JP5256645B2 - Thermosetting composition for protective film, cured product, and liquid crystal display device - Google Patents

Description

The present invention relates to a thermosetting composition for a protective film by light or heat. More specifically, for example, printed circuit boards, liquid crystal display elements, plasma displays, large scale integrated circuits, thin transistors, semiconductor packages, color filters, solder resist films and coverlay films in organic electroluminescence, etc., and insulation of various electronic components The present invention relates to a curable composition useful for forming a coating layer.
Further, the present invention is used in a liquid crystal panel such as a liquid crystal display, curable composition useful as a for Oh Bakoto, and the cured product formed by using the same, and a liquid crystal display device having the same.

  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 composition is known as a negative thermosetting composition (see, for example, Patent Document 2).
JP 2004-4733 A JP 2002-131899 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, although the above-mentioned coloring problem is hardly caused, there is still room for improvement from the viewpoint of repairability. Had. In other words, even if a defect is detected in the defect inspection after exposure / development, repair may be possible if the cured photosensitive composition film can be easily peeled off (improvement in product production cost). May be possible). Conventionally known negative photosensitive compositions tend to be difficult to peel.
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. It is done. Conventionally, it has been difficult to achieve both the chemical resistance and the peelability.

The present invention has been made in view of such circumstances.
That is, the main object of the present invention is to provide a thermosetting composition for a protective film which is excellent in peelability after exposure and development.
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, the other object of this invention is to provide the thermosetting composition for protective films which can form the protective layer excellent in the chemical resistance after thermosetting.
Still another object of the present invention is to provide a cured product formed from such a thermosetting composition for a protective film, and a liquid crystal display device comprising the cured product as a protective film.

  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 protective film of the present invention comprises the following components (A) to (D), (A) an alkali-soluble resin, (B) a compound having two or more ethylenically unsaturated groups, (C) a photopolymerization initiator, (D) (D-1) a compound having an epoxy group in the molecule and / or (D-2) a thermal crosslinking agent containing a nitrogen-containing thermally crosslinkable compound, The content of the ethylenically unsaturated group with respect to the total weight of the component (A) and the component (B) is 1 mmol / g or more and 5 mmol / g or less, and the component (B) contains 2 ethylenically unsaturated groups. And the ratio of the compound having two ethylenically unsaturated groups to the total weight of the component (A) and the component (B) is 10% by weight or more. 0.4% by weight tetramethyl of the exposed film cured by exposure at the optimum exposure amount The dissolution rate of in Nmo onium hydroxide aqueous solution (25 ° C.) is characterized in that not more than 2.3 .mu.m / min.

Here, Ingredient (A) may be characterized by any of the ethylenically unsaturated group, or an epoxy group is a component which does not contain. Furthermore, the dissolution rate in N-methylpyrrolidone (60 ° C.) of a thermosetting film obtained by baking at 220 ° C. for 1 hour after exposure at an optimal exposure amount is 0.1 μm / min or less. It can be.

On the other hand, the present invention is regarded as a cured product, and the cured product of the present invention is formed by any one of the above-described thermosetting compositions for protective films.
Further, the present invention is regarded as a liquid crystal display device, and the liquid crystal display device of the present invention is characterized by including the cured product as a protective film.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting composition for protective films which is excellent in the peelability after exposure and image development can be provided. Further, it is possible to provide a thermosetting composition for a protective film that is not colored during hard baking and has good light transmittance in the visible light region. Furthermore, the thermosetting composition for protective films which can form the protective layer excellent in the chemical resistance after thermosetting is provided. Furthermore, a cured product formed from such a thermosetting composition for a protective film is not colored during hard baking, and a protective film having good light transmittance in the visible light region is used. Quality. The TFT active matrix substrate and the liquid crystal display device of the present invention are of high quality because a high-quality cured product is used.

  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 Each component of (C),
(A) an alkali-soluble resin,
(B) a compound having two or more ethylenically unsaturated groups,
(C) a photopolymerization initiator,
The content of ethylenically unsaturated groups relative to the total weight of component (A) and component (B) (hereinafter sometimes abbreviated as “ethylenically unsaturated group equivalent”) is 1 mmol / g. The dissolution rate in a 0.4 wt% tetramethylammonium hydroxide aqueous solution (25 ° C.) (hereinafter referred to as “development dissolution rate”) of the exposed film cured by exposure at an optimal exposure amount and not less than 5 mmol / g. ”May be abbreviated as“ 2.3 μm / min or less ”.

  Further, the dissolution rate in N-methylpyrrolidone (60 ° C.) of a thermosetting film obtained by baking at 220 ° C. for 1 hour after exposure at an optimal exposure amount (hereinafter abbreviated as “NMP dissolution rate”). As for (it is), it is suitable that it is 0.1 micrometer / min or less.

  Hereinafter, first, “ethylenically unsaturated group equivalent”, “optimum exposure amount”, “development dissolution rate”, and “NMP dissolution rate” will be described.

