JP4992518B2 - Photopolymerizable composition - Google Patents

Description

The present invention relates to a photopolymerizable composition. Specifically, for example, printed wiring 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, and insulating coatings for various electronic components The present invention relates to a photopolymerizable composition useful for forming a layer.
The photopolymerizable composition of the present invention is also useful for color filters, black matrices, overcoats, ribs and spacers used in liquid crystal panels such as liquid crystal displays.

  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). A photopolymerizable composition containing an epoxy acrylate-modified alkali-soluble resin and an epoxy resin having a low softening point as a color filter protective film forming material is also known (see, for example, Patent Documents 3 and 4).
JP 2004-4733 A JP 2002-131899 A JP-A-10-177108 JP 2005-114992 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. In addition, the sensitivity is lower than that of the photopolymerizable negative photosensitive composition, and the productivity is inferior.

  On the other hand, in the photopolymerizable negative photosensitive composition as described in Patent Document 2, the above-mentioned coloring problem hardly occurs and high sensitivity can be easily obtained. Because of the tendency to swell due to, there is a problem that the resolution is deteriorated and the adhesion of the fine wire to the substrate is deteriorated. In order to solve such problems, if the solubility and affinity of the photocured film in the developing solution are lowered, there is a problem that the pattern after development deteriorates to form a trailing shape or a residue is generated. .

Furthermore, in the photopolymerizable color filter protective film forming material as described in Patent Documents 3 and 4, usually, the acid value of the alkali-soluble resin is low, so the developability is poor and a residue is generated. As a result of our examination, it has become clear that it is easy to perform and is not suitable for fine image formation.
That is, in the photopolymerizable negative photosensitive composition, it is difficult to improve both resolution and adhesion and solve the problem of pattern shape and residue.

  The present invention has been made in view of such circumstances. That is, the main object of the present invention is to provide a photopolymerizable composition having high sensitivity, high resolution, good fine line adhesion and good pattern shape and no generation of residue. Another object of the present invention is to provide a photopolymerizable composition which is not colored during hard baking and has a good light transmittance in the visible light region.

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

（但し、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ は、各々独立に、水素原子又はメチル基を表し、Ｒ ^４ は炭素数１以上２０以下のアルキル基、炭素数６以上２０以下のアリール基、炭素数２以上２０以下のアルケニル基、炭素数２以上２０以下のアルキニル基を表す。ｘ：ｙ：ｚは各構成単位のモル％を表し、ｘ＋ｙ＋ｚ＝１００である。） That is, the photopolymerizable resin composition for an interlayer insulating film of the present invention is
(A) An alkali-soluble resin having an acid value of 100 mg-KOH / g or more and 250 mg-KOH / g or less (B) a compound having an ethylenically unsaturated group (C) a photopolymerization initiator and (D) a softening point of 100 ° C. or less A photopolymerizable composition containing a resin , wherein the component (A) is an alkali-soluble resin represented by the following general formula (I), and the component (C) is an oxime ester compound: .

(However, R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. Represents an alkenyl group having 2 to 20 carbon atoms and an alkynyl group having 2 to 20 carbon atoms, x: y: z represents a mol% of each structural unit, and x + y + z = 100.

  According to the present invention, it is possible to provide a photopolymerizable composition having high sensitivity, high resolution, good fine-line adhesion and good pattern shape and no generation of residue. In addition, it is possible to provide a photopolymerizable composition that is not colored during hard baking and has a good light transmittance in the visible light region.

  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] Photopolymerizable composition The photopolymerizable composition of the present embodiment comprises:
(A) an alkali-soluble resin having an acid value of 100 mg-KOH / g to 250 mg-KOH / g,
(B) a compound having an ethylenically unsaturated group,
(C) a photopolymerization initiator,
And (D) a resin having a softening point of 100 ° C. or lower.

In addition, the acid value in this Embodiment is the value measured based on JIS-K0070 (The test method of the acid value of a chemical product, a saponification value, an ester value, an iodine value, a hydroxyl value, and an unsaponifiable substance). means.
The softening point of the resin conforms to JIS-K7234 (epoxy resin softening point test method) for the epoxy resin and conforms to JIS-K6863 (softening point test method for hot melt adhesive) for the other resins. The measured value.

  Moreover, the weight average molecular weight of resin mentioned later means the 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 stabilized with around 0.03% butyhydroxytoluene
[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.)

  When the acid value of the alkali-soluble resin of component (A) exceeds 250 mg-KOH / g, the photocured film is easily dissolved in the developer, and the sensitivity and resolution are lowered. On the other hand, when the acid value of the alkali-soluble resin of the component (A) is less than 100 mg-KOH / g, the film in the non-exposed area is difficult to dissolve in the developer, and pattern shape deterioration and residue generation are likely to occur.

