JP2015038607A - Photosensitive composition, cured product, spacer, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition that exhibits high resolution even when the composition is formed into a thick spacer, suppresses film reduction on a surface thereof, and has excellent compression characteristics and adhesiveness.SOLUTION: The photosensitive composition comprises (A) a photopolymerizable monomer, (B) a binder resin, and (C) a photopolymerization initiator, and contains, as the (C) photopolymerization initiator, (C-1) a specific hexaaryl biimidazole compound and (C-2) an acylphosphine oxide compound expressed by general formula (2). In the formula, R4 to R8 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent; and R9 and R10 each independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group having 1 to 10 carbon atoms which may have a substituent, or a benzoyl group having 1 to 10 carbon atoms which may have a substituent.

Description

  The present invention relates to a photosensitive composition used for forming color filters, black matrices, overcoats, ribs, spacers, etc. used in image display devices such as liquid crystal displays and organic EL displays, and further curing the photosensitive composition. The present invention relates to a cured product and a spacer, and an image display apparatus having these.

  Photosensitive composition containing a photopolymerizable monomer, a binder resin, a photopolymerization initiator and the like when forming a color filter, a black matrix, an overcoat, a rib, a spacer, etc. in the field of image display devices represented by liquid crystal displays In some cases, high curability and excellent mechanical properties are required for the photosensitive composition. For example, the spacer (in the present specification, the “spacer” is formed of a photosensitive composition and indicates a so-called columnar spacer, column spacer, photospacer, etc.) is two in the liquid crystal panel. It is preferably used for the purpose of keeping the distance between the substrates constant, and it is preferred that the substrate has a vertical shape and good compression characteristics and developability.

Patent Documents 1 and 2 report that two types of specific photopolymerization initiators are used in combination for the purpose of simultaneously forming a plurality of spacers having different heights into an optimum shape. Patent Document 3 reports that, when forming a spacer, two types of specific photopolymerization initiators are used in combination for the purpose of easily providing a thickness change due to exposure illuminance.
On the other hand, in Patent Document 4, when forming a colored pattern, two types of specific photopolymerization initiators are used in combination for the purpose of reducing the difference in line width between the surface portion, the intermediate portion, and the deepest portion. It has been reported.

JP 2010-020158 A JP 2012-098357 A Special table 2011-501816 gazette JP 2006-276221 A

In recent years, with higher functionality of image display devices, higher functionality of spacers has been demanded. For example, it is necessary to increase the thickness of the spacer, and in particular, it is required to increase the resolution when the thickness is increased, that is, to reduce the difference in width between the upper surface and the lower surface of the spacer.
When this inventor examined, patent documents 1-3 assumed the thin film, and no examination is made | formed about thickening more than 10 micrometers in thickness. In particular, when the inventors of the present invention examined the combination of photopolymerization initiators described in Patent Documents 1 and 3, the resolution when the film was thickened was insufficient, the surface was thinned, and the compression characteristics were further reduced. It was newly found that the adhesiveness was also insufficient.

  Further, Patent Document 4 assumes a coloring pattern using a pigment, and no consideration is given to using it as a spacer.

  The present invention has been made in view of the above-described prior art, and the object of the present invention is to provide high resolution and suppress surface thinning even when a spacer having a high film thickness is formed. And providing a photosensitive composition excellent in compression characteristics and adhesion.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be achieved by using two specific types of initiators together in the photosensitive composition, thereby completing the present invention. It came. That is, the gist of the present invention is as follows.
[1] A photosensitive composition containing (A) a photopolymerizable monomer, (B) a binder resin, and (C) a photopolymerization initiator, wherein (C-1) (C-1) ) A hexaarylbiimidazole compound represented by the following general formula (1-1) and / or the following general formula (1-2), and (C-2) an acylphosphine oxide compound represented by the following general formula (2). A photosensitive composition comprising:

(In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxy group having 1 to 4 carbon atoms. Represents a group or a halogen atom, and m, n and l each independently represents an integer of 0 to 5.)

(In formula, R < ⁴ > -R < ⁸ > is respectively independently a hydrogen atom, the C1-C4 alkyl group which may have a substituent, or the C1-C4 which may have a substituent. Represents an alkoxy group, and R ⁹ and R ¹⁰ each independently have an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group having 1 to 10 carbon atoms, or Represents a benzoyl group which may have a substituent having 1 to 10 carbon atoms.)
[2] The photosensitive composition according to [1], wherein the acylphosphine oxide compound represented by the general formula (2) (C-2) is a compound represented by the following structural formula.

[3] Content (mass%) of the hexaarylbiimidazole compound represented by (C-1) general formula (1-1) and general formula (1-2) in the (C) photopolymerization initiator. And (C-2) C-2 / C-1 which is a ratio of the content (% by mass) of the acylphosphine oxide compound represented by the general formula (2) is 0.5 or more and 15 or less. The photosensitive resin composition according to [1] or [2], which is characterized.
[4] The photosensitive composition according to any one of [1] to [3], wherein (D) a compound having a mercapto group is contained as a sensitizer.
[5] The photosensitive composition according to [4], wherein the compound having a mercapto group is 2-mercaptobenzothiazole and / or 2-mercaptobenzimidazole.
[6] The photosensitive composition according to any one of [1] to [5], wherein (E) a silane coupling agent having an imidazole group is contained as a silane coupling agent.
[7] The content of the (A) photopolymerizable monomer is 40% by mass or more based on the total content of the (A) photopolymerizable monomer and the (B) binder resin. 1]-[6] The photosensitive composition in any one.
[8] A cured product obtained by curing the photosensitive composition according to any one of [1] to [7].
[9] A spacer comprising the cured product according to [8].
[10] An image display device having the cured product according to [8].
[11] An image display device having the spacer according to [9].

The photosensitive composition of the present invention has the following effects when cured to form a spacer. (1) Even at a high film thickness, high resolution is exhibited, the surface and the inside are uniformly cured, and the difference in width between the upper surface and the lower surface can be reduced.
(2) Even when the film thickness is high, the surface is sufficiently cured, and film thickness reduction due to development can be suppressed.
(3) Excellent elastic recovery characteristics even at high film thickness.
(4) Excellent adhesion even at high film thickness.

It is a figure which shows the measurement result of the transmittance | permeability of Example 3. FIG.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not specified to these, unless the summary is exceeded.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and “total solids” means the total amount of components of the photosensitive composition excluding the solvent. Shall mean. Furthermore, the numerical range represented using “to” in the present invention means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[1] Photosensitive composition The photosensitive composition of the present invention contains (A) a photopolymerizable monomer, (B) a binder resin, and (C) a photopolymerization initiator, and (C) a photopolymerization initiator. (C-1) A hexaarylbiimidazole compound represented by the following general formula (1-1) and / or the following general formula (1-2), and (C-2) represented by the following general formula (2). It is characterized by containing an acylphosphine oxide compound.

In said formula, R < ¹ > -R < ³ > is respectively independently a hydrogen atom, the C1-C4 alkyl group which may have a substituent, and the C1-C4 alkoxy group which may have a substituent. Or a halogen atom, and m, n and l each independently represent an integer of 0 to 5.

In said formula, R < ⁴ > -R < ⁸ > is respectively independently a hydrogen atom, the C1-C4 alkyl group which may have a substituent, or the C1-C4 alkoxy which may have a substituent. R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group that may have a substituent, a phenyl group that may have a C 1-10 substituent, or carbon. The benzoyl group which may have a substituent of several 1-10 is represented.

Further, the double bond equivalent in the total solid content in the photosensitive composition is preferably 300 or less, more preferably 170 or less, and usually 100 or more. By setting it to the upper limit value or less, the polymerization density tends to increase. The double bond equivalent can be calculated by converting from the double bond-derived peak intensity and weight by ¹ H-NMR analysis using dimethyl terephthalate as a standard substance.

Moreover, it is preferable that the photosensitive composition of this invention contains (D) sensitizer and / or (E) silane coupling agent.
When the photosensitive composition of the present invention is used for solder resists, overcoats, ribs or spacers, a thermal polymerizable initiator, epoxy compound, epoxy curing agent, amino compound, polymerization accelerator Further, an inorganic filler or the like may be contained. Further, when the photosensitive composition of the present invention is used for a color filter or a black matrix, it may further contain a coloring material, a dispersant, and a dispersion aid.

<(A) Photopolymerizable monomer>
The photosensitive composition of the present invention contains (A) a photopolymerizable monomer. In the present invention, the term “monomer” means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes
Examples of the photopolymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule. For example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citracone Examples thereof include unsaturated carboxylic acids such as acids, alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, and styrene.

In addition, as the photopolymerizable monomer, two or more ethylenically unsaturated bonds are included in the molecule from the viewpoints of polymerizability, crosslinkability, and expansion of the difference in developer solubility between the exposed and unexposed areas. It is preferable that the acrylate compound has an unsaturated bond derived from a (meth) acryloyloxy group.
Examples of the compound having two or more ethylenically unsaturated bonds in the molecule include the following compounds.