[Equivalent ethylenically unsaturated group]
The ethylenically unsaturated group equivalent is calculated by the following formula. The value increases as the number of ethylenically unsaturated groups per unit weight increases.
<Relational expression>
Equivalent ethylenically unsaturated group (mmol / g) = number of millimoles containing ethylenically unsaturated group in composition / [weight of component (A) (g) + weight of component (B) (g)]

The larger the value of the ethylenically unsaturated group equivalent, the higher the polymerization density by exposure, and the more difficult it is to peel off after development. On the other hand, if the value of the ethylenically unsaturated group equivalent is small, the polymerization density due to exposure becomes small, and thus chemical resistance after hard baking may deteriorate. In addition, film loss during development increases, and resolution and pattern shape may deteriorate.
The upper limit of the ethylenically unsaturated group equivalent is 5 mmol / g or less, preferably 4.5 mmol / g or less, more preferably 4 mmol / g or less. Further, the lower limit is 1 mmol / g or more, preferably 1.5 mmol / g or more, more preferably 2 mmol / g or more.

  In addition, about said "ethylenically unsaturated group containing millimol number in a composition", when the chemical structural formula of component (B) and component (A) contain an ethylenically unsaturated group, the charging ratio of the monomer Is a value calculated from the chemical structural formula of the polymer expected from

In the present invention, methods for adjusting the ethylenically unsaturated group equivalent to 1 to 5 mmol / g include the following methods 1) to 3).
1) Adjust the amount of the compound having 2 or more ethylenically unsaturated groups.
2) When the alkali-soluble resin contains an ethylenically unsaturated group, the content thereof is adjusted.
3) In a compound having two or more ethylenically unsaturated groups, reduce the number of ethylenically unsaturated groups and increase the molecular weight.

[Optimal exposure]
The thermosetting composition of the present embodiment is applied on a glass substrate so that the dry film thickness is about 4 μm, and baked on a hot plate at 90 ° C. for 90 seconds. Then, it exposes with the illumination intensity of 30 mW / cm < ² > with a high pressure mercury lamp. As exposure conditions, the exposure energy amount is set in the range of 10 mJ / cm ² to 320 mJ / cm ² and the exposure energy amount is set at intervals of 2 ^1/2 times. After the exposure, the film is 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) is measured.
The film thickness of the obtained exposure film is plotted against the exposure amount. The minimum exposure amount at which the difference in the film thickness of the exposure film between a certain exposure amount and an exposure amount that is ^2½ times that amount is within 10% is defined as the optimum exposure amount (mJ / cm ² ).

[Development dissolution rate]
The thermosetting composition of this embodiment is applied on a glass substrate, and baked on a hot plate at 90 ° C. for 90 seconds to measure the dry film thickness. Then, it exposes with the illumination intensity of 30 mW / cm < ² > with a high pressure mercury lamp. The exposure amount is the optimum exposure amount. After exposure, the film is immersed (developed) in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for a certain period of time, then rinsed with pure water, and the film thickness of the remaining exposed film is measured.
A value obtained by dividing the difference (μm) between the dry film thickness after baking and the film thickness of the exposed film remaining after rinsing with pure water by the development time (minutes) is defined as the development dissolution rate.

The larger the value of the development dissolution rate, the worse the chemical resistance after hard baking, or the reduction in film thickness during development may lead to deterioration in resolution and pattern shape.
The developing dissolution rate in the present embodiment is 2.3 μm / min or less, preferably 2 μm / min or less, more preferably 1.8 μm / min or less. Moreover, although it does not specifically limit as a minimum, Usually, it is 0.01 micrometer / min or more.

  In the present embodiment, “hard baking” means baking processing performed after exposure and development processing. By the hard baking, the thermosetting composition of the present embodiment is sufficiently cured, and a thermosetting film is obtained.

In the present invention, the following i) to v) may be mentioned as means for reducing the developing dissolution rate to 2.3 μm / min or less. Of these, the methods iv) and v) are particularly preferable.
i) Lower the acid value of the alkali-soluble resin.
ii) In a compound having two or more ethylenically unsaturated groups, increase the number of ethylenically unsaturated groups.
iii) Increasing the amount of the compound having two or more ethylenically unsaturated groups relative to the total solid content.
iv) An alkali-soluble resin having an alicyclic group and / or an aryl group is used.
v) Use of a polymerization initiator (specific examples: acylphosphine oxide compounds, oxime derivatives) that is difficult to inhibit polymerization by oxygen.

[NMP dissolution rate]
The thermosetting composition of the present embodiment is applied on a glass substrate so that the dry film thickness is about 4 μm, and baked on a hot plate at 90 ° C. for 90 seconds. Then, it exposes with the illumination intensity of 30 mW / cm < ² > with a high pressure mercury lamp. The exposure amount is the optimum exposure amount. After exposure, it is further baked in an oven at 220 ° C. for 1 hour to obtain a thermosetting film.
This thermosetting film is immersed in N-methylpyrrolidone at 60 ° C. for 20 minutes, rinsed with pure water, and the film thickness of the remaining thermosetting film is measured.
The value obtained by dividing the difference (μm) between the film thickness of the thermosetting film and the film thickness of the thermosetting film remaining after rinsing with pure water by the N-methylpyrrolidone immersion time (minutes) is the NMP dissolution rate. Define.