  When the softening point of the resin of component (D) exceeds 100 ° C., the film shape of the photopolymerizable composition of the present invention becomes hard, so the pattern shape after development deteriorates due to the effect of curing shrinkage due to photopolymerization. Or the resolution is likely to deteriorate.

  Next, each component used for the photopolymerizable composition of this Embodiment is demonstrated.

In addition to the essential components (A) to (D), the following components can be blended in the photopolymerizable composition of the present embodiment.
(E) Thermal crosslinking agent (F) Other components (G) Additive (H) Organic solvent

  Hereinafter, each component will be described. In the present embodiment, “(meth) acryl” means “acryl and / or methacryl”. 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 the acid value is in the above-described range and is soluble in an alkaline solvent. A resin containing a hydroxyl group is preferred.

As such an alkali-soluble resin, for example, a carboxyl group of an α, β-unsaturated monocarboxylic acid such as (meth) acrylic acid, (meth) acrylic ester, maleic acid, vinyl acetate, maleimide, etc. is an epoxy resin epoxy. Unsaturated and carboxyl group-containing epoxy resin with ring-opening addition to the group; (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, chloride Hydroxyl group or carboxyl group-containing vinyl resin in which a hydroxyl group or carboxyl group is contained in vinylidene, maleimide or the like; and polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. . These may be used alone or in combination of two or more.
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.

Among these, an alkali-soluble resin is preferably an unsaturated group and carboxyl group-containing epoxy resin or a carboxyl group-containing vinyl resin 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) an ethylenically unsaturated group 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, the components of the unsaturated group- and carboxyl group-containing epoxy resin will be described.

(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 Resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, copolymer of glycidyl methacrylate and alkyl (meth) acrylate, etc. Is mentioned. These may be used alone or in combination of two or more.
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. These may be used alone or in combination of two or more.
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. These may be used alone or in combination of two or more.
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 photopolymerizable composition, the unsaturated group and carboxyl group-containing epoxy resin may be glycidyl methacrylate and alkyl (meta). ) A copolymer with an acrylate ester, preferably an α, β-unsaturated monocarboxylic acid is (meth) acrylic acid and a polyvalent carboxylic acid or anhydride thereof is tetrahydrophthalic anhydride.

Moreover, as an unsaturated group and a carboxyl group-containing epoxy resin, what has an acid value of 100-200 mg-KOH / g is preferable, and what is 110-180 mg-KOH / g is more preferable.
Furthermore, the molecular weight of the unsaturated group- and carboxyl group-containing epoxy resin is usually 1,000 or more, preferably 1,500 or more, and usually 30,000 or less, preferably 20,000 or less.

  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. These may be used alone or in combination of two or more.

  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. These may be used alone or in combination of two or more.

  Furthermore, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone. These may be used alone or in combination of two or more.

  The blending amount of the α, β-unsaturated monocarboxylic acid in the synthesis reaction is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 with respect to 1 chemical equivalent of the epoxy group of the epoxy resin. The amount can be one chemical equivalent. 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. In the following exemplary structural formulas, R represents a hydrogen atom or a methyl group.

(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 vinyl compounds include styrenes such as styrene, α-methylstyrene, and hydroxystyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. , Hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-ethyladamantyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (Meth) acrylates such as (meth) acrylate and N- (meth) acryloylmorpholine; (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -(Meth) acrylamides such as dimethylaminoethyl (meth) acrylamide; 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), from the viewpoint of pattern shape, sensitivity, and cured film strength, styrenes— (meth) acrylic acid copolymers, styrenes— (meth) acrylates— A (meth) acrylic acid copolymer is preferable, and among them, a copolymer composed of 5 to 85 mol% of styrenes, 0 to 60 mol% of (meth) acrylates, and 10 to 50 mol% of (meth) acrylic acid is more preferable. . In particular, a copolymer composed of 30 to 85 mol% of styrenes, 0 to 40 mol% of (meth) acrylates, and 10 to 35 mol% of (meth) acrylic acid is preferable.

（但し、Ｒ^１、Ｒ^２、Ｒ^３は、各々独立に、水素原子又はメチル基を表し、Ｒ^４は炭素数１以上２０以下のアルキル基、炭素数６以上２０以下のアリール基、炭素数２以上２０以下のアルケニル基、炭素数２以上２０以下のアルキニル基を表す。ｘ：ｙ：ｚは各構成単位のモル％を表し、ｘ＋ｙ＋ｚ＝１００である。） That is, the alkali-soluble resin of the component (A) according to the present invention is preferably an alkali-soluble resin represented by the following general formula (I).

(However, R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. Represents an alkenyl group having 2 to 20 carbon atoms and an alkynyl group having 2 to 20 carbon atoms, x: y: z represents a mol% of each structural unit, and x + y + z = 100.