(A-1) Esters of unsaturated carboxylic acid and polyhydroxy compound (hereinafter sometimes referred to as “ester (meth) acrylates”)
(A-2) (Meth) acryloyloxy group-containing phosphates (A-3) Urethane (meth) acrylates of hydroxy (meth) acrylate compounds and polyisocyanate compounds (A-4) (meth) acrylic acid or hydroxy ( Epoxy (meth) acrylates of (meth) acrylate compounds and polyepoxy compounds (A-5) (A-1) Phthalic anhydride and succinic anhydride modified products of esters of unsaturated carboxylic acids and polyhydroxy compounds

  Examples of the (A-1) ester (meth) acrylates include unsaturated carboxylic acid as described above, ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14). ), Trimethylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanolamine and other aliphatic poly A reaction product with a hydroxy compound may be mentioned.

  More specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Methylolpropane ethylene oxide addition tri (meth) 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 Sa (meth) acrylate, and crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

The (A-1) ester (meth) acrylates include unsaturated carboxylic acids as described above, aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or ethylene oxides thereof. A reaction product with an adduct is mentioned.
More specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate];

  Reaction product of unsaturated carboxylic acid as described above and heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate: Specifically, for example, di ( (Meth) acrylate, tri (meth) acrylate, etc .; reaction product of unsaturated carboxylic acid as described above, polycarboxylic acid and polyhydroxy compound: Specifically, for example, (meth) acrylic acid, phthalic acid and ethylene Condensate of glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol, condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, (meth) acrylic acid, adipic acid, butanediol and glycerin And a condensate thereof.

  The (A-2) (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group, but are represented by the following general formulas (Ia) to (Ic). Those are preferred.

In the above formulas (Ia), (Ib) and (Ic), R ⁵¹ represents a hydrogen atom or a methyl group, and Xa may have an alkylene group or a substituent which may have a substituent. Good arylene group. P and p ′ are each independently an integer of 1 to 25, and q is 1, 2 or 3.
Here, the alkylene group represented by Xa is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Moreover, as an arylene group, a C6-C10 thing is preferable and a phenylene group is still more preferable. Among these, an alkylene group is preferable in the present invention. Examples of the substituent which the alkylene group or arylene group of Xa may have include, for example, a halogen atom, a hydroxyl group, a C 1-15 alkyl group, preferably a C 1-10 alkyl group, and a C 2-10 alkenyl group. Group, phenyl group, carboxyl group, sulfanyl group, phosphino group, amino group, nitro group and the like.

  Here, p and p 'are preferably integers of 1 to 10, particularly integers of 1 to 4. Specific examples of such compounds include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and the like, manufactured by Kyoeisha Chemical Co., Ltd. "Ester P-1M" "Light ester P-2M" "Light acrylate P-1A" "Light acrylate P-2A", "KAYAMER (registered trademark) PM-2" "KAYAMER (registered trademark) PM-" manufactured by Nippon Kayaku Co., Ltd. 21 ". These may be used alone or as a mixture.

As said (A-3) urethane (meth) acrylates, the reaction material of a hydroxy (meth) acrylate compound and a polyisocyanate compound is mentioned, for example.
Examples of the hydroxy (meth) acrylate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylolethane tri (meth) acrylate, and the like.

  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), Examples include cycloaliphatic polyisocyanates such as isophorone diisocyanate and bicycloheptane triisocyanate; aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanatephenyl) thiophosphate; heterocyclic polyisocyanates such as isocyanurate, and the like. .

  As the (A-3) urethane (meth) acrylates, 4 or more (preferably 6 or more, more preferably 8 or more) urethane bonds [—NH—CO—O—] in one molecule, and It is preferably a compound having 4 or more (preferably 6 or more, more preferably 8 or more) (meth) acryloyloxy groups. Such a compound can be obtained, for example, by reacting the following compound (i) with the following compound (ii).

(I) 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. , A compound (i-1) obtained by reacting a diisocyanate compound such as tolylene diisocyanate;

Alternatively, for compounds having two or more hydroxyl groups in one molecule such as ethylene glycol, “DURANATE (registered trademark) 24A-100”, “DURANATE (registered trademark) 22A-75PX”, “DURANATE” manufactured by Asahi Kasei Kogyo Co., Ltd. (Registered trademark) 21S-75E "," Duranate (registered trademark) 18H-70B "and other biuret types," Duranate (registered trademark) P-301-75E ", and" Duranate (registered trademark) E-402-90T ". Compound (i-2) obtained by reacting a compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate (registered trademark) E-405-80T”;
Examples thereof include a compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate and the like.
A commercial item can be used as such a compound, for example, "Duranate (trademark) ME20-100" by Asahi Kasei Kogyo Co., Ltd. is mentioned.

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

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, particularly preferably 1,000 to 150,000. Moreover, it is preferable that it is 600-150,000 as molecular weight of the said (A-3) urethane (meth) acrylate. Unless otherwise specified, in the present invention, the molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured using a gel permeation chromatography method (GPC method).

In addition, such (A-3) urethane (meth) acrylates are, for example, the above compound (i) and the above compound (ii) in an organic solvent such as toluene or ethyl acetate at 10 ° C. to It can be produced by a method of reacting at 150 ° C. for about 5 minutes to 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.
In the present invention, among the above (A-3) urethane (meth) acrylates, those represented by the following general formula (II) are particularly preferably used.

In the formula (II), R ^a represents ^a group having a repeating structure of an alkyleneoxy group or an aryleneoxy group and having 4 to 20 oxy groups that can be bonded to R ^b . R ^b and R ^c each independently represent an alkylene group having 1 to 10 carbon atoms, and R ^d represents an organic residue having 1 to 10 (meth) acryloyloxy groups. R ^a , R ^b , R ^c , and R ^d may have a substituent. x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15.
Here, examples of the repeating structure of the alkyleneoxy group of ^Ra in formula (II) include those derived from propylene triol, glycerin, pentaerythritol, and the like. In addition, examples of the repeating structure of the aryleneoxy group represented by ^Ra include those derived from pyrogallol, 1,3,5-benzenetriol, and the like.

Moreover, it is preferable that carbon number of the alkylene group of R ^{< b>} and R ^<c > is 1-5 each independently. The number of (meth) acryloyloxy groups in R ^d is preferably 1-7. It is preferable that x is 4 to 15, y is 1 to 10, and z is 1 to 10.
Furthermore, as R ^a , the following formula [wherein, k is an integer of 2 to 10]. It is preferable that R ^b and R ^c are preferably each independently a dimethylene group, a monomethyldimethylene group, or a trimethylene group. Further, R ^d is preferably the following formula.

Examples of the (A-4) epoxy (meth) acrylates include a reaction product of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.
Examples of the polyepoxy compound include (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, and (poly) neo. Aliphatic polyepoxy compounds such as pentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether; phenol Aromatic polyepoxy such as novolac polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound Compound; sorbitan polyglycidyl ether, triglycidyl isocyanurate, heterocyclic polyepoxy compounds such as triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.

  Examples of the acid-modified product of the ester of (A-1) unsaturated carboxylic acid and polyhydroxy compound (A-5) above include succinic anhydride-modified products of reaction products of dipentaerythritol and acrylic acid, and phthalic anhydride. Acid modified products, tetrahydrophthalic anhydride modified products, pentaerythritol triacrylate succinic anhydride modified products, phthalic anhydride modified products, tetrahydrophthalic anhydride modified products, and the like are preferred. Furthermore, preferred are pentaerythritol triacrylate modified with succinic anhydride, modified phthalic anhydride, modified tetrahydrophthalic anhydride and the like. (A-5) has excellent development solubility.

  Other ethylenically unsaturated compounds used as photopolymerizable monomers include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl groups such as divinyl phthalate Compounds and thioether bond-containing compounds in which the crosslinking rate is improved by sulfidizing the ether bond of the ether bond-containing ethylenically unsaturated compound with phosphorus pentasulfide or the like to convert it to a thioether bond can be mentioned.

  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.))] containing isocyanate groups or mercapto groups Compounds bonded using silane coupling agents (compounds that have improved strength and heat resistance as cured products by reacting and bonding silica sol to ethylenically unsaturated compounds via silane coupling agents) Can be mentioned.

In the present invention, from the viewpoint of the mechanical strength of the cured product, (A-1) ester (meth) acrylates, (A-2) (meth) acryloyloxy group-containing phosphates, or (A-3) Urethane (meth) acrylates are preferred, and (A-1) ester (meth) acrylates are more preferred.
Moreover, among (A-1) ester (meth) acrylates, it contains polyoxyalkylene groups such as polyethylene glycol, polypropylene glycol, or polyethylene oxide adducts of bisphenol A, and contains two or more (meth) acryloyloxy groups. Particularly preferred are ester (meth) acrylates.