The higher the NMP dissolution rate, the worse the chemical resistance of the thermosetting film after hard baking may be.
The NMP dissolution rate is usually preferably 0.1 μm / min or less, more preferably 0.08 μm / min or less, and particularly preferably 0.06 μm / min or less. Moreover, although it does not specifically limit as a minimum, Usually, it is 0.0001 micrometer / min or more.

Means for reducing the NMP dissolution rate to 0.1 μm / min or less include the following means vi) and vii) in addition to the aforementioned development dissolution rate achievement means i) to v).
vi) Increase the amount of thermal crosslinking agent.
vii) Increase the number of crosslinking groups (epoxy groups, —N (CH ₂ OR) ₂ groups) in the thermal crosslinking agent molecule.

  In the present embodiment, the ethylenically unsaturated group equivalent of the thermosetting composition and the development dissolution rate are constant to provide a thermosetting composition for a protective film having excellent peelability after exposure and development. It is specified in the range. The problem of the present embodiment (improvement of peelability) was not a problem generally known to those skilled in the art.

Next, each component used for the thermosetting composition of this Embodiment is demonstrated.
In addition to the essential components (A) to (C) described above, the following components can be blended in the thermosetting composition of the present embodiment.
(D) Thermal crosslinking agent (E) Other components (F) Additive (G) Organic solvent

  Hereinafter, each component will be described.

In the present embodiment, “(meth) acryl” means “acryl and / or methacryl”. The same applies to “(meth) acrylate”, “(meth) acryloyl” and the like.
In addition, “poly” in front of the monomer name means that both the monomer and the polymer are included, and “(acid) anhydride”, “(anhydrous) ... acid” It means that both an acid and its anhydride are included, and "(polyvalent) carboxylic acid" means that both carboxylic acid and polyvalent carboxylic acid are included. The “total solid content” means the total amount of the components of the photopolymerizable 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 solvent, but is preferably a resin containing a carboxyl group or a hydroxyl group. .
As such an alkali-soluble resin, for example,
Unsaturated and carboxyl group-containing epoxy resins such as (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, vinyl acetate, maleimide and the like;
(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 .;
Is mentioned. These may be used alone or in combination of two or more.

Of these, unsaturated group and carboxyl group-containing epoxy resins and carboxyl group-containing vinyl resins are preferred from the viewpoints of alkali developability and image formability.
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.

(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 group-containing carboxylic acid adduct of an epoxy resin is further added to a polyvalent carboxylic acid. And / or an epoxy resin containing an unsaturated group and a carboxyl group to which an anhydride thereof is added. That is, (i) ethylenically unsaturated via an ester bond (—COO—) formed by ring-opening addition of a carboxyl group of an α, β-unsaturated monocarboxylic acid to an epoxy group of an epoxy resin. Examples thereof include those in which a bond is added and (iii) a carboxyl group of a polyvalent carboxylic acid or anhydride thereof is added to the hydroxyl group generated at that time. Hereinafter, although the structural component of an unsaturated group and a carboxyl group-containing epoxy resin is demonstrated, all the following structural components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

(A-1-1) 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 them, 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 methacrylate and alkyl (meth) acrylate, etc. preferable.

(A-1-2) α, β-unsaturated monocarboxylic acid As α, β-unsaturated monocarboxylic acid, for example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid And pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta ( Examples include meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, reaction product of (meth) acrylic acid and ε-caprolactone, and the like. Among these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

(A-1-3) 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, and 3-methyltetrahydrophthalic acid. 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid 4-ethylhexahydrophthalic acid, and anhydrides thereof.
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 What is a thing is preferable.

Moreover, as an unsaturated group and a carboxyl group-containing epoxy resin, what has an acid value of 20-200 mg-KOH / g is preferable, and what is 30-180 mg-KOH / g is more preferable. In addition, the “acid value” in the present embodiment is a value measured according to JIS-K0070 (standard oil and fat test method).
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] THF (tetrahydrofuran stabilized with 0.03% by weight of butylhydroxytoluene)
[Standard sample] Polystyrene (PSt) standard sample [calibration curve] Fifth [detection] RI (built-in device)
[Injection amount] 0.1% by weight 100 μL (sample is filtered in advance with GL Chromatodisc 13P manufactured by GL Science Co., Ltd.)

  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 performed, and a polyvalent carboxylic acid or anhydride thereof is further added. A method in which a reaction is continued by adding a substance can be used.

  Here, examples of the organic solvent include 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. And quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine.

  Furthermore, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.

  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 (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and the like. These may be used alone or in combination of two or more.

  Examples of the vinyl compound include styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meta ) Acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylami , N- methylol (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N- dimethylaminoethyl (meth) acrylamide, copolymers of vinyl compounds and vinyl acetate. These may be used alone or in combination of two or more.

  Among these, dicyclopentanyl (meth) acrylate is preferable in that it provides a wide latitude for development time and developer deterioration. Examples of such dicyclopentanyl (meth) acrylate include compounds described in JP-A-2001-89533, such as a dicyclopentadiene skeleton, a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, and a dicyclopentenyloxyalkyl skeleton. (Meth) acrylate and the like.

