowered, and the cured film after heat curing is reduced. Chemical resistance tends to decrease.

(E) Thermal crosslinking agent The thermosetting composition of this Embodiment may contain the thermal crosslinking agent in order to improve the heat resistance and chemical resistance of the film | membrane after thermosetting.
Any known thermal crosslinking agent can be used as long as it undergoes a crosslinking reaction by baking after image formation by exposure and development. Specific examples include the following.

(E-1) Compound having an epoxy group in the molecule The compound having an epoxy group in the molecule used in the present embodiment is obtained, for example, by reacting a monohydroxy compound or polyhydroxy compound with epichlorohydrin. (Poly) glycidyl ether compounds, polyglycidyl ester compounds obtained by reacting (poly) carboxylic acid compounds with epichlorohydrin, and (poly) glycidyl amine compounds obtained by reacting (poly) amine compounds with epichlorohydrin And compounds ranging from low molecular weight substances to high molecular weight substances.

(E-1-1) Polyglycidyl ether compound As the polyglycidyl ether compound, for example, diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), bis (3,5-dimethyl) -4-hydroxyphenyl) diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl ether type epoxy, tetramethylbisphenol A diglycidyl ether type epoxy, ethylene oxide-added bisphenol A diglycidyl ether Epoxy, dihydroxyoxyfluorene type epoxy, dihydroxyalkyleneoxylfluorene type epoxy, bisphenol A / aldehyde novolac type epoxy And phenol novolac type epoxy and cresol novolac type epoxy.

  The polyglycidyl ether compound includes a polyglycidyl ether resin. Polyglycidyl ether resins include bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentadiene polymerized epoxy resin, phenol and naphthalene polymerized epoxy resin, etc. A type epoxy resin is mentioned.

  These (poly) glycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride, a divalent acid compound, or the like to introduce a carboxyl group.

(E-1-2) Polyglycidyl ester compound Examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid, a diglycidyl ester type epoxy of phthalic acid, and the like.

(E-1-3) Polyglycidylamine compound Examples of the polyglycidylamine compound include diglycidylamine-type epoxy of bis (4-aminophenyl) methane and triglycidylamine-type epoxy of isocyanuric acid.

(E-1-4) Others As other examples, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meta ) Acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, etc. The polymer which reacted (meth) acrylate etc. which have the epoxy group of 1 type individually by 1 type or 2 or more types of combination is mentioned. Or the polymer which made the (meth) acrylate structural unit which has an epoxy group contain the other monomer for copolymerization normally 10-70 mol%, Preferably 15-60 mol% is mentioned.

  Examples of the monomer for copolymerization include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (meth) Esters of (meth) acrylic acid such as phenyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and , Vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, and vinylnaphthalene.

  The (meth) acrylate having an epoxy group is preferably glycidyl (meth) acrylate. Preferred examples of the monomer for copolymerization include dicyclopentanyl (meth) acrylate and α-styrene.

  When the epoxy compound is a resin (sometimes abbreviated as “epoxy resin”), the preferable molecular weight is that the protective film material (thermosetting composition) of the present embodiment is uniformly applied in a solution state. It is not particularly limited as long as it is possible, and it is appropriately selected according to the thickness of the coating film to be formed, coating conditions, purpose, and the like. The molecular weight is usually preferably in the range of 2,000 to 300,000, preferably 3,000 to 100,000, and more preferably 4,000 to 50,000.

  The epoxy group used in the epoxy compound or epoxy resin used in the present embodiment is usually a 1,2-epoxy group, but for the purpose of improving stability over time or imparting flexibility, 1 , 3-epoxy group (oxetane), 4,3-epoxycyclohexyl group can also be used.

  Moreover, as an epoxy compound which concerns on this Embodiment, it is what does not contain an aromatic ring, or it is unsubstituted or contains the phenyl group which has a substituent in p (para) position by heat processing of a protective film. This is preferable because discoloration (red coloring) can be suppressed. Examples of such epoxy compounds include bisphenol A type epoxy compounds and epoxy resins, epoxy compounds and epoxy resins having an optionally substituted fluorene skeleton, and copolymers of glycidyl (meth) acrylate. Can do.

  In the thermosetting composition of the present embodiment, a compound having an epoxy group in the molecule can also be contained. In that case, the content is usually 60% by weight or less, preferably based on the total solid content. Is 50% by weight or less, more preferably 30% by weight or less, and usually 1% by weight or more. When the content of the compound having an epoxy group in the molecule is excessively large, the storage stability of the thermosetting composition solution is lowered and the peelability after exposure / development is easily lowered.