<(B) Binder resin>
The (B) binder resin used in the photosensitive composition of the present invention is preferably an alkali-soluble resin, and more preferably an alkali-soluble resin having a carboxyl group.
Further, the binder resin used in the photosensitive composition of the present invention is such that when the photosensitive composition is irradiated with actinic rays, it undergoes addition polymerization by the action of a photopolymerization initiator, and in some cases, crosslinks and cures. A compound having at least one radical polymerizable ethylenically unsaturated bond in the molecule (hereinafter sometimes abbreviated as “ethylenically unsaturated compound”) is preferable. Specific examples include the following specific ethylenically unsaturated compounds and ethylenically unsaturated group-containing resins.

(B-1) Specific ethylenically unsaturated compound In order to achieve the mechanical properties of the cured product, the photosensitive composition of the present invention has an ethylenically unsaturated compound having a double bond equivalent of 400 or less (hereinafter "" It may be referred to as “specific ethylenically unsaturated compound”).
As the double bond equivalent of the specific ethylenically unsaturated compound used in the present invention is smaller and the number of double bonds per unit weight is larger, the elastic recovery rate and recovery rate of the obtained cured product tend to increase. Therefore, the double bond equivalent of the specific ethylenically unsaturated compound used in the present invention is usually 400 or less, preferably 350 or less, and more preferably 200 or less. The lower limit of the double bond equivalent of the specific ethylenically unsaturated compound is usually 100 or more. In addition, the double bond equivalent of a specific ethylenically unsaturated compound can be calculated by the following formula.

  Compound double bond equivalent = weight of compound (g) / number of moles containing double bond of compound

  The specific ethylenically unsaturated compound preferably has an acid group. Here, “having an acid group” means having a group giving a value greater than 0 as an acid value determined by titration with KOH (potassium hydroxide). Specifically, it means having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, it is particularly preferred to have a carboxyl group.

Further, the specific ethylenically unsaturated compound is preferably obtained from an epoxy compound as described later.
The weight average molecular weight (Mw) of the specific ethylenically unsaturated compound is preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more. Further, the weight average molecular weight (Mw) of the specific ethylenically unsaturated compound is usually 100,000 or less, preferably 10,000 or less. If the weight average molecular weight (Mw) of the specific ethylenically unsaturated compound is excessively small, the amount of deformation of the resulting photosensitive composition tends to be small, and if it is excessively large, the photosensitive composition tends to be poorly developed. Tend.

In the present specification, the weight average molecular weight (Mw) is measured as a molecular weight converted to standard polystyrene by GPC (gel permeation chromatography).
The specific ethylenically unsaturated compound used in the present invention is not particularly limited as long as the double bond equivalent is 400 or less, but is preferably obtained from an epoxy group-containing compound. It is preferable to contain.
Examples of the specific ethylenically unsaturated compound obtained from such an epoxy group-containing compound include compounds represented by the following general formula (BI).

In the above formula (BI), R ¹¹ represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R ¹² represents an ethylenically unsaturated group-containing carbonyloxy group which may have a substituent. R ¹³ and R ¹⁴ each independently represents an arbitrary substituent. b is an integer of 0-10. a is an integer of 1 or more. X represents an arbitrary organic group which may have a substituent.
In the general formula (BI), the alkylene group represented by R ¹¹ is preferably one having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Moreover, as an arylene group, a C6-C10 thing is preferable and a phenylene group is still more preferable. Among these, an alkylene group is preferable in the present invention.

Examples of the substituent that the alkylene group or arylene group of R ¹¹ may have include, for example, a halogen atom, a hydroxyl group, a C 1-15 alkyl group, preferably a C 1-10 alkyl group, and a C 2-10 carbon atom. Examples include alkenyl group, phenyl group, carboxyl group, sulfanyl group, phosphino group, amino group, nitro group and the like.
Moreover, b is an integer of 0-10, it is preferable that it is an integer of 0-5, and it is still more preferable that it is an integer of 0-3. When b exceeds the above range, when the resulting photosensitive composition is cured, there is a tendency that the film thickness of the pattern portion is reduced during development or the heat resistance is lowered.

The lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent for R ¹² in formula (BI) is usually 3, preferably 5, and more preferably 10. The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. Whether the carbon number is excessively large or excessively small, the mechanical properties of the cured product formed by the photosensitive composition of the present invention may not be obtained.
The ethylenically unsaturated group-containing carbonyloxy group which may have a substituent represented by R ¹² is more preferably a group represented by the following general formula (B-II).

In the above formula (B-II), R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, and U represents an arbitrary divalent group.
In the formula (B-II), U preferably includes an alkylene group which may have a substituent and / or an arylene group which may have a substituent, and a carbonyloxy group. A divalent group is shown. More preferably, U represents an alkylene group having 1 to 10 carbon atoms which may have a substituent and / or an arylene group having 1 to 10 carbon atoms which may have a substituent, a carbonyloxy group, , A divalent group containing
In formula (BI), R ¹³ preferably represents a hydrogen atom, a substituent represented by the following general formula (B-IIIa), or a substituent represented by the following general formula (B-IIIb). .

In the above formulas (B-IIIa) and (B-IIIb), R ²¹ and R ²² have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An cycloalkyl group that may be substituted, a cycloalkenyl group that may have a substituent, or an aryl group that may have a substituent.
Here, as the alkyl group for R ²¹ and R ²² , those having 1 to 20 carbon atoms are preferable. Moreover, as an alkenyl group, a C2-C20 thing is preferable. Moreover, as a cycloalkyl group, what is C3-C20 is preferable. Further, as the cycloalkenyl group, those having 3 to 20 carbon atoms are preferable. The aryl group is preferably one having 6 to 20 carbon atoms.

Examples of the substituent that R ²¹ and R ²² may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, Examples include a carbonyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group. Among these, R ²¹ preferably has a carboxyl group as a substituent.

Although it does not specifically limit as a substituent represented by R < ¹⁴ > in the compound represented by the general formula (BI) mentioned above, For example, the substituent represented by the following general formula (B-IV) is mentioned. .

In said formula (B-IV), R < ¹¹ >, R <^12> , R <^13> and b are synonymous with the said general formula (BI).
When R ¹⁴ is a substituent represented by the above general formula (B-IV), R ¹¹ , R ¹² , R ¹³ and b in the formula (B-IV) are the same as those in the general formula (BI). ) May be the same as or different from R ¹¹ , R ¹² , R ¹³ and b.
X in the compound represented by the general formula (BI) described above represents an arbitrary organic group which may have a substituent. This X has a basic function of bonding a double bond-containing group, and serves as a site for bonding an appropriate molecular weight and an appropriate number of substituents so as not to increase the double bond equivalent of the entire compound. There is a function to provide a functional group.

The molecular weight of X in the compound represented by formula (BI) is usually 14 or more, preferably 28 or more, and usually 1000 or less, preferably 800 or less.
In the present invention, specific examples of the organic group that can be used as X include a linear or cyclic organic group.
Examples of the linear organic group include organic groups derived from alkanes and alkenes; (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate , Organic groups derived from homo- or copolymers such as vinylidene chloride and maleimide; derived from acid-modified epoxy acrylate, polyolefin, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. An organic group is mentioned.

In addition, as the cyclic organic group, an organic group derived from an alicyclic ring, an aromatic hydrocarbon ring, a heterocyclic ring or the like, or a condensed ring thereof, and these rings are bonded via a linking group. Examples include organic groups derived from things.
Among these, examples of the alicyclic ring include a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, and a tricyclodecane ring.

Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, biphenylene ring, indene ring and the like.
As the heterocyclic ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine Ring, pyrazine ring and the like.

  Examples of the linking group via the bond of the cyclic organic group include a direct bond or a divalent or higher valent linking group. As the divalent or higher linking group, known ones can be used. For example, alkylene, polyoxyalkylene, amine, O atom, S atom, ketone group, thioketone group, -C (= O) O-, amide , Se, Te, P, As, Sb, Bi, Si, B, and other metals, heterocycles, aromatic rings, heteroaromatic rings, and any combination thereof.

  The organic group represented by X is, for example, an alkylene group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms; an arylene group having 6 to 10 carbon atoms; 2 to 50 carbon atoms, preferably 2 to 30 carbon atoms. Polyether groups of: bisphenols such as bisphenol A and bisphenol F shown below: trisphenol; residues obtained by removing hydroxyl groups of polyol compounds such as novolak ((X-1) to (X-21)).

  In the exemplary formula of the organic group represented by X, w represents an integer of 0 or more. In the exemplified (X-13), (X-15), (X-18), (X-19), and (X-20), * represents a bond. In these exemplary structures, when there are three or more bonds *, the number of bonds as the linking group X covers at least two of these bonds. In this case, the substituent linked to the remaining one or more bonds is not particularly limited and is preferably a group represented by the general formula (B-IV).