  Among the above copolymers (carboxyl group-containing vinyl resins), a (meth) acrylate- (meth) acrylic acid copolymer is preferable from the viewpoint of image shape, sensitivity, and cured film strength. A copolymer comprising 30 to 80 mol% of acrylate and 20 to 70 mol% of (meth) acrylic acid is more preferable. In particular, a copolymer comprising 50 to 75 mol% (meth) acrylate and 25 to 50 mol% (meth) acrylic acid is preferable.

Moreover, as an acid value of these carboxyl group-containing vinyl-type resin, it is 30-250 mg-KOH / g normally, Preferably, it is 50-200 mg-KOH / g, More preferably, it is 70-150 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. When the carboxyl group-containing vinyl resin in the above range is used, it 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;
An adduct compound obtained by adding an α, β-unsaturated group-containing carboxylic acid to a bisphenol A type epoxy compound or epoxy resin, or an epoxy compound or epoxy resin having a fluorene skeleton which may have a substituent;
A compound obtained by further adding a polyvalent carboxylic acid and an anhydride thereof to the adduct compound;
Is mentioned.

  The alkali-soluble resin in the present embodiment is preferably a component that does not contain any ethylenically unsaturated group or epoxy group. That is, an alkali-soluble resin containing an ethylenically unsaturated group or an epoxy group is not preferable because the storage stability of the composition tends to be lowered.

Specific examples of the alkali-soluble resin that does not contain an ethylenically unsaturated group or an epoxy group include (A-2) a carboxyl group-containing vinyl resin.
More specifically, alkyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / alkyl (meth) acrylate / (meth) acrylic acid copolymer, hydroxyalkyl (meth) acrylate / alkyl (meth) acrylate / (Meth) acrylic acid copolymer, styrene / hydroxyalkyl (meth) acrylate / alkyl (meth) acrylate / (meth) acrylic acid copolymer, alkyl (meth) acrylate / maleic acid copolymer, styrene / alkyl ( (Meth) acrylate / maleic acid copolymer, hydroxyalkyl (meth) acrylate / alkyl (meth) acrylate / maleic acid copolymer, styrene / hydroxyalkyl (meth) acrylate / alkyl (meth) acrylate / maleic acid copolymer, etc. To mention That.

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 content of the alkali-soluble resin having a molecular weight (M3) that is 10 ^−1/2 times the molecular weight (M1) corresponding to the maximum peak value. )

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

  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.

  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.

Examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylate compounds. And urethane (meth) acrylates of polyisocyanate compounds and epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds.
These can be used alone or in combination of two or more.

(B-1) Esters of Unsaturated Carboxylic Acid and Polyhydroxy Compound Esters of Unsaturated Carboxylic Acid and Polyhydroxy Compound (hereinafter may be abbreviated as “ester (meth) acrylates”). Specifically, the following compounds can be exemplified.

  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 include 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. Examples of the alkylene oxide adduct include an ethylene oxide adduct or a propylene oxide adduct.

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

More specifically, the following compounds can be exemplified as the esters of the unsaturated carboxylic acid and the polyhydroxy compound.
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.

In addition, as the esters of the unsaturated carboxylic acid and the polyhydroxy compound, the unsaturated carboxylic acid and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, and bisphenol A, or addition of ethylene oxide thereof. And a reaction product with the product. Specific examples include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], and the like.
Furthermore, examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include a reaction product of the unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate. Specific examples include di (meth) acrylate and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate.
Still further, examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include a reaction product of the unsaturated carboxylic acid, the polyvalent carboxylic acid, and the polyhydroxy compound. Specifically, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, a condensate of (meth) acrylic acid, maleic acid and diethylene glycol, (meth) acrylic acid, terephthalic acid and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

(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、Ｒ^１０は水素原子又はメチル基を示し、ｐ及びｐ’は１〜２５の整数、ｑは１、２、又は３である。）

(In formulas (Ia), (Ib) and (Ic), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3.)

  Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4, respectively. 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.

(B-3) Urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound Examples of the hydroxy (meth) acrylate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylol. Examples include hydroxy (meth) acrylate compounds such as ethanetri (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;
Aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate, tris (isocyanatephenyl) thiophosphate;
Heterocyclic polyisocyanates such as isocyanurates;
Allophanate-modified polyisocyanurate produced by the method described in JP-A-2001-260261;
And polyisocyanate compounds such as

  As urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, urethane (meth) acrylates containing the allophanate-modified polyisocyanurate are particularly 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.

  Commercially available products can be used as the urethane (meth) acrylates in the present embodiment. Specifically, for example, trade names “U-4HA” “UA-306A” “UA-MC340H” “UA-MC340H” “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and compounds having an allophanate skeleton manufactured by Bayer Japan “ AGROR 4060 "etc. are mentioned.

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

(i) a compound having four or more urethane bonds in one molecule;
Compound (i) obtained by reacting a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate -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 ”, etc. 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) Compounds having four 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. The molecular weight of the urethane (meth) acrylates is preferably 600 to 150,000.

  In addition, such urethane (meth) acrylates include, for example, the above compound (i) and the above 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, 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 ( Examples include a reaction product with a (meth) acrylate compound.