In the general formula (I), as R ⁴ , specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert- Linear or branched alkyl group such as butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decanyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group Alicyclic alkyl groups such as cyclopentadienyl group and tricyclododecanyl group; aryls such as phenyl group, p-toluyl group, 2,4,6-trimethylphenyl group, α-naphthyl group and β-naphthyl group Group: alkenyl group such as ethylene group, allyl group, iso-propenyl group; acetylene group, 2-butyn-1-yl group, 3-butyn-2-yl group, etc. The alkynyl group of can be mentioned.
In the general formula (I), R ⁴ is preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 14 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

  In general formula (I), x: y = z is preferably x: y: z = 5 to 85: 0 to 60:10 to 50, more preferably 30 to 85: 0 to 40:10 to 35. It is.

  Moreover, as an acid value of these carboxyl group-containing vinyl-type resin, it is 100-250 mg-KOH / g normally, Preferably, it is 100-200 mg-KOH / g, More preferably, it is 11-150 mg-KOH / g.

Furthermore, the molecular weight of these carboxyl group-containing vinyl resins is usually 1,000 or more, preferably 1,500 or more, and usually 30,000 or less, preferably 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 not containing a phenolic hydroxyl group are suitable. In this case, discoloration (red coloring) due to the heat treatment of the protective film is suppressed, and cracking due to heat tends to be suppressed.

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

  The alkali-soluble resin in the present embodiment is preferably a component that does not contain any ethylenically unsaturated group or epoxy group.

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

[Relational expression]
V2 / V3 ≧ 1.3
However, V2 and V3 are as follows.
V2: When a differential molecular weight distribution curve is obtained by the GPC method using polystyrene as a standard substance
The molecular weight (M2) of 10 ^1/2 times the molecular weight (M1) corresponding to the maximum peak value
The weight content of the alkali-soluble resin having
V3: molecular weight (M3) 10 ^−1/2 times the molecular weight (M1) corresponding to the maximum peak value
The weight content of the alkali-soluble resin having

  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. Thus, by using an alkali-soluble resin having a low molecular weight component and a low molecular weight distribution, the image-forming property is improved, and the strength of the protective film using the alkali-soluble resin is improved and formed on such a protective film. Generation of crack defects in the ITO film can be suppressed.

  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 can be precipitated by mixing with a poor solvent of the alkali-soluble resin, and the precipitated resin is filtered, and then, for example, air-dried at 40 ° C. under reduced pressure for 12 hours.

  The content of the alkali-soluble resin of component (A) in the photopolymerizable composition of the present embodiment is usually 30% by weight or more, preferably 40% by weight or more, based on the total solid content, Usually, it is 70% by weight or less, preferably 60% 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.

  In addition, in the photopolymerizable composition of this Embodiment, only 1 type of the alkali-soluble resin as a component (A) may contain, and 2 or more types may contain.

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

  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 include 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, 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^１１は水素原子又はメチル基を示し、ｐ及びｐ’は、各々独立に、１〜２５の整数、ｑは１、２、又は３である。）

(In formulas (Ia), (Ib) and (Ic), R ¹¹ represents a hydrogen atom or a methyl group, p and p ′ are each independently an integer of 1 to 25, 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.

  Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane; cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone. Alicyclic polyisocyanates such as diisocyanate and bicycloheptane triisocyanate; Aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanatephenyl) thiophosphate; Heterocyclic polyisocyanates such as isocyanurate; JP-A-2001-260261 Allophanate-modified polyisocyanurate produced by the method described in Japanese Patent Publication No. Aneto compounds.

  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) Compound having four or more urethane bonds in one molecule For example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate is added to a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol. Compound (i-1) obtained by reacting a diisocyanate compound such as tolylene diisocyanate; or a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-” manufactured by Asahi Kasei Kogyo Co., Ltd. 100 "," Duranate 22A-75PX "," Duranate 21S-75E "," Duranate 18H-70B "and other biuret types," Duranate P-301-75E "," Duranate F-302-90T ", "Duranai" Compound (i-2) obtained by reacting a compound having 3 or more isocyanate groups in one molecule, such as adduct type such as “F-305-80T”; or isocyanate ethyl (meth) acrylate, etc. And the compound (i-3) obtained by polymerizing or copolymerizing.
A commercial item can be used as such a compound, for example, "Duranate ME20-100" by Asahi Kasei Kogyo Co., Ltd. is mentioned.

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

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates is preferably 600 to 150,000.

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

(B-4) Epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound Examples of the polyepoxy compound include (poly) ethylene glycol polyglycidyl ether and (poly) propylene. Glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylol Aliphatic polyepoxy compounds such as propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether; Aromatic polyepoxy compounds such as lacpolyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds; sorbitan poly And polyepoxy compounds such as heterocyclic polyepoxy compounds such as glycidyl ether, triglycidyl isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate;

  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 of component (B) 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. These may be used alone or in combination of two or more.