  In addition, when the compound represented with the said general formula (BI) has a benzene ring, as a substituent which the benzene ring may have, a C1-C15 alkyl group, carbon number 1 is mentioned, for example. -15 alkoxy group, C2-C15 acyl group, C6-C14 aryl group, carboxyl group, hydroxyl group, C1-C16 alkoxycarbonyl group, carboxyl group, halogen atom and the like. Among these, a C1-C5 alkyl group, a phenyl group, and a halogen atom are still more preferable.

The method for producing the compound represented by the general formula (BI) is not particularly limited as long as it is a production method capable of obtaining a compound having a structure represented by the general formula (BI).
Here, for example, a production method using an epoxy group-containing compound represented by the following general formula (B-V) will be described as an example. That is, a compound obtained by using a compound represented by the following general formula (B-V) as a raw material, forming an ethylenically unsaturated group-containing carbonyloxy group thereon, and then forming this ethylenically unsaturated group-containing carbonyloxy group A compound represented by the general formula (BI) by reacting with one or more compounds selected from the group consisting of a polyvalent carboxylic acid, its anhydride, and a compound having an isocyanate group. it can.

In the above formula (BV), R ¹¹ , X and b have the same meanings as in the general formula (BI). R ¹⁸ has the same meaning as R ¹¹ in formula (BI).
Examples of the epoxy group-containing compound represented by the general formula (B-V) include (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, ( Poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) Aliphatic polyepoxy compounds such as sorbitol polyglycidyl ether;

Phenol novolac polyepoxy compound, brominated phenol novolak polyepoxy compound, (o-, m-, p-) cresol novolac polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound, bis (hydroxyphenyl) fluorene type poly Aromatic polyepoxy compounds such as epoxy compounds;
And polyepoxy compounds such as heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.

The epoxy group-containing compound represented by the general formula (B-V) may be used alone or in combination of two or more.
In addition, the lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group formed in the epoxy group-containing compound represented by the general formula (B-V) is usually 3, preferably 5, and more preferably 10. . The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. When the number of carbon atoms is less than the above range, when the photosensitive composition is cured, the flexibility tends to be insufficient and the adhesion to the substrate tends to be poor. On the other hand, when the carbon number is excessively large, the heat resistance tends to decrease.

These ethylenically unsaturated group-containing carbonyloxy groups are preferably groups represented by the general formula (B-II).
Here, as a formation method of the ethylenically unsaturated group containing carbonyloxy group represented by the said general formula (B-II), as a result of the reaction which uses the compound represented by the said general formula (BV) as a raw material The method is not particularly limited as long as the ethylenically unsaturated group-containing carbonyloxy group is formed.

  Specifically, a method of reacting a compound represented by the general formula (BV) with an ethylenically unsaturated group-containing carboxylic acid (a); first, represented by the general formula (BV) And a compound (c) having a functional group that reacts with a hydroxyl group or a carboxyl group to be produced, and the like. Examples of the “ethylenically unsaturated group-containing carboxylic acid (a)” used in the above-described method for forming an ethylenically unsaturated group-containing carbonyloxy group include a haloalkyl group, an alkoxyl group, a halogen atom, and a nitro group at the α-position. An unsaturated monocarboxylic acid substituted with a cyano group, etc .; a reaction product of (meth) acrylic acid with a lactone or polylactone; a saturated or unsaturated dicarboxylic acid anhydride and one or more hydroxyl groups in one molecule. And a half ester obtained by reacting a (meth) acrylate derivative with a half ester obtained by reacting a saturated or unsaturated dicarboxylic acid anhydride with an unsaturated group-containing glycidyl compound.

Here, examples of the unsaturated monocarboxylic acid in which the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, etc. include acrylic acid, methacrylic acid, crotonic acid, o-, m- , P-vinylbenzoic acid and the like.
Examples of the saturated or unsaturated dicarboxylic acid anhydride include succinic anhydride, adipic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydroxyphthalic anhydride, hexahydrophthalic anhydride. Examples include acid, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and the like.

  Examples of (meth) acrylate derivatives having one or more hydroxyl groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  Examples of the unsaturated group-containing glycidyl compound include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] ( And (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] oxymethyl (meth) acrylate, and the like. In the present invention, as the “ethylenically unsaturated group-containing carboxylic acid (a)”, among these, a saturated or unsaturated dicarboxylic acid anhydride and a (meth) acrylate having one or more hydroxyl groups in one molecule A half ester obtained by reacting with a derivative is preferred.

In this case, the saturated or unsaturated dicarboxylic acid anhydride is preferably succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or phthalic anhydride. In addition, (meth) acrylate derivatives having one or more hydroxyl groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentaerythritol tri (meth) acrylate. Dipentaerythritol penta (meth) acrylate is preferred.
These ethylenically unsaturated group-containing carboxylic acids (a) may be used alone or in combination of two or more.

  Next, examples of the “carboxylic acids not containing an ethylenically unsaturated group (b)” used in the above-described method for forming an ethylenically unsaturated group-containing carbonyloxy group include hydroxyl group-containing carboxyls such as lactic acid and dihydroxypropionic acid. Examples thereof include acids and anhydrides thereof; saturated or unsaturated dicarboxylic acids such as succinic acid, maleic acid, tetrahydrophthalic acid, phthalic acid, and tartaric acid, and anhydrides thereof.

Examples of the “compound (c) having a functional group reactive with a hydroxyl group or a carboxyl group” used in the above-described method for forming an ethylenically unsaturated group-containing carbonyloxy group include an epoxy group, a carboxyl group, and an isocyanate group. The compound which has is preferable.
Specifically, compounds exemplified in the above-mentioned “ethylenically unsaturated group-containing carboxylic acid (a)”; unsaturated group-containing used for obtaining the “ethylenically unsaturated group-containing carboxylic acid (a)” Examples thereof include, but are not limited to, ethylenically unsaturated group-containing compounds such as glycidyl compounds.

The above-mentioned “carboxylic acid (b) containing no ethylenically unsaturated group” and “compound (c) having a functional group that reacts with a hydroxyl group or a carboxyl group” can be used alone or in combination of two types. You may use the above together.
In addition, as an epoxy group-containing compound represented by the general formula (B-V) as a raw material, an ethylenically unsaturated group-containing carbonyloxy group is formed thereon, and then further reacted as a polyvalent carboxylic acid or an anhydride thereof. Include the following compounds.

  For example, saturated or unsaturated dicarboxylic acids such as succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, phthalic acid, chlorendic acid, etc. Acids and their acid anhydrides; trimellitic acid and its anhydrides; pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, etc. Examples thereof include tetracarboxylic acids and acid anhydrides thereof.

  Among these, as a photosensitive composition, from the viewpoint of dissolution and removal of non-image areas during alkali development, dicarboxylic acids such as oxalic acid, tetrahydrophthalic acid, phthalic acid, maleic acid, and acid anhydrides thereof, trimellitic acid And acid anhydrides thereof, pyromellitic acid, biphenyltetracarboxylic acid, tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, and acid dianhydrides thereof are preferred.

  Further, among these, acid anhydrides of polyvalent carboxylic acids having an acid dissociation constant (first dissociation constant) of 3.5 or more are preferable. The acid dissociation constant is preferably 3.8 or more, and particularly preferably 4.0 or more. Examples of acid anhydrides of polycarboxylic acids having an acid dissociation constant (first dissociation constant) of 3.5 or more include oxalic acid anhydride, tetrahydrophthalic acid anhydride, 1, 2, An acid dianhydride of 3,4-butanetetracarboxylic acid may be mentioned. Of these, succinic acid anhydride and 50 tetrahydrophthalic acid anhydride are particularly preferred.

Here, for the acid dissociation constant, reference can be made to Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (Brown, HC, et al.).
From the viewpoint of the storage stability of the photosensitive composition, oxalic acid, tetrahydrophthalic acid, phthalic acid, hexahydroxyphthalic acid, maleic acid, itaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. It is preferable to use dicarboxylic acid and its acid anhydride, trimellitic acid and its acid anhydride.

The selection of the carboxylic acid and its anhydride is appropriately adjusted according to the required properties of the photosensitive composition.
In the present invention, these polycarboxylic acids and acid anhydrides thereof may be used alone or in combination of two or more.
Moreover, the following compounds are mentioned as a compound which has the isocyanate group made to react after forming an ethylenically unsaturated group containing carbonyloxy group in the epoxy group containing compound represented by the said general formula (BV). It is done.

For example, organic monoisocyanates such as butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, 3-isopropenoyl-α, α-dimethylbenzyl isocyanate;
Aromatic diisocyanates such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate;
Aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate;
Cycloaliphatic diisocyanates such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω′-diisocyanate dimethylcyclohexane; xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate Aliphatic diisocyanates having aromatic rings such as
Lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), Triisocyanates such as tris (isocyanatephenyl) thiophosphate;
Furthermore, the trimer of the isocyanate compound mentioned above, a water adduct, these polyol adducts, etc. are mentioned.