(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 is improved by sulfurizing ether bonds of ether-containing ethylenically unsaturated compounds with phosphorus pentasulfide to convert them into thioether bonds. It is done.
Further, for example, a polyfunctional (meth) acrylate compound described in Japanese Patent No. 3164407 and JP-A-9-100111 and a silica sol having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (manufactured by 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.)) and the like, containing isocyanate groups or mercapto groups Examples thereof include compounds bonded using a 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 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 these, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable, and ester (meth) acrylates are more preferable. Among the ester (meth) acrylates, aromatic polyhydroxy compounds such as bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], or Particularly preferred are those reactants with ethylene oxide adducts.

  In addition, in the ethylenically unsaturated compound according to the present embodiment, the one that does not contain an aromatic ring, or one that contains no phenyl group or a phenyl group having a substituent at the p (para) position is the heating of the protective film. This is preferable because discoloration (red coloring) due to the treatment 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 ethylenically unsaturated compound in the thermosetting composition of the present embodiment is usually 10% by weight or more, preferably 20% by weight or more, and usually 70% by weight with respect to the total solid content. % Or less, preferably 60% 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 40% by weight or less, and the lower limit is usually 5% by weight or more.
Although the effect that the hardness of a cured film becomes high by using the compound which has 3 or more of ethylenically unsaturated groups is show | played, when the content is too much, it will be easy to cause the fall of the peelability after exposure.

  The compounding ratio of the component (B) to the component (A) is usually 150 parts by weight or less, preferably 120 parts by weight or less, more preferably 110 parts by weight as the blending 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.

(i) 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
(ii) halomethylated oxadiazole derivative, 2- (o-chlorophenyl) -4,5-
Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, Imidazole derivatives such as 2- (o-methylphenyl) -4,5-diphenylimidazole dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer

(iii) Benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether
(iv) Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone
(v) Benzanthrone derivatives
(vi) Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone
(vii) 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
(viii) Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone

(ix) Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate
(x) Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine
(xi) Phenazine derivatives such as 9,10-dimethylbenzphenazine
(xii) 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

(xiii) 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-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
(xiv) acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
(xv) 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl]-, 1- (O-acetyloxime)
(xvi) JP 2000-80068, JP 2001-233842, JP 2001-235858, JP 2005-182004, WO 02/00903, and Japanese Patent Application 2005-305074 Oxime derivatives represented by the compounds described in

  These photopolymerization initiators are used alone or in combination. Examples of the combination 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. In addition, a combination of initiators may be mentioned.

  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.

  The compounding ratio of the component (C) to the component (B) is usually 20 parts by weight or less, preferably 10 parts by weight or less as the compounding amount of the component (C) with respect to 100 parts by weight of the component (B). 1 part by weight or more, preferably 0.5 part by weight or more.

(D) 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 hard baking after image formation by exposure and development. Specific examples include the following, and these may be used singly or in combination of two or more.

(D-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 a 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.

(D-1-1) Polyglycidyl ether compound Examples of the polyglycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and 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 Type 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.

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

(D-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.

(D-1-4) Other As other examples, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth ) 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 copolymerization monomer normally 10 to 70 mol%, Preferably 15 to 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) (Meth) acrylic acid esters 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.

Moreover, the epoxy group used for the epoxy compound or epoxy resin used in this 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.

  When the thermosetting composition of this Embodiment contains the compound which has an epoxy group in a molecule | numerator as (D) thermal crosslinking agent, the inclusion of the compound which has an epoxy group in a molecule | numerator occupied in a thermosetting composition The amount is usually 60% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less, and usually 1% by weight or more based on the total solid content. 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.

(D-2) Nitrogen-containing thermally crosslinkable compound As the nitrogen-containing thermally crosslinkable compound used in the present embodiment, melamine, benzoguanamine, glycoluril, or a compound obtained by causing formalin to act on urea, or alkyl modification thereof. A compound can be mentioned.
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.

Examples of the compound obtained by allowing formalin to act on benzoguanamine or an alkyl-modified product thereof include “Cymel” (registered trademarks) 1123, 1125, 1128, and the like.
Examples of compounds obtained by allowing formalin to act on glycoluril or alkyl-modified products thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172, “Nicarak” (registered trademark) MX-270, and the like. Can do.
Further, examples of a compound in which formalin is allowed to act on urea or an alkyl-modified product thereof include “UFR” (registered trademark) 65 and 300, “Nicarak” (registered trademark) MX-290 manufactured by Cytec Industries, and the like. be able to.

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

When the thermosetting composition of the present embodiment contains a nitrogen-containing thermally crosslinkable compound as the thermal crosslinking agent (D), the content of the nitrogen-containing thermally crosslinkable compound in the thermosetting composition is as follows: It is usually 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, based on the total solid content. When the amount of the nitrogen-containing thermally crosslinkable compound is excessively large, the remaining film ratio during development and the resolution are liable to be lowered.
Among these, particularly preferred compounds as the thermal crosslinking agent (D) include compounds having —N (CH ₂ OR) ₂ group (wherein R represents an alkyl group or a hydrogen atom) in the molecule. Specifically, a compound obtained by allowing formalin to act on urea or melamine or an alkyl-modified product thereof is particularly preferable.