  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 of component (B) in the photopolymerizable composition of the present embodiment is usually 10% by weight or more, preferably 20% by weight or more, based on the total solid content. It is usually 70% by weight or less, preferably 60% by weight or less. If the amount of the ethylenically unsaturated compound is excessively small, the sensitivity and the development dissolution rate are likely to be decreased. If the amount is excessively large, the reproducibility of the image cross-sectional shape 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 of the weight is usually 10% by weight or more, preferably 20% by weight or more, and 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.
If the content of the compound having 3 or more ethylenically unsaturated groups is excessively large, the peelability after exposure is likely to be lowered.

  The compounding ratio of the component (B) to the component (A) is usually 150 parts by weight or less, preferably 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 can be used in the photopolymerizable composition of the present embodiment, and an ethylenically unsaturated group is polymerized from ultraviolet to visible light. And a compound capable of generating a radical to be generated.

Specific examples of the polymerization initiator that can be used in the present embodiment are listed below.
(1) 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 Halomethylated triazines such as-(4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine Derivative.
(2) halomethylated oxadiazole derivative, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3-methoxyphenyl) imidazole dimer , 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methylphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4 , Imidazole derivatives such as 5-diphenylimidazole dimer.
(3) Benzoin and benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.
(4) Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
(5) A benzanthrone derivative.
(6) Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone.
(7) 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- ( p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl -Acetophenone derivatives such as (p-butylphenyl) ketone.
(8) Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.
(9) Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
(10) Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine.
(11) Phenazine derivatives such as 9,10-dimethylbenzphenazine.
(12) Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6- Pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-difluoropheny 1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6- Di-fluoropheny 1-yl, di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl.
(13) 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 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.
(14) Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
(15) 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl]-, 1- (O-acetyloxime)
(16) JP 2000-80068, JP 2001-233842, JP 2001-235858, JP 2005-182004, WO 02/00903, and Japanese Patent Application 2005-305074 Oxime derivatives represented by the compounds described in 1).

  Specific examples of the oxime derivative include oxime ester compounds exemplified below.

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

  Among the photopolymerization initiators described above, particularly preferred photopolymerization initiators are oxime ester compounds or acylphosphine oxide compounds.

The content of the photopolymerization initiator of component (C) in the photopolymerizable composition of the present embodiment is usually 0.1% by weight or more, preferably 0.5% by weight with respect to the total solid content. %, Usually 40% by weight or less, preferably 30% by weight or less.
Moreover, as a compounding ratio of the component (C) with respect to the component (B), the compounding amount of the component (C) with respect to 100 parts by weight of the component (B) is usually 200 parts by weight or less, preferably 150 parts by weight or less. 5 parts by weight or more, preferably 10 parts by weight or more.
If the amount of the photopolymerization initiator is excessively small, the sensitivity is likely to decrease, and if it is excessively large, generation of a residue is likely to occur.

(D) Resin having a softening point of 100 ° C. or lower Resin having a softening point of component (D) in the photopolymerizable composition of the present embodiment of 100 ° C. or lower (hereinafter sometimes referred to as “low softening point resin”) It is essential that the softening point is 100 ° C. or lower, but preferably the softening point of this resin is 80 ° C. or lower, more preferably 65 ° C. or lower.

In order to set the softening point of the resin to 100 ° C. or lower, (i) lower the molecular weight of the resin; (ii) lower the acid value of the resin; (iii) substitution that lowers the softening point in the repeating unit of the resin. There are means such as containing a group.
(I) When the softening point is made 100 ° C. or lower by lowering the molecular weight of the resin, the weight average molecular weight of the low softening point resin is usually 10,000 or less, preferably 5,000 or less, usually 300 Above, preferably 500 or more.
(Ii) When the softening point is made 100 ° C. or lower by lowering the acid value of the resin, the acid value of the low softening point resin is usually 100 or less, preferably 70 or less.
(Iii) In the case where the softening point is 100 ° C. or less by containing a substituent that lowers the softening point in the repeating unit of the resin, the substituent includes n-propyl group, n-butyl group, and n-hexyl. Group, an alkyl group having 3 or more carbon atoms such as 2-ethylhexyl group, n-octyl group, n-nonyl group and iso-decyl group; alkoxyalkyl group such as ethoxyethyl group, ethoxyethoxyethyl group and 2-ethoxypropyl group A cyclic ether group such as an epoxy group, a glycidyl group, an oxetanyl group or a tetrahydrofuryl group.
The methods (i) to (iii) can be used in combination.

  Specific examples of the resin having a softening point of 100 ° C. or lower contained in the photopolymerizable composition of the present embodiment include the following.

(D-1) Acrylic Resin As the acrylic resin used as component (D) in the present embodiment, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (Meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-ethyladamantyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) (Meth) acrylates such as acrylate) and N- (meth) acryloylmorpholine; (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N A polymer of one or more compounds selected from (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide; and one or more compounds selected from the (meth) acrylates and (meth) acrylamides And a copolymer of (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids.
These may be used alone or in combination of two or more.