(E-2) Nitrogen-containing thermally crosslinkable compound As the nitrogen-containing thermally crosslinkable compound used in the present embodiment, a compound obtained by allowing formalin to act on melamine, benzoguanamine, glycoluril, or urea, or an alkyl thereof. Mention may be made of modifying compounds.

Specifically, as an example of a compound in which formalin is allowed to act on melamine or an alkyl-modified product thereof, “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771 manufactured by Cytec Industries, Ltd. 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, “Nikarak” (registered trademark) E-2151, Sanwa Chemical Co., MW -100LM, MX-750LM, and the like.
Moreover, “Cymel” (registered trademark) 1123, 1125, 1128, and the like can be given as examples of a compound obtained by allowing formalin to act on benzoguanamine or an alkyl-modified product thereof.

As the (E) thermal cross-linking agent in the present embodiment, a compound having —N (CH ₂ OR) ₂ group (wherein R represents an alkyl group or a hydrogen atom) in the molecule is preferable, A compound obtained by allowing formalin to act on urea or melamine or an alkyl-modified product thereof is particularly preferable.

  The content of the nitrogen-containing thermally crosslinkable compound in the thermosetting composition of the present embodiment is usually 40% by weight or less, preferably 30% by weight or less, more preferably 20%, based on the total solid content. % By weight or less, usually 0.3% by weight or more. If the amount of the nitrogen-containing heat-crosslinkable compound is excessively large, the remaining film ratio during development and the resolution are likely to decrease, and if it is small, the hardness of the film after thermosetting tends to decrease.

(F) Other component (F-1) Adhesion aid An adhesive aid can be blended with the thermosetting composition of the present embodiment for the purpose of improving the adhesion to the substrate. Examples of the adhesion assistant include a silane coupling agent.

  More specifically, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxy Examples include silane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

  Further, the silane coupling agent has not only a function as an adhesion assistant but also a function of imparting appropriate heat melting (thermal fluidity) to the protective film in heat treatment to improve flatness. As a silane coupling agent mix | blended for such a purpose, the silane coupling agent which has an epoxy group is mentioned, for example. More specifically, γ-glycidoxypropylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

  The amount of the above-mentioned adhesion assistant is usually 0.1% by weight or more, usually 20% by weight or less, preferably 10% by weight or less based on the total solid content in the thermosetting composition.

(F-2) Surfactant The thermosetting composition of the present embodiment has the above-mentioned (D) for the purpose of improving applicability as a coating liquid of the composition and developing property of the thermosetting composition layer. ) Nonionic surfactants other than nonionic surfactants, anionic, cationic, amphoteric surfactants, or fluorine or silicone surfactants may be contained.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy And ethylene sorbite fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.

  Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfate esters. , Aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymers And surface active agents. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

  Commercially available products can be used as such anionic surfactants. For example, for alkyl sulfate esters, Kao's trade name Emar 10 and the like, for alkyl naphthalene sulfonates, Kao's trade name Plex NB-L Examples of special polymer surfactants include trade names such as homogenol L-18 and homogenol L-100 manufactured by Kao Corporation.

  Furthermore, the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, amine salts, and the like, and the amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids, and the like. Is mentioned. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include trade name Acetamine 24 manufactured by Kao Corporation for alkylamine salts and trade name Cotamin 24P, Cotamin 86W manufactured by Kao Corporation for quaternary ammonium salts.

  On the other hand, as the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain is suitable.

  Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di ( 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2- Tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9, Examples include 9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane.

  These commercially available products include BM Chemie's trade names BM-1000, BM-1100, Dainippon Ink and Chemicals trade names MegaFuck F142D, MegaFuck F172, MegaFuck F173, MegaFuck F183, MegaFuck F470, Examples include MegaFuck F475, Sumitomo 3M trade name FC430, Neos trade name DFX-18, and the like.

Examples of the silicone-based surfactant include trade names DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 manufactured by Toray Dow Corning, and trade names TSF-4440, TSF-4300, TSF manufactured by Toshiba Silicone. -4445, TSF-444 (4) (5) (6) (7) 6, TSF-4460, TSF-4442, Shin-Etsu Silicone brand name KP341, BYK Chemie brand name BYK323, BYK330 etc. be able to.
Of these, silicone surfactants and fluorine surfactants are preferred, (F-2) fluorine surfactants as surfactants, and (D) nonionic surfactants having an HLB value of 0.5 to 5 as nonionic surfactants. A combination using a silicone surfactant is more preferable.