(E) Other components (E-1) Adhesion aid An adhesive aid can be blended with the thermosetting composition of the present embodiment for the purpose of improving 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 thermal 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, for example, γ-gridoxypropylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.
In the case of using an adhesion aid, the amount of the adhesion aid is usually 0.1% by weight or more, usually 20% by weight or less, preferably 10% with respect to the total solid content of the thermosetting composition. % By weight or less.

(E-2) Surfactant The thermosetting composition of the present embodiment is nonionic for the purpose of improving applicability as a coating liquid of the composition and developing property of the thermosetting composition layer, and the like. 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 sulfates. Ester salts, 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 Examples thereof include polymer surfactants. 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, such as “Emar 10” manufactured by Kao Corporation for alkyl sulfates, and “Perex NB-” manufactured by Kao Corporation for alkylnaphthalene sulfonates. Special polymeric surfactants such as “L” include “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 “Acetamine 24” manufactured by Kao Corporation for alkylamine salts, and “Cotamine 24P” and “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, for example, 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, Examples include 9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and the like.
As these commercially available products, “BM-1000” and “BM-1100” manufactured by BM Chemie, “Mega-Fuck F142D”, “Mega-Fak F172”, “Mega-Fak F173” manufactured by Dainippon Ink and Chemicals, Inc. Mention may be made of “Megafuck F183”, “Megafuck F470”, “Megafuck F475”, “FC430” manufactured by Sumitomo 3M Co., Ltd. and “DFX-18” manufactured by Neos Co., Ltd.

Examples of the silicone-based surfactants include “Toray Silicone DC3PA”, “Same SH7PA”, “Same DC11PA”, “Short SH21PA”, “Short SH28PA”, “Short SH29PA”, “Same SH30PA "," SH8400
“TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5) (6) (7) 6”, “TSF-4460” manufactured by Toshiba Silicone Co., Ltd., Commercial products such as “TSF-4442”, “KP341” manufactured by Silicone Co., Ltd., “BYK323”, “BYK330” manufactured by BYK Chemie, and the like can be mentioned.

Among these surfactants, fluorine-based surfactants and silicone-based surfactants are preferable from the viewpoint of uniformity of the coating film thickness.
Two or more kinds of surfactants may be combined. Silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer surfactant Examples include combinations of agents. Of these, silicone surfactants / fluorine surfactants are preferred.
In this silicone surfactant / fluorine surfactant combination, for example, “TSF4460” manufactured by GE Toshiba Silicone / “DFX-18” manufactured by Neos, “BYK-300” or “BYK-330” manufactured by BYK Chemie. / "S-393" manufactured by Seimi Chemical Co., Ltd. "KP340" manufactured by Shin-Etsu Silicone Co., Ltd. "F-478" or "F-475" manufactured by Dainippon Ink Co., Ltd. "SH7PA" manufactured by Toray Silicone Co., Ltd. "DS-" manufactured by Daikin 401 ”,“ L-77 ”manufactured by Nippon Unicar Co., Ltd.,“ FC4430 ”manufactured by Sumitomo 3M Co., Ltd., and the like.

  When the thermosetting composition of the present embodiment contains a surfactant, the content of the surfactant in the thermosetting composition is preferably 10% by weight or less with respect to the total solid content. 1 to 5% by weight is more preferable.

(E-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 has different curing conditions depending on the manufacturing process of each element. It 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 a thermosetting agent.

(E-3-1) Benzoic acid compound As the benzoic acid compound, a hydroxyl group, a halogen group, an alkyl group, an acyl group, an acyloxyl group are located 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.

(E-3-2) Polyvalent carboxylic acid (anhydride)
As polyvalent carboxylic acid (anhydride), for example,
Cycloaliphatic polycarboxylic acids (anhydrides) such as methylhymic 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;
Examples include hydrolysates of aromatic acid anhydrides. Among these, trimellitic acid (anhydride) and phthalic anhydride are preferable.

(E-3-3) Polymer containing polyvalent carboxylic acid (anhydride) As polymer containing polyvalent carboxylic acid (anhydride), (anhydrous) polyvalent carboxylic acid such as maleic acid And a polymer with a compound having at least one ethylenically unsaturated bond in the molecule, a partial half ester modified polymer of a polyvalent carboxylic acid (anhydride) portion in such a polymer, and the like. .
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 locating group such as
As a polymer containing a polyvalent carboxylic acid (anhydride), maleic anhydride and an alkylene having a locating group such as (poly) alkyleneoxy or alkyl are particularly preferable from the viewpoint of light transmittance and cured film strength. A copolymer is preferred.

(E-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) sulfonium tetrafluoroborate , Tri (p-chlorophenyl) sulfonium hexafluorophosphate, tri (p-chlorophenyl) sulfonium hexafluoroantimonate, 4-t-butyltriphenylsulfonium hexafluorophosphate, and the like.

  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.

(E-3-5) Amine compound As an 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 amines (first, second, third) such as DBU (1,8-diazabiscyclo (5,4,0) undecene-1) and DBU tetraphenylborate salts;
Metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, benzyldimethylamine, dimethylamino-p-cresol, 2- (dimethylaminejomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, Aromatic amines such as pyridine, picoline, DBU (1,8-diazabiscyclo (5,4,0) undecene-1), tri-2-ethylhexylate of 2,4,6-tris (dimethylaminomethyl) phenol ( First, second, third);
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- Liazine, 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;
Examples include diethylenetriamine, iminobispropylamine, and bis (hexamethylene) triamine.
Among these, dicyanamide and DBU tetraphenylborate salts are preferable from the viewpoint of the cured film strength.