(D-2) Epoxy resin As an epoxy resin used as component (D) in this embodiment, for example, a glycidyl ether group-containing resin obtained by reacting a hydroxyl group-containing resin with epichlorohydrin, and a carboxyl group Examples thereof include glycidyl ester group-containing resins obtained by reacting the containing resin with epichlorohydrin.
These may be used alone or in combination of two or more.

(D-2-1) Glycidyl ether group-containing resin Specific examples of the glycidyl ether group-containing resin include bisphenol A / aldehyde novolac type epoxy, phenol novolac type epoxy, cresol novolac type epoxy, bisphenol S epoxy resin, and phenol novolac epoxy. Examples thereof include phenol resin type epoxy resins such as resins, cresol novolac epoxy resins, trisphenol epoxy resins, polymerized epoxy resins of phenol and dicyclopentadiene, and polymerized epoxy resins of phenol and naphthalene.
As commercially available products, Japan Epoxy Resin Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1055, Epicoat 1004; Nippon Kayaku EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, XD-1000, NC-3000, NC-3000H, CER-3000L, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L, EPPN-201L, BREN-S, BREN-105, BREN-304, etc. be able to.

(D-2-2) Glycidyl ester group-containing resin As the glycidyl ester group-containing resin, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid Examples thereof include a copolymer of one or more compounds selected from glycidyl esters of α, β-unsaturated carboxylic acids such as glycidyl and one or more compounds selected from the following ethylenically unsaturated compounds.
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid; styrenes such as styrene, α-methylstyrene, hydroxystyrene; methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) Acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-e (Meth) acrylates such as ruadamantyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine; (meth) acrylonitrile; (meth) acrylamide, (Meth) acrylamides such as N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; vinyl acetate

(D-4) Other resins Examples of other resins include polyvinyl acetal resins obtained by reacting polyvinyl alcohol with aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, and benzaldehyde; and ethylene / vinyl acetate copolymer resins. .
These may be used alone or in combination of two or more.
Specific examples of the ethylene / vinyl acetate copolymer resin include Tosoh Corporation ultra-low molecular weight ultracene 7A55A, 8A56A, 0A52A, and 0A53A.

  Among these low softening point resins, (D-1) acrylic resins and (D-2) epoxy resins are preferred from the viewpoint of compatibility with the components (A) and (B), and (D-2) epoxy Resins are more preferred, and (D-2-1) glycidyl ether group-containing resins are particularly preferred.

In the photopolymerizable composition of the present embodiment, the content of the low softening point resin of the component (D) is usually 40% by weight or less, preferably 30% by weight or less, more preferably based on the total solid content. It is 20 wt% or less, usually 1 wt% or more, preferably 2 wt% or more, more preferably 4 wt% or more.
When the content of the component (D) is large, the film of the photopolymerizable composition formed on the substrate becomes strongly tacky, and the work becomes difficult due to sticking, or foreign matter is easily adsorbed on the film surface. There is a tendency. Moreover, when there is little content of (D) component, it exists in the tendency for adhesiveness with a board | substrate, resolution, etc. to fall.

(E) Thermal crosslinking agent The photopolymerizable composition of this Embodiment may contain the thermal crosslinking agent in order to improve the heat resistance and chemical resistance of the film | membrane after thermosetting.

  Any known thermal crosslinking agent can be used as long as it undergoes a crosslinking reaction by baking after image formation by exposure and development. Specifically, the following (E-1) compound having an epoxy group in the molecule and (E-2) a nitrogen-containing thermally crosslinkable compound may be mentioned.

(E-1) Compound having an epoxy group in the molecule The compound having an epoxy group in the molecule used in the present embodiment is obtained, for example, by reacting a monohydroxy compound or 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. These may be used alone or in combination of two or more.

(E-1-1) Polyglycidyl ether compound As the polyglycidyl ether compound, for example, diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), bis (3,5-dimethyl) -4-hydroxyphenyl) diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl ether type epoxy, tetramethylbisphenol A diglycidyl ether type epoxy, ethylene oxide-added bisphenol A diglycidyl ether Epoxy, dihydroxyoxyfluorene type epoxy, dihydroxyalkyleneoxylfluorene type epoxy, bisphenol A / aldehyde novolac type epoxy And phenol novolac type epoxy and cresol novolac type epoxy.
The polyglycidyl ether compound includes a polyglycidyl ether resin. Polyglycidyl ether resins include bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentadiene polymerized epoxy resin, phenol and naphthalene polymerized epoxy resin, etc. A type epoxy resin is mentioned.
These (poly) glycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride, a divalent acid compound, or the like to introduce a carboxyl group.

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

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

(E-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.