  In the thermosetting composition of the present embodiment, the content ratio of (F-2) surfactant is preferably 10% by weight or less, and preferably 5% by weight or less, based on the total solid content. Further preferred. Moreover, it is preferable that the content rate of (F-2) surfactant with respect to (D) nonionic surfactant is 100 weight part or less with respect to 100 weight part of (D) nonionic surfactant, 50 More preferably, it is at most parts by weight.

(F-3) Curing Agent The thermosetting composition of the present embodiment further contains a curing agent for shortening the time under curing conditions and changing the set temperature, and varies depending on the manufacturing process of each element. Conditions can be selected appropriately.

  Such a curing agent is not particularly limited as long as it does not impair the required function. For example, it contains a benzoic acid compound, a polyvalent carboxylic acid (anhydride), and a polyvalent carboxylic acid (anhydride). Examples include polymers, thermal acid generators, amine compounds, polyamine compounds, and block carboxylic acids.

  In particular, when the epoxy group-containing compound is contained as a thermal crosslinking agent, it is preferable to use these curing agents.

(F-3-1) Benzoic acid-based compound As the benzoic acid-based compound, a hydroxyl group, a halogen group, an alkyl group, an acyl group, an acyloxyl group at positions 2 to 6 on the benzene ring of benzoic acid or benzoic acid. And those having a substituent such as an alkoxyl group, an aryl group, and an allyl group. Among them, those having a hydroxyl group having high curing ability for epoxy as a substituent are preferable, and those having two or more hydroxyl groups are particularly preferable. Examples of such benzoic acid compounds include 3,4,5-trihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4 , 6-trihydroxybenzoic acid and the like.

(F-3-2) Polyvalent carboxylic acid (anhydride)
As polyvalent carboxylic acid (anhydride), for example,
Cycloaliphatic polycarboxylic acids (anhydrides) such as methyl hymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride;
Aromatic polycarboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tricarboxylic anhydride, benzophenone tetracarboxylic anhydride;
Alicyclic acid anhydrides such as succinic acid, trimellitic acid, maleic acid, cyclopentanetetracarboxylic acid;
A hydrolyzate of an aromatic anhydride;
Etc.
Among these, trimellitic acid (anhydride) and phthalic anhydride are preferable.

(F-3-3) Polymer containing polyvalent carboxylic acid (anhydride) As a polymer containing polyvalent carboxylic acid and / or anhydride thereof, (anhydrous) maleic acid (maleic acid and / or its) (Anhydrides) and other (anhydrous) polyvalent carboxylic acids and compounds having at least one ethylenically unsaturated bond in the molecule, and polyvalent carboxylic acid (anhydride) moieties in such polymers And a partial half ester modified polymer.

  Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include (meth) acrylic acid and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, (poly) alkyleneoxy groups or alkyls. And alkylene having a substituent such as.

  As a polymer containing a polyvalent carboxylic acid (anhydride), a copolymer of maleic anhydride and an alkylene having a substituent such as (poly) alkyleneoxy or alkyl is particularly preferable from the viewpoint of light transmittance and cured film strength. Polymers are preferred.

(F-3-4) Thermal acid generator Examples of the thermal acid generator include various oniums such as aromatic diazonium salts, diaryliodonium salts, monophenylsulfonium salts, triallylsulfonium salts, and triallylselenium salts. Examples thereof include salt compounds, sulfonic acid esters, and halogen compounds.

  Specific examples of the aromatic diazonium salt include chlorobenzenediazonium hexafluorophosphate, dimethylaminobenzenediazonium hexafluoroantimonate, naphthyldiazonium hexafluorophosphate, dimethylaminonaphthyldiazonium tetrafluoroborate, and the like.

  Examples of the diaryl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium triflate, 4,4′-di-t-butyl-diphenyl iodonium triflate, 4 4,4′-di-t-butyl-diphenyliodonium tetrafluoroborate, 4,4′-di-t-butyl-diphenyliodonium hexafluorophosphate, and the like.

  Further, monophenylsulfonium salts include benzyl-p-hydroxyphenylmethylsulfonium hexafluorophosphate, p-hydroxyphenyldimethylsulfonium hexafluoroantimonate, p-acetoxyphenyldimethylsulfonium hexafluoroantimony. And monophenylsulfonium salt types such as benzyl-p-hydroxyphenylmethylsulfonium hexafluoroantimonate, compounds represented by the following general formula (II), and benzylphenylsulfonium salt types.

（式中、Ｚはフェニル基を示す。）

(In the formula, Z represents a phenyl group.)