Among these, diisocyanate di- or trimer and these polyol adducts are preferable, and trimethylolpropane adduct of tolylene diisocyanate, trimer of tolylene diisocyanate, and trimer of isophorone diisocyanate are most preferable. In addition, the said compound may be used individually by 1 type, or may use 2 or more types together.
The acid value of the compound represented by formula (BI) used in the present invention is preferably 30 to 150 mg-KOH / g, more preferably 40 to 100 mg-KOH / g. is there.

An example of a specific method for synthesizing the compound represented by formula (BI) used in the present invention is as follows.
For example, based on a conventionally known method described in JP-A-4-355450, an epoxy compound dissolved in an organic solvent and the ethylenically unsaturated group-containing carboxylic acid are mixed with a predetermined catalyst and a thermal polymerization inhibitor. The target compound can be synthesized by performing an addition reaction at a predetermined temperature in the coexistence, and then continuing the reaction by adding a polyvalent carboxylic acid or an anhydride thereof.

Here, examples of the organic solvent include methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate and the like.
Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; fourth catalysts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride. Secondary ammonium salts; Phosphorus compounds such as triphenylphosphine; and stibins such as triphenylstibine.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.
The ethylenically unsaturated group-containing carboxylic acid is usually 0.8 chemical equivalent to 1.5 chemical equivalents, preferably 0.9 chemical equivalents to 1.1 chemical equivalents per one chemical equivalent of the epoxy group of the epoxy compound. An equivalent amount is added.

The addition reaction between the bis (hydroxyphenyl) fluorene type epoxy compound and the ethylenically unsaturated group-containing carboxylic acid is usually performed at a temperature of 60 ° C to 150 ° C, preferably 80 ° C to 120 ° C.
In addition, the polyvalent carboxylic acid or its anhydride is usually 0.05 chemical equivalent to 1.0 chemical equivalent to 1 chemical equivalent of the hydroxyl group generated by the addition reaction of the epoxy compound and the ethylenically unsaturated group-containing carboxylic acid. It is added in an amount that will be equivalent, preferably 0.5 chemical equivalent.

In the present invention, the compound represented by the above general formula (BI) synthesized in this way is generally affected by the influence of the mixture contained in the raw material and thermal polymerization during the reaction of double bonds. Compounds other than the compound represented by formula (BI) may be included.
Examples of the specific ethylenically unsaturated compound used in the present invention include compounds represented by the following general formula (B-VI) in addition to the compounds represented by the above general formula (BI).

In said formula (B-VI), R < ¹² >, R <^13> , R < ¹⁴ > is synonymous with a formula (BI), respectively.
The method for producing the compound represented by the general formula (B-VI) is not particularly limited as long as the compound having the structure represented by the general formula (B-VI) is obtained.
For example, as in the case of the method for producing the compound represented by the general formula (BI) described above, diglycidyl ether is used as a raw material, and an ethylenically unsaturated group-containing carbonyloxy group is formed thereon. Examples thereof include a production method in which one or more compounds selected from a compound having a carboxylic acid and its anhydride and an isocyanate group are reacted.
In the photosensitive composition of the present invention, the specific ethylenically unsaturated compound having a double bond equivalent of 400 or less can be used alone or as a mixture of two or more.

(B-2) Ethylenically Unsaturated Group-Containing Resin The photosensitive composition of the present invention is (B-2) in addition to or instead of the specific ethylenically unsaturated compound of (B-1) described above. It may contain an ethylenically unsaturated group-containing resin (hereinafter sometimes simply referred to as a resin). As resin mix | blended, 1 type (s) or 2 or more types of resin which has at least 1 ethylenically unsaturated group can be used among resin used for the well-known liquid crystal display device.

  Examples of such resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Combined; acid-modified epoxy acrylate, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, and the like.

Among these, from the viewpoints of alkali developability and the like, carboxyl group-containing vinyl resins having an ethylenically unsaturated group in the side chain and relate are preferable.
Examples of the carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain include the following.
(B-2-1) Reaction product of carboxyl group-containing vinyl resin and epoxy group-containing unsaturated compound As the carboxyl group-containing vinyl resin used in the present invention, specifically, unsaturated carboxylic acid and vinyl Examples include copolymers with compounds.

  Here, 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. Examples of the vinyl compound include styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl. (Meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl ( (Meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meta Acrylonitrile, (meth) acrylamide, N- methylol (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N- dimethylaminoethyl (meth) acrylamide, vinyl acetate, and the like.

  Among the carboxyl group-containing vinyl resins, a (meth) acrylate- (meth) acrylic acid copolymer and a styrene- (meth) acrylate- (meth) acrylic acid copolymer are preferable. In the (meth) acrylate- (meth) acrylic acid copolymer, a copolymer composed of 5 to 80 mol% (meth) acrylate and 20 to 95 mol% (meth) acrylic acid is more preferable, A copolymer comprising 10 to 90 mol% of (meth) acrylate and 10 to 90 mol% of (meth) acrylic acid is particularly preferable.

  Moreover, in a styrene- (meth) acrylate- (meth) acrylic acid copolymer, styrene 3-60 mol%, (meth) acrylate 10-70 mol%, (meth) acrylic acid 10-60 mol%, A copolymer consisting of 5 to 50 mol% of styrene, 20 to 60 mol% of (meth) acrylate, and 15 to 55 mol% of (meth) acrylic acid is particularly preferable.

  In addition, the acid value of these carboxyl group-containing vinyl resins is adjusted according to the amount of the epoxy group-containing unsaturated compound to be reacted with these and the acid value required in the resulting reaction product, Usually, it is 50-500 mg-KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene of the carboxyl group-containing vinyl resin is preferably 1,000 to 300,000.

  Examples of the epoxy group-containing unsaturated compound include an aliphatic epoxy group-containing unsaturated compound and an alicyclic epoxy group-containing unsaturated compound. Examples of the aliphatic epoxy group-containing unsaturated compound include allyl glycidyl ether. Glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumarate monoalkyl monoglycidyl ester, maleic acid monoalkyl A monoglycidyl ester etc. are mentioned.

Examples of the alicyclic epoxy group-containing unsaturated compound include 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2. .1.0] dec-2-yl] oxymethyl (meth) acrylate and the like.
The carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound are generally an epoxy group-containing unsaturated compound in an amount of 5 to 90 mol%, preferably 30 to 70 mol%, based on the carboxyl group of the carboxyl group-containing vinyl resin. It is made to react by the ratio of%. The reaction can be carried out by a known method.
The acid value of the reaction product of the carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound is preferably 30 to 250 mg-KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1,000 to 300,000.

(B-2-2) Copolymer of compound having two or more unsaturated groups and unsaturated carboxylic acid or unsaturated carboxylic acid ester As the compound having two or more unsaturated groups, for example, Allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl (meth) acrylamide, vinyl (meth) ) Acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide and the like.

Examples of the unsaturated carboxylic acid or unsaturated carboxylic acid ester include (meth) acrylic acid or (meth) acrylic acid ester.
The proportion of the compound having two or more kinds of unsaturated groups in the entire copolymer is about 10 to 90 mol%, preferably about 30 to 80 mol%.
The acid value of the copolymer of a compound having two or more unsaturated groups and an unsaturated carboxylic acid or unsaturated carboxylic acid ester is preferably 30 to 250 mg-KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1,000 to 300,000.

<(C) Photopolymerization initiator>
(C) The photopolymerization initiator generates an active species such as a radical, an acid, or a base when the photosensitive composition is irradiated with actinic rays, and (B) an activity that leads to polymerization of the binder resin. A compound.
The photosensitive composition of the present invention comprises (C) a photopolymerization initiator as (C-1) a hexaarylbiimidazole represented by the following general formula (1-1) and / or the following general formula (1-2). The compound and (C-2) an acylphosphine oxide compound represented by the following general formula (2) are contained as essential components.

In said formula, R < ¹ > -R < ³ > is respectively independently a hydrogen atom, the C1-C4 alkyl group which may have a substituent, and the C1-C4 alkoxy group which may have a substituent. Or a halogen atom, and m, n and l each independently represent an integer of 0 to 5.
Examples of the alkyl group having 1 to 4 carbon atoms of R ^{1 to} R ³ include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and among them, a methyl group and an ethyl group are preferable. As the substituent that the alkyl group having 1 to 4 carbon atoms of R ^{1 to} R ³ may have, a monovalent non-metallic atomic group other than hydrogen is used. As a preferable example, a halogen atom (— F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, and an alkyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms of R ^{1 to} R ³ include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group, and among them, a methoxy group and an ethoxy group are preferable. Examples of the substituent that the alkoxy group having 1 to 4 carbon atoms of R ^{1 to} R ³ may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.
Examples of the halogen atom of R ^{1 to} R ³ include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom, and among them, a chlorine atom and a fluorine atom are preferable.

m represents an integer of 0 to 5, n represents an integer of 0 to 5, l represents an integer of 0 to 5, preferably m represents an integer of 1 to 2, n represents an integer of 1 to 2, and l represents It is an integer of 1-2.
(C-1) Examples of the hexaarylbiimidazole compound represented by formula (1-1) or formula (1-2) include 2,2′-bis (o-chlorophenyl) -4,5, 4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- Tora (o, p-dibromophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like. Among them, hexaphenylbiimidazole compounds are preferable, and those in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a methyl atom, a methoxy group, or a halogen atom are more preferable. A benzene ring bonded to the 4,4 ′, 5,5′-position on the imidazole ring is preferably unsubstituted or substituted with a halogen atom or a methoxy group.