(E-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.

(E-3-7) Blocked carboxylic acid As the block carboxylic acid, for example, the (polyvalent) carboxylic acid and the carboxylic acid of a polymer containing them are 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 the compounds represented by the general formula (II), and benzylphenylsulfonium salt types.

These curing agents may be used alone or in combination of two or more.
As the curing agent, among them, the polyvalent carboxylic acid copolymer and the benzoic acid compound are excellent in improving the adhesion to the support, and the monosulfonium salt is 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.

  When the thermosetting composition of this embodiment contains a curing agent, the content of the curing agent in the thermosetting composition is usually 0.05% by weight or more, preferably 0, based on the total solid content. .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.

(F) 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, for example, esters of amino acids such as N-phenylglycine or dipolar compounds thereof, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1, Contains mercapto groups such as 2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate Compounds, hexanedithiol, trimethylolpropane tristhioglyconate, polyfunctional thiol compounds such as pentaerythritol tetrakisthiopropionate, N, N-dialkylaminobenzoic acid ester, N Derivatives such as phenylglycine or its ammonium salt or sodium salt, 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 250 nm and 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, SEESORB105, SEESORB105, SEESORB105, 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, EVERSORB76, EVERSORBVER234, EVERSORB234 Benzotriazole compounds, such as 100, Tomissorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, and SEESORB709 (made by Cypro Kasei);
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 these ultraviolet absorbers are added, the blending ratio is usually 0.01% by weight to 15% by weight, preferably 0.05% by weight to 10% by weight, based on the total solid content of the thermosetting composition. % Or less. If the blending ratio of the UV absorber 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 are decreased. Tend.

(G) Organic solvent Each of the above-described components is usually used by preparing 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, for example, 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 , Tetrahydrofuran, diethylene glycol dimethyl ether, methoxybutyl acetate, Best, 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, 2 or more types may be mixed and used. 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, sorbest, and carbitol can be given.
Furthermore, in the above mixed solvent, the blending ratio of one or more organic solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbest 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 for Forming Protective Film Next, a method for forming a protective film using the thermosetting composition of the present embodiment will be described.

[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 A volatile component is removed (dried) from the coating film to 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.

[2-3] Exposure / Development Step Next, a photomask is placed on the dried coating film of the thermosetting composition layer, 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 as the cross-sectional shape of the fine line image after development is developed such as development time, developer aging, development shower physical stimulation, etc. 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, and 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.

The solvent used for the development treatment is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured portion, but as mentioned above, points such as environmental pollution, harm to the human body, fire risk, etc. Therefore, it is preferable to use an alkali developer instead of an organic solvent.
Examples of such alkali developer include inorganic alkali compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethylamine, An aqueous solution containing an organic alkali compound such as ethanolamine or tetramethylammonium hydroxide can be mentioned.

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 thermosetting composition film image-formed by the exposure / development step is then subjected to a heat treatment (hard baking) step to become a cured product (thermosetting film). In some cases, after the development, the entire surface exposure is performed for the purpose of suppressing the generation of outgas at the time of hed baking before hard baking.
When performing full exposure before hard baking, ultraviolet light or visible light is used as the light source. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp. 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 100 to 250 ° C. and drying time 30 seconds to 90 minutes.

[3] Liquid crystal display device (panel)
Next, a manufacturing method of the liquid crystal display device (panel) according to the present embodiment 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 creating an ITO wiring using a photolithography method. Created by.

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 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. Note that 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 vacuum 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. As heating temperature, it is 30 degreeC or more normally, Preferably it is 50 degreeC or more, and is 100 degrees C or less normally, Preferably it is the range of 90 degrees C or less.
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, The liquid crystal conventionally known, such as an aromatic type, an aliphatic type, a polycyclic compound, can be used. Either a lyotropic liquid crystal or a thermotropic liquid crystal may be used. 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.

  In addition, the structural component of the thermosetting composition used in the following Examples and Comparative Examples is as follows.

(A) Alkali-soluble resin

(B) Compound having two or more ethylenically unsaturated groups

(C) Photopolymerization initiator

(D) Thermal crosslinking agent

(E) Other component S1: fluorinated surfactant. F475 made by Dainippon Ink

(F) Additive R1: Polymerization accelerator. 2-mercaptobenzimidazole Y2: UV absorber. It has the following structural formula.

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

  Moreover, the prepared thermosetting composition, the exposure film | membrane, and the evaluation method of a thermosetting film | membrane are as follows.

(Ethylenically unsaturated group equivalent)
About the thermosetting composition, when the chemical structural formula of the component (B) and the component (A) contain an ethylenically unsaturated group, it calculated from the chemical structural formula of the polymer estimated from the charging ratio of the monomer.

(Development dissolution rate)
In the exposure film forming procedure, the difference (μm) between the film thickness after coating / drying and the film thickness after development is measured, and the value obtained by dividing the development time (min) by the development dissolution rate (μm / min) did.