  Furthermore, as the triallylsulfonium salt, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tri (p-chlorophenyl) sulfosulfonium hexafluoro Antimonate, 4-t-butyltriphenylsulfonium hexafluorophosphate and the like can be mentioned.

  Triaryl selenium salts include triallyl selenium tetrafluoroborate, triallyl selenium hexafluorophosphate, triallyl selenium hexafluoroantimonate, di (chlorophenyl) phenyl selenium tetrafluoroborate, di (chlorophenyl) phenyl selenium hexafluorophosphate , Di (chlorophenyl) phenyl selenium hexafluoroantimonate and the like.

  Examples of the sulfonate esters include benzoin tosylate, p-nitrobenzyl-9,10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, and 2,4-dinitrobenzyl. And tosylate. Examples of the halogen compound include 2-chloro-2-phenylacetophenone, 2,2 ′, 4′-trichloroacetophenone, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, bis-2- (4-chlorophenyl) -1,1,1-trichloroethane Bis-1- (4-chlorophenyl) -2,2,2-trichloroethanol, bis-2- (4-methoxyphenyl) -1,1,1-trichloro Tan, and the like.

  Among these thermal acid generators, the monophenylsulfonium salt type or the benzylphenylsulfonium salt type is preferable from the viewpoints of light transmittance and cured film strength.

(F-3-5) Amine compound As the amine compound, for example,
Ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, piperidine, pyrrolidine, triethylenediamine, trimethylhexamethylenediamine, dimethylcyclohexylamine, tetramethylguanidine, tri Ethanolamine, N, N′-dimethylpiperazine, dicyanamide, or a derivative thereof;
Aliphatic (primary, secondary, tertiary) amines such as DBU (1,8-diazabiscyclo (5,4,0) undecene-1), DBU-based tetraphenylborate salts;
Metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, benzyldimethylamine, dimethylamino-p-cresol, 2- (dimethylaminejomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, Aromatic compounds such as pyridine, picoline, DBU (1,8-diazabiscyclo (5,4,0) undecene-1) and tri-2-ethylhexylate of 2,4,6-tris (dimethylaminomethyl) phenol 1, secondary, tertiary) amines;
2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1 -Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium Isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 2,4-diamino-6- [2-ethylimidazolyl] -(1)]-ethyl-S- Riazine, 2,4-diamino-6- [2-undecylimidazolyl- (1)]-ethyl-S-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl- Imidazole compounds such as 5-hydroxymethylimidazole and 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole;
Diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine;
Etc.

  Among these, dicyanamide and DBU tetraphenylborate salts are preferable from the viewpoint of the cured film strength.

(F-3-6) Polyamine compound Examples of the polyamine compound include triethyltetramine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropylamine, diethylaminopropylamine, N-aminoethylpiperazine, mensendiamine, isofluorodiamine, Aliphatic polyamines such as bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylamine, N, N-dimethylcyclohexylamine, m-xylenediamine, xylylenediamine, xylylenediamine derivatives, xylylenediamine trimers And aromatic polyamines such as Among these, N, N-dimethylcyclohexylamine is preferable.

(F-3-7) Block Carboxylic Acid Examples of the block carboxylic acid include, for example, the above (polyvalent) carboxylic acids and carboxylic acids of polymers containing them as disclosed in JP-A-4-218561 and JP-A-2003-66223. Examples thereof include block carboxylic acids to which vinyl ether is added by the methods described in JP-A-2004-339332, JP-A-2004-339333, and the like.

  Among the curing agents, polymers containing polyvalent carboxylic acids (anhydrides), onium salt compounds, block carboxylic acid compounds, and benzoic acid compounds are excellent in curing reaction activity and have high hardness and support. It is preferable at the point that adhesiveness of this is obtained.

More specifically,
Among maleic anhydride and ethylene, butylene, or propylene compounds containing styrene, alkyl group having 1 to 20 carbon atoms, polypropyleneoxypropylene group having 1 to 15 carbon atoms or polyethyleneoxypropylene group having 1 to 15 carbon atoms, styrene A polyvalent carboxylic acid copolymer with at least one selected ethylene compound;
Block carboxylic acid compound consisting of adduct of trimellitic acid or maleic acid and ethyl vinyl ether;
Benzoic compounds such as 2,5-dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid;
Benzyl-p-hydroxyphenylmethylsulfonium hexafluorophosphate, p-hydroxyphenyldimethylsulfonium hexafluoroantimonate, p-acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-p-hydroxyphenylmethylsulfo And monophenylsulfonium salts such as nium hexafluoroantimonate, monophenylsulfonium salt types such as compounds represented by the general formula (II), and benzylphenylsulfonium salt types.