  (C) As a photopolymerization initiator, either a hexaarylbiimidazole compound represented by the general formula (1-1) or a hexaarylbiimidazole compound represented by the general formula (1-2) may be used. Both may be used in combination. When used in combination, the ratio is not particularly limited. In addition, (C-1) used in the Example has a structure that satisfies the general formula (1-1).

In said formula, R < ⁴ > -R < ⁸ > is respectively independently a hydrogen atom, the C1-C4 alkyl group which may have a substituent, or the C1-C4 alkoxy which may have a substituent. R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group that may have a substituent, a phenyl group that may have a C 1-10 substituent, or carbon. The benzoyl group which may have a substituent of several 1-10 is represented.
Examples of the alkyl group having 1 to 4 carbon atoms of R ^{4 to} R ⁸ include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group, and among them, a methoxy group and an ethoxy group are preferable. Examples of the substituent that the alkyl group having 1 to 4 carbon atoms of R ^{4 to} R ⁸ may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.

Examples of the alkoxy group having 1 to 4 carbon atoms of R ^{4 to} R ⁸ include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group. Among them, a methoxy group and an ethoxy group are preferable. Examples of the substituent that the alkoxy group having 1 to 4 carbon atoms of R ^{4 to} R ⁸ may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.
Examples of R ⁹ include a linear or branched pentyl group, hexyl group, or the like or a phenyl group which may have a substituent in addition to the alkyl group having 1 to 4 carbon atoms. Examples of R ¹⁰ include the same alkyl group and phenyl group as R ^9, and a benzoyl group which may have a substituent. Examples of the substituent for the phenyl group or benzoyl group include the same groups as R ^{4 to} R ⁸ . If it illustrates concretely, the compound shown below can be mentioned, for example.

(In the above structural formula, Me represents a methyl group.)
Of the above compounds, bisacylphosphine oxide derivatives are preferred, more preferred are bisacylphenylphosphine oxide derivatives, and most preferred is an absorption region at a long wavelength when used in combination with a bisimidazole initiator (c- It is a compound shown in 1).

  If the photosensitive composition of this invention is a grade which does not impair the effect of this invention, other photoinitiators normally used in this field | area may further be used together as (C) photoinitiator. it can. Examples of such photopolymerization initiators include oxime photo radical initiators, triazine photo radical initiators, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, titanocenes, halogenated compounds. Examples include hydrocarbon derivatives, organoborates, onium salts, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, and the like.

  Examples of the oxime radical initiator include oxime ester compounds described in Japanese Patent Application Laid-Open No. 2000-80068 and Japanese Patent Application No. 2004-183593, among which acetophenone oxime-o-acetate, 1,2- Octanedione-1- [4- (phenylthio) -2- (o-benzoyloxime)], 1- [9-ethyl-6- (2-benzoyl) -9H-carbazol-3-yl] ethanone-1- ( (o-acetyloxime) and the like can be mentioned as preferable examples.

  As triazine photo radical initiators, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) Preferred examples include -s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine.

  Examples of acetophenones include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 1-hydroxy -1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-2-methylphenylpropanone, α-aminoacetophenone described later, and the like, Examples of benzophenones include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Michler's ketone, and the like. Examples of sibenzenes include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-benzylbenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4-di-t-butyl. Phenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like, and as thioxanthones, for example, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc., as anthraquinones, for example, 2-methylanthraquinone, etc., and as ketals, for example, benzyldimethyl ketal, etc. Can be mentioned.

  Examples of titanocenes include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), dicyclopentadienyl titanium bis (2, 6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadi Enyltitanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2 , 3,4,5,6-pentafluorophenyl) Dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like. Of these, titanium compounds having a dicyclopentadienyl structure and a bisphenyl structure are preferred, and those in which the o-position of the bisphenyl ring is substituted with a halogen atom are particularly preferred.

  Halogenated hydrocarbon derivatives include halomethylated s-triazine derivatives such as 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl)- s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis ( Trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s -Triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4 , 6-Bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl)- s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- And halomethylated s-triazine derivatives such as bis (tribromomethyl) -s-triazine, among which bis (trihalomethyl) -s-triazine Are preferred.

  Examples of the organoborates include, for example, organoboron ammonium complexes, organoboron phosphonium complexes, organoboron sulfonium complexes, organoboron oxosulfonium complexes, organoboron iodonium complexes, organoboron transition metal coordination complexes, etc. Examples of the organic boron anion include n-butyl-triphenyl boron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n -Butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (3-fluoro-4-methylphenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n-butyl-to (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion Alkyl-triphenyl boron anions such as n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) boron anion are preferred, and the counter cations include ammonium cation, phosphonium cation, sulfonium cation and iodonium cation. An onium compound such as tetraalkylammonium cation is particularly preferable.

  Examples of the onium salts include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate, dicyclohexyliodonium hexasulfonate. Iodonium salts such as fluoroarsenate, dicyclohexyliodonium tetrafluoroborate, dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfone Um p- toluenesulfonate, triphenylsulfonium camphorsulfonate, tri-cyclohexyl hexafluoroarsenate, tri-cyclohexyl sulfonium tetrafluoroborate, tri-cyclohexyl sulfonium p- toluenesulfonate, sulfonium salts such as tri-cyclohexyl sulfonium camphorsulfonate, and the like.

  Examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, bis (α-naphthylsulfonyl) methane, and bis (β- Bis (sulfonyl) methane compounds such as naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenylsulfonyl) ) Methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, phenylcal Carbonyl (sulfonyl) methane compounds such as bonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) Diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane compounds , Phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, phenyl Carbonyl (sulfonyl) diazomethane compounds such as carbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane Etc.

  Examples of the carbamic acid derivatives include benzoyl cyclohexyl carbamate, 2-nitrobenzyl cyclohexyl carbamate, 3,5-dimethoxybenzyl cyclohexyl carbamate, 3-nitrophenyl cyclohexyl carbamate, and the sulfonamide includes, for example, N-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide and the like, and triarylmethanols thereof include, for example, triphenylmethanol, tri (4-chlorophenyl) methanol, Each is listed.

<(D) Sensitizer>
The photosensitive composition of the present invention may contain (D) a sensitizer, and since the bond energy is small, bond cleavage is likely to occur, and a mercapto group that is liable to cause a hydrogen scavenging reaction or chain transfer. A compound having is preferred. Examples of the compound having a mercapto group include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline. , Β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and other mercapto group-containing compounds; hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol Tetrakisthiopropionate. Xanthodithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropio , Trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis (3-mercapto Butyrate), butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) Pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Functional thiol compounds can be mentioned, and various of these can be used alone or in combination of two or more. And from the viewpoint of the rectangularity of the pattern, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and the above hexaarylbiimidazole derivative, acylphosphine It is suitable to use in combination with a photopolymerization initiator system in the present invention. For example, as the sensitizer (D), 2-mercaptobenzothiazole may be used, 2-mercaptobenzothiazole may be used, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are used in combination. Also good. The photopolymerization initiator system in the present specification means a set of (C) photopolymerization initiator and (D) sensitizer, and (D) when no sensitizer is used ( C) Only a photoinitiator is meant.

<(E) Silane coupling agent>
In order to improve the adhesion to the substrate, the photosensitive composition of the present invention preferably contains (E) a silane coupling agent. Various types of silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used, preferably epoxy and imidazole silane coupling agents, more preferably imidazole (imidazole). A silane coupling agent having a group). A silane coupling agent containing an imidazole group is preferable from the viewpoint that curing at the substrate interface is promoted.

<(F) Other ingredients>
Unless the effect of this invention is impaired, the photosensitive composition of this invention may contain the following (F) other component. These may be contained alone or in combination of two or more.

(F-1) Thermal polymerization initiator The photosensitive composition of the present invention may contain (F-1) a thermal polymerization initiator. The thermal polymerization initiator that may be contained in the photosensitive composition of the present invention generates active species such as radicals when the photosensitive composition is heated, and the ethylenically unsaturated compound (B) binder resin. Is an active compound that leads to polymerization, and examples thereof include organic peroxides and azo compounds.

  Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, Isobutyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, etc. Diacyl peroxides, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide P-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,4,4-trimethylpentyl-2- Hydroperoxides such as hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) -bis (t-butylperoxyisopropyl) benzene Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, , 1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-to Peroxyketals such as methylcyclohexane, 2,2-bis (t-butylperoxy) butane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester, t-butylperoxyacetate, t-butyl peroxyoctoate, t-butyl peroxypivalate, t-butylperoxyneodecanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate Alkyl peresters such as di-t-butylperoxytrimethyladipate, t-butylperoxybenzoate, α-cumylperoxyneodecanoate, 2,4,4-trimethylpentylperoxyphenoxyacetate, di-2 -Ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxy Dicarbonate, diisopropylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylperoxyisopropylcarbonate And peroxycarbonates such as t-butyl peroxyallyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, acetylcyclohexylsulfonyl peroxydicarbonate, and the like.

  Examples of the azo compounds include 1,1′-azobiscyclohexane-1-carbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (methylisobutyrate), α, α'-azobis (isobutyronitrile), 4,4'-azobis (4-cyanovaleric acid), etc. Is mentioned.

(F-2) Epoxy Compound The photosensitive composition of the present invention may further contain an epoxy compound. In particular, when the photosensitive composition of the present invention is used for solder resist, overcoat, rib or spacer, it contains an epoxy compound for the purpose of improving the heat resistance and chemical resistance of the cured product. Preferably it is. As the epoxy compound, constituting a repeating unit of the epoxy resin, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and Examples include compounds ranging from low molecular weight substances to high molecular weight substances such as polyglycidylamine compounds obtained by reacting a polyamine compound and epichlorohydrin.

  Examples of the polyglycidyl ether compounds include diglycidyl ethers of alkylene glycols having 1 to 20 carbon atoms such as ethylene glycol, propylene glycol, butanediol, and hexanediol, and those having 2 to 50 carbon atoms such as polyethylene glycol and polypropylene glycol. Polyglycidyl ether of polyalkylene glycol, polyglycidyl ether of polyol such as glycerol, pentaerythritol, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, bisphenol Polyglycidyl ether, phenol novolak, cresol novolak, one molecule of compounds having aromatic hydroxyl groups such as A, bisphenol F, bisphenol S, and oligomers thereof Or polyglycidyl ethers of such compounds with a polyaddition structure of the cyclic hydrocarbon compounds and phenols having two or more unsaturated groups, and the like. These polyglycidyl ether compounds may be those in which a carboxyl group is introduced by reacting a remaining hydroxyl group with a polyvalent carboxylic acid or an anhydride thereof.

  Examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid and a diglycidyl ester type epoxy of phthalic acid, and examples of the polyglycidyl amine compound include bis ( 4-glycerylamine type epoxy of 4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like.

(F-3) Epoxy curing agent The photosensitive composition of the present invention may further contain an epoxy curing agent. The epoxy curing agent is preferably used in combination with an epoxy compound for the purpose of improving curability as a photosensitive composition. Examples of the epoxy curing agent include succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic acid. Anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3- Multivalent carboxylic acid anhydrides such as ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, trimellitic anhydride, biphenyltetracarboxylic anhydride, tributylphosphine, triphenylphosphine, Tris-2 -Organic phosphines such as cyanoethylphosphine, imidazole, 2-methyl Ruimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2- Imidazoles such as ethyl-4-methylimidazole, dicyandiamide, benzylmethylamine, 4-methylbenzyl-N, N-dimethylamine, 4-methoxybenzyl-N, N-dimethylamine, 4-dimethylaminobenzyl-N, N -Amine compounds such as dimethylamine, 2,4,6-triamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine, isocyanuric Acid adduct, 2,4-diamino-6-methacryloyloxyethyl- -Triazine, 2,4-diamino-6-methacryloyloxyethyl-amino-s-triazines such as s-triazine and isocyanuric acid adducts, quaternary ammonium salts such as benzyltributylammonium chloride, phenyltributylammonium chloride, tri- Examples thereof include phosphonium salts such as n-butyl-2,5-dihydroxyphenyl-phosphonium bromide and hexadecyltributylphosphonium chloride. Among these, those having an —NH— group are preferred, and amine compounds and amino-s -Triazines are preferred, with dicyandiamide and 2,4,6-triamino-s-triazine being particularly preferred.

(F-4) Amino Compound The photosensitive composition of the present invention may further contain an amino compound. An amino compound is preferably contained for the purpose of improving curability (curing speed of cured product, mechanical properties), adhesion to the substrate, and improving heat resistance and chemical resistance of the cured product. Examples of the amino compound include a methylol group as a functional group and an amino compound having at least two alkoxymethyl groups obtained by condensation condensation with an alcohol having 1 to 8 carbon atoms. For example, a melamine resin obtained by polycondensation of melamine and formaldehyde Benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde, glycoluril resin obtained by polycondensation of glycoluril and formaldehyde, urea resin obtained by polycondensation of urea and formaldehyde, melamine, benzoguanamine, glycoluril, urea, etc. Examples thereof include resins obtained by copolycondensation of two or more types with formaldehyde, and modified resins obtained by alcohol condensation modification of methylol groups of these resins. Among them, in the present invention, a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin of 80% or more is particularly preferable.

  As specific examples of amino compounds, as melamine resins and modified resins thereof, Mitsui Cytec “Cymel” (registered trademark) 300, 301, 303, 350, 36, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nikarak” (registered trademark) E-2151, MW-100LM, MX-750LM of Sanwa Chemical Co., Ltd. As benzoguanamine resins and modified resins thereof, “Cymel” (registered trademark) 1123, 1125, 1128, and as glycol uril resins and modified resins thereof, “Cymel” (registered trademark) 1170, 1171, 1174, 1172, And “Nicarak” (registered trademark) MX-270, As-containing resins and modified resins, Mitsui Cytec's "UFR" (registered trademark) 65,300, and "NIKALAC" (registered trademark) MX-290, include like.

(F-5) Polymerization accelerator The photosensitive composition of the present invention may contain a polymerization accelerator for the purpose of improving the polymerization initiation ability of the photosensitive composition. As the polymerization accelerator, an ester of an amino acid or a bipolar ion compound is preferable, and as the ester or bipolar ion compound of the amino acid, one represented by the following general formula (Xa) or (Xb) is preferable.

In the above formulas (Xa) and (Xb), R ³⁹ and R ⁴⁰ are each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent. , Represents an optionally substituted heterocyclic group, or a hydrogen atom, R ⁴¹ and R ⁴² each independently represents an optionally substituted alkyl group, or a hydrogen atom, R ⁴³ represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, and R ⁴⁴ has a substituent. An alkyl group that may be substituted, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, and s is an integer of 0 to 10.

Here, the alkyl groups represented by R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ in formulas (Xa) and (Xb) are those having 1 to 8 carbon atoms. Those having 1 to 4 carbon atoms are more preferable. Examples of the alkenyl group for R ⁴³ include a vinyl group, allyl group, and isopropenyl group. Examples of the aryl group for R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴⁴ include a phenyl group and naphthyl group. Examples of the heterocyclic group of R ³⁹ , R ⁴⁰ , and R ⁴⁴ include a furyl group, a furanyl group, a pyrrolyl group, and a pyridyl group.

  Examples of the substituent in the alkyl group and alkenyl group include an alkoxy group, an alkoxycarbonyl group, an alkenyloxy group, an alkenyloxycarbonyl group, a phenyl group, and a halogen atom. Examples of the substituent in the cyclic group include an alkyl group which may further have a substituent such as an alkoxy group or a phenyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an acyl group, an acyl group. And alkoxycarbonyl groups, phenoxy groups, alkylthio groups, alkylsulfonyl groups, aldehyde groups, carboxyl groups, hydroxyl groups, sulfo groups, nitro groups, cyano groups, halogen atoms, and the like.

In the present invention, one of R ³⁹ and R ⁴⁰ in the formula (Xa) among the ester of an amino acid represented by the above general formula (Xa) or (Xb) or a dipolar compound. Is a hydrogen atom and the other is an optionally substituted phenyl group, R ⁴¹ and R ⁴² are both hydrogen atoms, and R ⁴³ is an optionally substituted alkyl group, or a substituent. An amino acid ester in which s is 0, 1, or 2, or R ³⁹ and R ⁴⁰ in formula (Xb) are both hydrogen atoms, or Is an alkyl group which may have a substituent, R ⁴¹ and R ⁴² are both hydrogen atoms, and R ⁴⁴ has an alkyl group which may have a substituent, or a substituent. Preferred is an amino acid zwitterionic compound which is a good phenyl group and s is 0, 1, or 2. Ku, esters of the general formula (X-a) in s is 0, while the other is a phenyl group whose hydrogen atom R ³⁹ and R ^40, R ⁴¹ and R ⁴² is a both a hydrogen atom N- phenylglycine, wherein Among them, N-phenylglycine benzyl ester in which R ⁴³ is a benzyl group, or, in the general formula (Xb), s is 0, and all of R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴² are hydrogen atoms, A dipolar ionic compound of N-phenylglycine in which R ⁴⁴ is a phenyl group is particularly preferred.
In addition, in this invention, as a polymerization accelerator of (F-5) component, you may contain polymerization accelerators other than the ester of the said amino acid, or a bipolar ion compound.