  Moreover, “Cymel” (registered trademark) 1123, 1125, 1128, and the like can be given as examples of a compound obtained by allowing formalin to act on benzoguanamine or an alkyl-modified product thereof.

  Examples of a compound obtained by allowing formalin to act on glycoluril or an alkyl-modified product thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172, “Nicarac” (registered trademark) MX-270, and the like. Can do.

  Further, examples of a compound obtained by allowing formalin 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. These may be used alone or in combination of two or more.

As the (E-2) nitrogen-containing thermally crosslinkable compound in the present embodiment, among others, —N (CH ₂ OR ′) ₂ group (wherein R ′ represents an alkyl group or a hydrogen atom) is included in the molecule. A compound having formalin acting on urea or melamine or an alkyl-modified product thereof is particularly preferable.

  In the photopolymerizable composition of the present embodiment, when a nitrogen-containing thermally crosslinkable compound is contained as a thermal crosslinking agent, the content of the nitrogen-containing thermally crosslinkable compound is usually 40 wt. % Or less, preferably 30% by weight or less, more preferably 20% by weight or less. If 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 reduced.

  In addition, as a thermal-crosslinking agent of a component (E), you may contain both (E-1) the compound which has an epoxy group in a molecule | numerator, and (E-2) a nitrogen-containing thermal crosslinkable compound. In that case, the total of the compound having an epoxy group in the molecule and the nitrogen-containing thermally crosslinkable compound is usually 40% by weight or less, preferably 30% by weight or less, more preferably based on the total solid content of the photopolymerizable composition. Is 20% by weight or less.

Among the above-mentioned thermal crosslinking agents, as a particularly preferred compound as the thermal crosslinking agent of component (E), —N (CH ₂ OR ′) ₂ group in the molecule (wherein R ′ represents an alkyl group or a hydrogen atom) And a compound obtained by allowing formalin to act on urea or melamine or an alkyl-modified product thereof is particularly preferable.

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

  More specifically, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxy Examples include silane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  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.

These silane coupling agents may be used alone or in combination of two or more.
In addition, when the photopolymerizable composition of the present embodiment contains the above-mentioned adhesion assistant, the blending amount thereof is usually 0.1% by weight or more with respect to the total solid content, usually 20% by weight or less, Preferably it is 10 weight% or less.

(F-2) Surfactant The photopolymerizable composition of the present embodiment is nonionic for the purpose of improving applicability as a coating liquid of the composition and developability of the photopolymerizable composition layer, etc. 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.
These commercially available products include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafac F142D”, “Megafac F172”, “Megafac F173”, “ 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 surfactant include “Toray Silicone DC3PA”, “Same SH7PA”, “Same DC11PA”, “Short SH21PA”, “Short SH28PA”, “Short SH29PA”, “Shortcut” “SH30PA”, “SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5) (6) (7) 6” manufactured by Toshiba Silicone Corporation, Commercially available products such as “TSF-4460”, “TSF-4442”, “KP341” manufactured by Silicone Co., Ltd., “BYK323”, “BYK330” manufactured by BYK Chemie may be used.

  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.

  In the photopolymerizable composition of the present embodiment, the content of the surfactant is preferably 10% by weight or less, more preferably 0.1 to 5% by weight, based on the total solid content. .

(F-3) Curing Agent The photopolymerizable composition of the present embodiment may further contain a curing agent in order to shorten the time under thermosetting conditions or change the set temperature. Different curing conditions can be appropriately selected depending on the manufacturing process of each element.
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.

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

(F-3-2) Polyvalent carboxylic acid (anhydride)
Examples of the polyvalent carboxylic acid (anhydride) include alicyclic polyvalent carboxylic acids such as methyl hymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride. Acid (anhydride); aromatic polycarboxylic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tricarboxylic anhydride, benzophenone tetracarboxylic anhydride; succinic acid, trimellitic acid, Examples thereof include alicyclic acid anhydrides such as maleic acid and cyclopentanetetracarboxylic acid; hydrolysates of aromatic acid anhydrides, and the like. Among these, trimellitic acid (anhydride) and phthalic anhydride are preferable.

(F-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 substituent such as.

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

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

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

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

  Further, monophenylsulfonium salts include benzyl-p-hydroxyphenylmethylsulfonium hexafluorophosphate, p-hydroxyphenyldimethylsulfonium hexafluoroantimonate, p-acetoxyphenyldimethylsulfonium hexafluoroantimony. And benzyl-p-hydroxyphenylmethylsulfonium hexafluoroantimonate, monophenylsulfonium salt types such as compounds represented by the following structural 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.