  Among these, polyvalent carboxylic acid copolymers and benzoic acid compounds are excellent in improving the adhesion to the support, and monosulfonium salts are excellent in improving the hardness.

  A benzoic acid compound is particularly preferable because it is excellent in thermosetting, has high light transmittance, and is less affected by color change due to heat.

  In the thermosetting composition of the present embodiment, (F-3) a curing agent can also be added. In that case, the content of the curing agent is usually 0.05 wt. % Or more, preferably 0.1% by weight or more, usually 20% by weight or less, preferably 10% by weight or less. When the amount of the curing agent is excessively small, adhesion to the support and hardness are liable to be reduced. On the other hand, when the amount is excessively large, decrease in thermal weight is likely to be increased.

(G) Additive In addition to the above components, the thermosetting composition of the present embodiment includes various additives such as o-hydroxybenzophenone, hydroquinone, and p-methoxyphenol, which may have a substituent. , 2,6-di-t-butyl-p-cresol can be blended. The compounding ratio of these compounds is usually 10% by weight or less, preferably 2% by weight or less, based on the total solid content.

  Moreover, you may contain plasticizers, such as a dioctyl phthalate, didodecyl phthalate, and tricresyl phosphate, similarly in the ratio of 40 weight% or less, Preferably it is 20 weight% or less.

  Furthermore, a polymerization accelerator can be added to the thermosetting composition of the present embodiment as necessary. Specific examples of the polymerization accelerator include esters of amino acids such as N-phenylglycine or dipolar compounds thereof, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2, Mercapto group-containing compounds such as 4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate , Polyfunctional thiol compounds such as hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, N, N-dialkylaminobenzoic acid ester, N-pheny Derivatives such as glycine or its ammonium and sodium salts, phenylalanine, or salts such as its ammonium and sodium salts, amino acids or derivatives thereof and the like having an aromatic ring such as derivatives of esters.

  In the thermosetting composition of the present embodiment, when a polymerization accelerator is added, the content is preferably 20% by weight or less, and preferably 1 to 10% by weight with respect to the total solid content. More preferably.

  Furthermore, an ultraviolet absorber can be added to the thermosetting composition of the present embodiment as necessary. The ultraviolet absorber absorbs a specific wavelength of the light source used for exposure by the ultraviolet absorber, and thereby the photocuring speed when the film of the thermosetting composition of the present embodiment formed on the substrate is exposed. It is added for the purpose of controlling. By adding an ultraviolet absorber, it is possible to improve the pattern shape after exposure / development and to eliminate residues remaining in the non-exposed areas after development.

As the ultraviolet absorber, for example, a compound having an absorption maximum between wavelengths of 250 nm to 400 nm can be used. More specifically, for example,
Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Yongkou Chemical Industries, Taiwan), Thomsorb 800 (manufactured by API Corporation), SESORB101, SESORB101S, SESORB102, SEESORB103, SEESORB103, SEESORB105, SEESORB105, SEESORB105, SEESORB105 Benzophenone compounds such as
Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry), TINUVIN PS, TINUVIN99-2, TINUVIN1092, TINUVIN384-2, TINUVIN900-2 , TINUVIN928, TINUVIN1130 (manufactured by Ciba Specialty Chemicals), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERORB76, EVERSORBVER234, EVERSORB234 100, (manufactured by API Corporation) Tomisobu 600, SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Shipro Kasei) benzotriazole compounds, such as
Benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate;
Examples thereof include hydroxyphenyltriazine compounds such as TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477DW, and TINUVIN479 (manufactured by Ciba Specialty Chemicals).

  Among these, benzotriazole compounds and hydroxyphenyltriazine compounds are preferable, and benzotriazole compounds are particularly preferable.

  When an ultraviolet absorber is added to the thermosetting composition of the present embodiment, the blending ratio is usually 0.01% by weight or more and 15% by weight or less, preferably 0.05% by weight with respect to the total solid content. % To 10% by weight. Further, the blending ratio with respect to component (C) is usually 1 part by weight or more, preferably 5 parts by weight or more, and more preferably 10 parts by weight or more as the blending amount of the ultraviolet absorber with respect to 100 parts by weight of component (C). The amount is usually 150 parts by weight or less, preferably 100 parts by weight or less, and more preferably 80 parts by weight or less. If the blending ratio is less than this range, effects such as improvement of the pattern shape and / or removal of the residue tend to be difficult to obtain, and if it is large, the sensitivity and / or the remaining film ratio tend to decrease.