(NMP dissolution rate)
The thermosetting film obtained by the procedure for forming the thermosetting film was immersed in N-methylpyrrolidone at 60 ° C. for 20 minutes, and then rinsed with pure water. The value obtained by dividing the difference in film thickness before and after immersion (μm) by the immersion time (20 minutes) was taken as the NMP dissolution rate after hard baking (μm / min).

(Optimal exposure)
Measurement was performed in accordance with the method described in the above embodiment (mJ / cm ² ).

(Resolution)
The image of the thermosetting film obtained by the procedure for forming 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 obtained by the thermosetting film forming procedure 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 obtained by the procedure for forming the thermosetting film was observed with an optical microscope, and the residue of 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

(Peelability)
The thermosetting film obtained by the procedure for forming the thermosetting film was immersed in N-methylpyrrolidone at 60 ° C. for 10 minutes together with a glass substrate, and evaluated according to the following criteria.
○: No thermosetting film remained on the substrate.
X: The thermosetting film remained on the substrate.

(chemical resistance)
The thermosetting film obtained by the procedure for forming 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) are not observed by surface observation with an optical microscope.
won.
X: Holes and surface roughness (unevenness) were observed by surface observation with an optical microscope.
Or cloudiness was observed by visual observation.

(Light transmittance)
A cured film was obtained by the procedure for forming the thermosetting film except that the entire surface was exposed without using a mask. The light transmittance of the cured film was measured with a spectrophotometer UV3100PC manufactured by Shimadzu Corporation, and the minimum transmittance (%) in the wavelength range of 600 nm to 400 nm was determined.

(Examples 1-7, Comparative Examples 1-3)
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 above-mentioned optimum exposure amount.
Next, a 0.4% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution, and the substrate was immersed in the developing solution at 25 ° C. for 70 seconds, followed by rinsing with pure water to form an exposed film. Obtained. 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.

As is apparent from the results in Table 1, the thermosetting film formed with the thermosetting composition of the present embodiment is not only excellent in chemical resistance, light transmittance, pattern shape, and residue characteristics, but also peeled off. It was a thermosetting film that has both properties. In particular, in Example 4 in which a polymerization accelerator and an ultraviolet absorber were used in combination, a thermosetting film having both a pattern shape and residual characteristics was obtained.
The thermosetting films formed of the thermosetting compositions of Comparative Examples 1 and 2 were thermosetting films having inferior peelability although the development dissolution rate was not more than a specified value. Thus, when an ethylenically unsaturated group equivalent exceeds 5 mmol / g, peelability will fall.
In addition, the thermosetting film formed of the thermosetting composition of Comparative Example 3 has good releasability because the ethylenically unsaturated group equivalent is not more than the specified value, but the development dissolution rate is the specified value. It was a thermosetting film that was inferior in chemical resistance. Further, the resin P3 used as the component (A) has a relatively large molecular weight and tends to have poor resolution.

According to the present invention, for example, there is no coloring at the time of hard baking, the light transmittance in the visible light region is good, the peelability after exposure and development is excellent, and the chemical resistance after thermosetting In addition, an excellent thermosetting composition for a protective film can be formed. This also provides a high-quality liquid crystal display device. Therefore, industrial applicability is extremely high in the field of the thermosetting composition for protective films and the liquid crystal display device.
Further, according to the present invention, for example, a printed wiring board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, a solder resist film or a coverlay film in organic electroluminescence, and the like. A thermosetting composition useful for forming an insulating coating layer of an electronic component is provided. In addition, for example, a thermosetting composition suitable for an overcoat used for a liquid crystal panel such as a liquid crystal display is provided. Therefore, industrial applicability is extremely high also in this field.

Claims (5)

Each component of the following (A)-(D),
(A) an alkali-soluble resin,
(B) a compound having two or more ethylenically unsaturated groups,
(C) a photopolymerization initiator,
(D) (D-1) a compound having an epoxy group in the molecule and / or (D-2) a thermal crosslinking agent containing a nitrogen-containing thermally crosslinkable compound,
The content of the ethylenically unsaturated group with respect to the total weight of the component (A) and the component (B) is 1 mmol / g or more and 5 mmol / g or less, and the component (B) is ethylenic The ratio of the compound having two unsaturated groups and the compound having two ethylenically unsaturated groups to the total weight of the component (A) and the component (B) is 10% by weight. or more, and, the dissolution rate of in 0.4 wt% tetramethylammonium hydroxide aqueous solution exposed film cured by exposure at the optimum amount (25 ° C.) is less 2.3 .mu.m / min A thermosetting composition for a protective film. Wherein component (A) is an ethylenically unsaturated group, or a protective film for a heat-curable composition according to claim 1, characterized in that both a component which does not contain epoxy groups. The dissolution rate in N-methylpyrrolidone (60 ° C.) of a thermosetting film obtained by baking at 220 ° C. for 1 hour after exposure at an optimal exposure amount is 0.1 μm / min or less. The thermosetting composition for protective films according to claim 1 or 2 . The hardened | cured material formed using the thermosetting composition for protective films of any one of Claims 1 thru | or 3 . A liquid crystal display device comprising the cured product according to claim 4 as a protective film.