(F-3-5) Amine compound Examples of the amine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, piperidine, pyrrolidine, Ethylenediamine, trimethylhexamethylenediamine, dimethylcyclohexylamine, tetramethylguanidine, triethanolamine, N, N′-dimethylpiperazine, dicyanamide, or a derivative thereof; DBU (1,8-diazabiscyclo (5,4,0) undecene-1 ), Aliphatic amines such as DBU-based tetraphenylborate salts (first, second, third); metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, benzyldimethyl Min, dimethylamino-p-cresol, 2- (dimethylaminejomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, pyridine, picoline, DBU (1,8-diazabiscyclo (5,4,0 ) Aromatic amines (first, second, third) such as undecene-1), tri-2-ethylhexylate of 2,4,6-tris (dimethylaminomethyl) phenol; 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-cyanoe Tyl-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-triazine, 2,4-diamino-6- [2- Undecylimidazolyl- (1)]-ethyl-S-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl Imidazole compounds such as -4,5-di (cyanoethoxymethyl) imidazole; Min, iminobispropylamine, bis (hexamethylene) triamine, and the like.

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

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

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

  These curing agents may be used alone or in combination of two or more.

  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, maleic anhydride and ethylene, butylene, or propylene containing an alkyl group having 1 to 20 carbon atoms, a polypropyleneoxypropylene group having 1 to 15 carbon atoms, or a polyethyleneoxypropylene group having 1 to 15 carbon atoms. Compound, polyvalent carboxylic acid copolymer with at least one ethylene compound selected from styrene; block carboxylic acid compound comprising trimellitic acid or adduct of maleic acid and ethyl vinyl ether; 2,5-dihydroxy Benzoic compounds such as benzoic acid and 3,4,5-trihydroxybenzoic acid; benzyl-p-hydroxyphenylmethylsulfonium hexafluorophosphate, p-hydroxyphenyldimethylsulfonium hexafluoroantimonate, p-acetoxy Phenyldimethyl Sulfonium hexafluoroantimonate, benzyl-p-hydroxyphenylmethylsulfonium hexafluoroantimonate, monophenylsulfonium salt type such as compound represented by the structural formula (II), or benzylphenylsulfonium salt type And monophenylsulfonium salts.

Among these, polyvalent carboxylic acid copolymers and benzoic acid compounds are excellent in improving the adhesion to the support, and monosulfonium salts are excellent in improving the hardness.
A benzoic acid compound is particularly preferable because it is excellent in thermosetting, has high light transmittance, and is less affected by color change due to heat.

  When the photopolymerizable composition of the present embodiment contains a curing agent, the content of the curing agent in the photopolymerizable composition is usually 0.05% by weight or more based on the total solid content, Preferably it is 0.1 weight% or more, Usually 20 weight% or less, Preferably it is 10 weight% or less. When the amount of the curing agent is excessively small, adhesion to the support and hardness are liable to be reduced. On the other hand, when the amount is excessively large, decrease in thermal weight is likely to be increased.

(G) Additive In addition to the above components, the photopolymerizable 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, in the ratio of 40 weight% or less with respect to a total solid, Preferably it is 20 weight% or less.

  Furthermore, a polymerization accelerator can be added to the photopolymerizable 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 photopolymerizable 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 photopolymerizable 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 photopolymerizable 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), Tomissorb 800 (manufactured by API Corporation), SESORB100, SESORB101, SESORB101S, SEESORB102, SEESORB103, SEESORB103, SEESORB103, SEESORB103 Benzophenone compounds such as SEESORB106, SEESORB107, SEESORB151 (manufactured by Sipro Kasei); Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (Johoku Chemical Industries) , TINUVIN PS, TINUVIN 99-2, TINUV N109, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by Ciba Specialty Chemicals), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERORB76, EVERSORB75, EVERSORB75 , Tomisosorb 100, Tomisosorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Sipro Kasei) Benzotriazole compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.), benzoate compounds such as phenyl salicylate; hydroxyphenyl triazine compounds such as TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477DW, and TINUVIN 479 (manufactured by Ciba Specialty Chemicals). it can.

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

  When these ultraviolet absorbers are added to the photopolymerizable composition of the present embodiment, the blending ratio is usually 0.01% by weight or more and 15% by weight or less, preferably 0.8%, based on the total solid content. It is 05 weight% or more and 10 weight% or less. If the blending ratio is less than this range, effects such as improvement of the pattern shape and / or removal of the residue tend to be difficult to obtain, and if it is large, the sensitivity and / or the remaining film ratio tend to decrease.

(H) Organic solvent In the photopolymerizable composition of the present embodiment, each of the above-described components is usually in the range of 5 to 60% by weight, preferably 10 to 50% by weight, using an organic solvent. It is prepared and used so that

  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, Besso, 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, a mixture of PGMAc with one or more organic solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbeso, 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, sorbesso and carbitol is usually 10% by weight or more, preferably 30% by weight or more based on PGMAc. It is usually 80% by weight or less, preferably 70% by weight or less.

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

The photopolymerizable composition of the present invention includes, 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 used for forming insulating coating layers of various electronic components.
The photopolymerizable composition of the present invention is also useful for color filters, black matrices, overcoats, ribs and spacers used in liquid crystal panels such as liquid crystal displays.