(H) Organic solvent The above-mentioned components are usually used after being prepared using an organic solvent so that the solid content concentration is in the range of 5 to 60% by weight, preferably 10 to 50% by weight.
The organic solvent is not particularly limited as long as it can dissolve and disperse the above-described components and has good handleability.

  Specifically, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as “PGMAc”), methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, 3-methoxymethyl propionate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether, methanol, ethanol, propanol, butanol, tetra Hydrofuran, diethylene glycol dimethyl ether, methoxybutyl acetate, solvesso Carbitol, and the like.

  The boiling point of the organic solvent is preferably in the range of 100 to 200 ° C, more preferably in the range of 120 to 170 ° C.

  Moreover, the organic solvent can also be used individually by 1 type, However, You may mix and use 2 or more types. As a combination of organic solvents used by mixing, for example, PGMAc mixed with one or more organic solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbeso and carbitol can be mentioned.

  Furthermore, in the above mixed solvent, the blending ratio of one or more organic solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbesso and carbitol is usually 10% by weight or more, preferably 30% by weight or more based on PGMAc. It is usually 80% by weight or less, preferably 70% by weight or less.

  Further, among the above mixed solvents, a mixed solvent of PGMAc and methoxybutyl acetate is suitable for flattening the unevenness of the substrate because it induces appropriate fluidity of the coating film in the coating and drying step.

[2] Method of forming protective film (cured product) Next, a method of forming a cured product using the thermosetting composition of the present embodiment will be described. A case where a protective film is formed by applying a functional composition will be described as an example. The thermosetting composition of the present invention is useful for forming an overcoat or an organic insulating film (an interlayer insulating film made of an organic compound) used for a liquid crystal panel such as a liquid crystal display. The effect is remarkable when it is used for forming an insulating film.

[2-1] Coating process First, a spinner, a wire bar, a flow coater, a die coater, a roll coater, a spray or the like is applied to the thermosetting composition of the present embodiment described above on a substrate on which a TFT array is formed. Apply using equipment.
The coating film thickness of the thermosetting composition is usually 0.5 to 5 μm.

[2-2] Drying step The coating film is dried to remove volatile components and form a dry coating film. For drying, vacuum drying, hot plate, IR oven, convection oven or the like can be used. Preferred drying conditions are a temperature of 40 to 150 ° C. and a drying time of 10 seconds to 60 minutes. In addition, a method of performing heat drying with a hot plate after vacuum drying is preferable because a film with less coating unevenness can be formed. In this case, preferable vacuum drying conditions are a pressure of 10 to 10000 Pa and a drying time of 30 seconds to 10 minutes, and preferable heating and drying conditions are a temperature of 60 to 120 ° C. and a time of 30 seconds to 10 minutes.

[2-3] Exposure / Development Step Next, a photomask is placed on the dried coating film of the thermosetting composition, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel.

  Note that post-exposure baking may be performed after exposure for the purpose of improving sensitivity before development. For baking in this case, a hot plate, an IR oven, a convection oven, or the like can be used. Post-exposure bake conditions are usually in the range of 40 to 150 ° C. and drying time of 10 seconds to 60 minutes.

  Usually, an image obtained after development is required to have a fine line reproducibility of 20 μm width. In addition, in order to realize a high-quality display, higher fine line reproducibility tends to be required. In order to stably reproduce high-definition fine lines, a rectangular shape with a clear contrast between the non-image and the image area is used as the cross-sectional shape of the fine line image after development. A wide margin is preferable.

  Examples of the light source used in the exposure process of the dried coating film include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, and the like, an argon ion laser, a YAG laser. And laser light sources such as excimer laser and nitrogen laser. When only light of a specific wavelength is used, an optical filter can be used.

  Examples of the exposure method include a contact exposure method, a proximity exposure method, a step-and-repeat exposure method, a step-and-scan exposure method, and a mirror projection exposure method. Further, exposure by a direct drawing method without using a mask can also be used.

  The solvent used for the development processing is not particularly limited as long as it is a solvent capable of dissolving the dry film of the uncured part, but as described above, environmental pollution, harm to human body, fire risk, etc. In view of this, it is preferable to use an alkali developer instead of an organic solvent.

  Examples of such an alkali developer include one or more inorganic alkali compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide. Or an aqueous solution containing one or more organic alkali compounds such as diethanolamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide.

  The alkaline developer may contain a surfactant, a water-soluble organic solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, etc., if necessary. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.

  Examples of the surfactant used in the developer include an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And cationic surfactants.

  Although there is no particular limitation on the development processing method, it is usually carried out by a method such as immersion development, paddle development, spray development, brush development, ultrasonic development at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C. Is called.

[2-4] Heat treatment step The cured film on which an image has been formed by the exposure / development step is then subjected to a heat treatment (hard baking) step to become a cured product (thermosetting film). In addition, after the development, the entire surface exposure may be performed for the purpose of suppressing the generation of outgas during the hard baking before the hard baking.

  When performing full exposure before hard baking, ultraviolet light or visible light is used as the light source. And a laser light source such as an argon ion laser, a YAG laser, an excimer laser, and a nitrogen laser.

  Moreover, a hot plate, IR oven, convection oven, etc. can be used for hard baking. The hard baking conditions are usually in the range of 100 to 250 ° C. and heating time of 30 seconds to 90 minutes.

  The thickness of the protective film thus formed is usually 0.5 to 5 μm.

[3] TFT active matrix substrate and liquid crystal display device (panel)
Next, a manufacturing method of the TFT active matrix substrate and the liquid crystal display device (panel) according to the present embodiment including the protective film formed as described above will be described. The liquid crystal display device according to the present embodiment usually includes a TFT active matrix substrate.

  First, the TFT active matrix substrate is formed by forming the above-mentioned cured product as a protective film on the substrate on which the TFT element array is formed, forming an ITO film thereon, and then forming an ITO wiring using a photolithography method. It is formed by.

Then, the liquid crystal display device according to the present embodiment is completed by bonding the TFT active matrix substrate to the counter substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and further connecting the counter electrode. be able to.
In general, a color filter substrate having an alignment film is preferably used as the counter substrate.

As the alignment film, a resin film such as polyimide is suitable.
For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted. A protective film similar to the above may be further formed on the alignment film.

  The bonding gap between the TFT active matrix substrate and the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin.

  As such a sealing material, a material that can be cured by UV irradiation and / or heating is usually used, and the periphery of the liquid crystal cell is sealed. After the liquid crystal cell whose periphery is sealed is cut into panels, the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. Can do.

The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. It is. In addition, it is preferable to warm the liquid crystal cell during decompression. The heating temperature in this case is usually 30 ° C. or higher, preferably 50 ° C. or higher, and is usually 100 ° C. or lower, preferably 90 ° C. or lower.

  The heating and holding condition during decompression is usually in the range of 10 minutes to 60 minutes. Thereafter, the liquid crystal cell is immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected cures the UV curable resin and seals the liquid crystal injection port. In this way, a liquid crystal display device (panel) can be completed.

  In addition, there is no restriction | limiting in particular in the kind of liquid crystal, A liquid crystal conventionally known, such as an aromatic type, an aliphatic type, a polycyclic compound, can be used, Any of a lyotropic liquid crystal, a thermotropic liquid crystal, etc. may be sufficient. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.
[Structural component]
The components used for the preparation of the thermosetting compositions in the following examples and comparative examples are as follows.

(A) Alkali-soluble resin

(B) Ethylenically unsaturated compound

(C) Photopolymerization initiator

(D) Nonionic surfactant S1: FZ-2110 manufactured by Toray Dow Corning
(Polyether-modified silicone HLB value: 1)
S2: Shin-Etsu Silicon KF-6015
(Polyether-modified silicone HLB value: 4.5)
S3: Shin-Etsu Silicon KF-6013
(Polyether-modified silicone HLB value: 10)

(E) Thermal crosslinking agent

(F) Other components Y1 (adhesion aid): γ-glycidoxypropyltrimethoxysilane Y2: Fluorosurfactant FC4432 (HLB value:> 5) manufactured by Sumitomo 3M

(G) Additive

(H) Organic solvent PGMAc: Propylene glycol monomethyl ether acetate

[Evaluation methods]
Evaluation methods of the thermosetting compositions, exposure films and thermosetting films obtained in the following examples and comparative examples are as follows.

(Applicability)
A thermosetting composition was applied on a glass plate “AN100” glass plate for color filter manufactured by Asahi Glass Co., Ltd., and dried on a hot plate at 90 ° C. for 90 seconds to obtain a coating film having a dry film thickness of 4 μm. The coating unevenness on the film surface was evaluated by visual observation under a sodium lamp according to the following criteria.
A: No coating unevenness.
B: There are coating irregularities with a large period.
C: There is fine coating unevenness on the entire surface.