[2] Method for Forming Protective Film Next, a method for forming a protective film using the photopolymerizable composition of the present embodiment will be described.

[2-1] Coating process First, the photopolymerizable composition of the present embodiment described above is coated on a substrate using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray. To do.
The coating film thickness of the photopolymerizable 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 dry coating film of the photopolymerizable composition, and image exposure is performed through the photomask. After the exposure, an unexposed uncured portion is removed by development to form an image. 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, etc. 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, residue and the like.

  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 photopolymerizable composition film on which an image has been formed by the exposure / development step is then subjected to a heat treatment (hard baking) step to become a cured product (thermosetting film). In 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 the hard baking.

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

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

  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, each component of the photopolymerizable composition used in the following is as follows.

(A) Alkali-soluble resin P1: Styrene / α-methylstyrene / acrylic acid (molar ratio: 70/10/20)
Copolymer
In the general formula (I), x = 80, y = 0, z = 20
Acid value: 108 mg-KOH / g
Mw: 4,600
P2: Dicyclopentanyl methacrylate / methyl methacrylate / styrene /
Methacrylic acid (molar ratio: 20/35/10/35) copolymer
In the general formula (I), x = 10, y = 55, z = 35
Acid value: 157 mg-KOH / g
Mw: 17,000
P3: Styrene / methyl acrylate / acrylic acid (molar ratio: 35/25/40)
Copolymer
In the general formula (I), x = 35, y = 25, z = 40
Acid value: 259 mg-KOH / g
Mw: 28,300

(B) Ethylenically unsaturated compound

(C) Photopolymerization initiator

(D) Resin having a softening point of 100 ° C. or lower

(D ′) Resin having a softening point higher than 100 ° C.

(H) Organic solvent H1: Propylene glycol monomethyl ether acetate (PGMAc)

In addition, the measuring method of the acid value of the used alkali-soluble resin is as follows.
(Acid value)
About alkali-soluble resin, it measured based on JIS-K0070 (standard oil-fat test method).

  Moreover, the various evaluation methods of the photopolymerizable composition, the exposure film, and the thermosetting film in Examples and Comparative Examples are as follows.

(sensitivity)
The photopolymerizable composition was applied on a glass substrate so that the dry film thickness was about 4 μm, baked on a hot plate at 90 ° C. for 90 seconds, and then at an illuminance of 30 mW / cm ^{2 with} a high-pressure mercury lamp. Exposed. As exposure conditions, the exposure energy amount was set in the range of 10 mJ / cm ² to 320 mJ / cm ² and the exposure energy amount was set at intervals of 2 ^1/2 times. After exposure, the film is immersed in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 110 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 dose, and the minimum exposure dose at which the difference in exposure film thickness between a certain exposure dose and the exposure dose that is ^21/2 times is within 10%. Was defined as sensitivity (mJ / cm ² ).

(Resolution)
The image of the thermosetting film formed in each example 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 formed in each example 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 formed in each example was observed with an optical microscope, and the residue in the space portion was evaluated according to the following criteria.
A: No residue B: Residue is slightly seen in the periphery of the resist C: Residue is seen in the center of the space part

(Light transmittance)
The light transmittance of the thermosetting film formed in each example 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 1-3, Comparative Examples 1-3)
A photopolymerizable composition was prepared according to the formulation shown in Table 1.
The obtained photopolymerizable composition was applied on a glass plate “AN100” for color filters 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 width of 5 micrometers-50 micrometers from the coating film side. As the exposure conditions, the image plane illuminance measured with an illuminometer with a wavelength of 365 nm was 30 mW / cm ² , and the exposure amount was the optimum exposure amount described later.
Next, a 0.4% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution, and the substrate was immersed in the developing solution for 110 seconds at 25 ° C., 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.

  From Table 1, it can be seen that the photopolymerizable composition of the present invention has high sensitivity, high resolution, good pattern shape, and no generation of residue.

Claims (2)

A photopolymerizable composition containing the following components (A) to (D) ,
A photopolymerizable composition for an interlayer insulating film, wherein the component (A) is an alkali-soluble resin represented by the following general formula (I), and the component (C) is an oxime ester compound .
(A) Alkali-soluble resin having an acid value of 100 mg-KOH / g or more and 250 mg-KOH / g or less (B) Compound having an ethylenically unsaturated group (C) Photopolymerization initiator (D) Resin having a softening point of 100 ° C. or less

(However, R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. Represents an alkenyl group having 2 to 20 carbon atoms and an alkynyl group having 2 to 20 carbon atoms, x: y: z represents a mol% of each structural unit, and x + y + z = 100. The photopolymerizable composition for an interlayer insulating film according to claim 1, wherein the component (D) is a resin containing an epoxy group.