(Optimal exposure)
The coating film obtained by the procedure for evaluating the coating property was exposed with a high-pressure mercury lamp at an illuminance of 30 mW / cm ² . As exposure conditions, the exposure energy amount was set in the range of 10 mJ / cm ² to 320 mJ / cm ² and the exposure energy amount was set at intervals of 2 ^1/2 times. After exposure, the film was immersed in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 70 seconds, rinsed with pure water, and the film thickness of the remaining cured film (exposure film) was measured.
The film thickness of the obtained exposure film is plotted against the exposure dose, and the minimum exposure dose at which the difference in exposure film thickness between a certain exposure dose and the exposure dose that is ^21/2 times is within 10%. Was the optimum exposure (mJ / cm ² ).

(Resolution)
The image of the thermosetting film was observed with an optical microscope, and the minimum line width (μm) resolved was defined as the resolution.

(Pattern shape)
By observing a line pattern shape having a line width of 20 μm of the thermosetting film with a scanning electron microscope, the pattern shape was evaluated according to the following criteria.
A: Good rectangularity and no bottoming B: Good rectangularity but slightly bottoming C: Poor rectangularity or no resolution

(Residue)
A space pattern with a line width of 30 μm of the thermosetting film was observed with an optical microscope, and the residue in the space portion was evaluated according to the following criteria.
A: No residue B: Residue is slightly seen in the periphery of the resist C: Residue is seen in the center of the space part

(chemical resistance)
The thermosetting film was immersed in 20 wt% hydrochloric acid at 40 ° C. for 20 minutes and evaluated according to the following criteria.
○: Holes and surface roughness (unevenness) were not observed by surface observation with an optical microscope.
X: Holes and surface roughness (unevenness) were observed by surface observation with an optical microscope. Or cloudiness was observed visually.

(Light transmittance)
Except for exposing the entire surface without using a mask, the light transmittance of a cured film formed in the same manner was measured with a spectrophotometer UV3100PC manufactured by Shimadzu Corporation, and the minimum transmittance (% in a wavelength range of 600 nm to 400 nm) )

[Examples 1-5, Comparative Examples 1-2]
Thermosetting compositions were prepared with the formulations shown in Table 1.

The obtained thermosetting composition was applied on a glass plate “AN100” for color filter manufactured by Asahi Glass Co., Ltd. and dried on a hot plate at 90 ° C. for 90 seconds to obtain a coating film having a dry film thickness of 4 μm. It was. Then, it exposed using the 3kW high pressure mercury lamp through the mask which has a thin line pattern with a line | wire width of 10 micrometers-50 micrometers from the coating film side. As the exposure conditions, the image plane illuminance measured with an illuminometer with a wavelength of 365 nm was 30 mW / cm ² , and the exposure amount was the optimum exposure amount described later.

  Next, a 0.4 wt% aqueous solution of tetramethylammonium hydroxide was used as a developing solution, and development was performed by immersing the substrate in the developing solution at 25 ° C. for 70 seconds, followed by rinsing with pure water and exposure film. Got. The obtained exposure film was heated at 220 ° C. for 1 hour in a convection oven to obtain a thermosetting film.

  Various evaluations were performed on the thermosetting composition, the exposure film, and the thermosetting film. The results are also shown in Table 1.

  From Table 1, it can be seen that the thermosetting composition of the present invention is excellent in coating property, sensitivity, resolution, etc., has good chemical resistance, and can form a protective film excellent in light transmittance.

Claims (7)

A thermosetting composition for a protective film comprising the following components (A) to (D):
(A) Alkali-soluble resin (B) Compound having ethylenically unsaturated group (C) Photopolymerization initiator (D) Nonionic surfactant having an HLB value of 0.5 to 5   The component (A) is an alkali-soluble resin containing an alkyl (meth) acrylate, (meth) acrylic acid and a styrene derivative as a copolymerization component, and has an acid value of 80 mg-KOH / g or more. The thermosetting composition for protective films according to claim 1.   The thermosetting composition for a protective film according to claim 1, wherein the component (D) is a silicon atom-containing surfactant. Furthermore, the following component (E) is contained, The thermosetting composition for protective films of any one of Claim 1 thru | or 3 characterized by the above-mentioned.
(E) Thermal crosslinking agent   Hardened | cured material formed using the thermosetting composition for protective films of any one of Claims 1 thru | or 4.   A TFT active matrix substrate comprising the cured product according to claim 5 as a protective film.   A liquid crystal display device comprising the cured product according to claim 5 as a protective film.