(F-6) Inorganic filler The photosensitive composition of the present invention may contain an inorganic filler for the purpose of improving the strength as a cured product. Examples of the inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide and the like.

(F-7) Surfactant The photosensitive composition of the present invention may contain a surfactant for the purpose of improving coatability. As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.

  Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (Dainippon Ink & Chemicals), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 Nippon Unicar Co., Ltd.), FC4430 (Sumitomo 3M Co., Ltd.) and the like.

(F-8) Sensitizing dye The photosensitive composition of the present invention preferably contains a sensitizing dye for the purpose of improving the photosensitivity of the photosensitive composition. The sensitizing dye is a light-absorbing dye having an absorption maximum in a blue-violet region having a wavelength of 350 to 430 nm, and examples thereof include dialkylaminobenzene compounds, pyromethene compounds, and trihydroxypyrimidine derivatives. System compounds are preferred.

As the dialkylaminobenzene compound, in particular, a dialkylaminobenzophenone compound, a dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring, and on the benzene ring A dialkylaminobenzene compound having a substituent containing a sulfonylimino group at a carbon atom in the p-position with respect to the amino group and a dialkylaminobenzene compound having a carbostyryl skeleton are preferred.
As the dialkylaminobenzophenone-based compound, those represented by the following general formula (XI) are preferable.

In the above formula (XI), R ²³ , R ²⁴ , R ²⁷ and R ²⁸ each independently represents an alkyl group which may have a substituent, and R ²⁵ , R ²⁶ , R ²⁹ and R ³⁰ each independently represents an alkyl group which may have a substituent, or a hydrogen atom, and R ²³ and R ²⁴ , R ²³ and R ²⁵ , R ²⁴ and R ²⁶ , R ²⁷ and R ²⁸ , R ²⁷ and R ²⁹ , and R ²⁸ and R ³⁰ may each independently form a nitrogen-containing heterocyclic ring.

Here, the carbon number of the alkyl group of R ²³ , R ²⁴ , R ²⁷ , and R ²⁸ in formula (XI) and the carbon when R ²⁵ , R ²⁶ , R ²⁹ , and R ³⁰ are an alkyl group It is preferred that each number is independently 1-6. When forming a nitrogen-containing heterocyclic ring, it is preferably a 5- or 6- membered ring, and R ²³ and R ²⁵ , R ²⁴ and R ²⁶ , R ²⁷ and R ²⁹ , or R ²⁸ and R ³⁰ are 6-membered rings. It is preferable that R ²³ , R ²⁴ , R ²⁵ and R ²⁶ , and / or R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ form a julolidine ring. Particularly preferred. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred.
Specific examples of the compound represented by the general formula (XI) include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and compounds having the following structures. It is done.

  In addition, the heterocyclic group in the dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring includes a nitrogen atom, an oxygen atom, or a sulfur atom. Alternatively, a 6-membered ring is preferable, a 5-membered ring having a condensed benzene ring is particularly preferable, and a dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring Are preferably those represented by the following general formula (XII).

In the formula (XII), R ³¹ and R ³² each independently represents an alkyl group which may have a substituent, and R ³³ and R ³⁴ each independently have a substituent. R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³⁴ may be independently bonded to each other to form a nitrogen-containing heterocyclic ring. , X represents an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and the benzene ring condensed to the heterocyclic ring containing X may have a substituent.

Here, the number of carbon atoms of the alkyl group of R ³¹ and R ³² in formula (XII) and the number of carbon atoms when R ³³ and R ³⁴ are an alkyl group are preferably 1 to 6 each independently. . When R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³⁴ are independently bonded to each other to form a nitrogen-containing heterocyclic ring, it is preferably a 5- or 6-membered ring, and R ³¹ and R ³³ or R ³² and R ³⁴ preferably form a tetrahydroquinoline ring together with the benzene ring to which they are bonded, and R ³¹ , R ³² , R ³³ and R ³⁴ are bonded to each other. It is particularly preferable to form a julolidine ring together with the benzene ring. Further, R ³¹ and R ³³ or R ³² and R ³⁴ together with the benzene ring to which they are bonded form a tetrahydroquinoline ring having an alkyl group at the 2-position, or R ³¹ and R It is particularly preferable that ³² , R ³³ and R ³⁴ together with the benzene ring to which they are bonded form a julolidine ring containing a tetrahydroquinoline ring having an alkyl group at the 2-position. In addition, when X is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when it is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.

  Specific examples of the compound represented by the general formula (XII) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl). ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole, Beauty, include compounds having the following structure.

  Examples of the dialkylaminobenzene compound other than the compound represented by the general formula (XII) having a heterocyclic group as a substituent at a carbon atom at the p-position with respect to the amino group on the benzene ring include: 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) ) Pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-diethylaminophenyl) -1,3 , 4-thiadiazole and the like.

  The photosensitive composition of the present invention preferably has a maximum spectral sensitivity peak in the wavelength region of 350 to 430 nm, and more preferably has a maximum spectral sensitivity peak in the wavelength region of 390 to 430 nm. When having a maximum peak of spectral sensitivity in a wavelength range less than the above range, the sensitivity to laser light having a wavelength of 350 to 430 nm tends to be inferior as a photosensitive composition, whereas, when having in a wavelength range exceeding the above range. The safe light property under a yellow light tends to be inferior. The wavelength range of the maximum peak of these spectral sensitivities can be adjusted by appropriately selecting each component constituting the photosensitive composition, but in particular, depending on the type and content of the photopolymerization initiator and sensitizing dye, Can be adjusted.

  In the present invention, the maximum peak of spectral sensitivity is, for example, as described in detail in “Photopolymer Technology” (Akio Yamaoka, published by Nikkan Kogyo Shimbun, 1988, page 262), etc. Light spectrally divided from a light source such as a xenon lamp or a tungsten lamp using a photosensitivity image-forming material sample having a photocurable composition layer formed on the substrate surface is linearly exposed in the horizontal axis direction. In particular, the exposure intensity is set to change logarithmically in the vertical axis direction, and exposure is performed after irradiation, and then development processing is performed, whereby an image corresponding to the sensitivity of each exposure wavelength is obtained. The exposure energy capable of image formation is calculated from the above, and the maximum peak in the spectral sensitivity curve obtained by plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis is indicated.

(F-9) Coloring material When the photosensitive composition of the present invention is used for a color filter, a black matrix, or the like, it is preferable to contain a coloring material. Here, a coloring material means what colors the photosensitive composition which concerns on this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Moreover, when forming a black matrix using the photosensitive composition of this invention, a black coloring material can be used. The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, the average particle size is preferably 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). ), Safranin OK70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  Among these, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black. Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, manufactured by Degussa: Printex (registered trademark; the same applies hereinafter) .) 3, Printex3OP, Printex30, Printex30OP, Printex40, rintex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexL, PrintexG, PrintexP, PrintexU, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColorBlackFW1, ColorBlackFW2, ColorBlackFW2V, ColorBlackFW18, ColorBlackFW18, ColorBlackFW200, Color blackS160, ColorBlackS170, manufactured by Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, and Monarch 1400, Mon REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) 8, Colombia Yang Carbon Co., Ltd.: RAVEN (registered trademark. same as below. ) 11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040, Raven1020, Raven1040, Raven1040, Raven1040, Raven1040, Raven1040 RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000.

As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.
In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

These various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
The average particle size of these pigments is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less.

Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

(F-10) Pigment derivative A pigment derivative or the like may be added to improve the dispersibility and dispersion stability of the pigment. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable, among which quinophthalone is preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.

(F-11) Dispersant and / or dispersion aid When the photosensitive composition of the present invention is used for a color filter, a black matrix, or the like, particularly when a pigment is used as the above-mentioned color material. In order to improve the dispersibility and dispersion stability of the pigment, it is preferable to use a dispersant and / or a dispersion aid in combination. Among them, it is particularly preferable to use a polymer dispersant as the pigment dispersant because it is excellent in dispersion stability with time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (registered trademark, manufactured by BYK Chemie), and Disparon (registered trademark, Enomoto Kasei). SOLPERSE (registered trademark, manufactured by Zeneca Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. These dispersants can be used alone or in admixture of two or more.

(F-12) Other additives The photosensitive composition of the present invention further includes various additives such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol and the like. 2% by mass or less of the thermal polymerization inhibitor, 20% by mass or less of the colorant comprising an organic or inorganic dye / pigment, and the same plasticizer as dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, etc. 40% by mass or less, 10% by mass or less of a sensitivity characteristic improving agent such as tertiary amine or thiol, 30% by mass or less of a dye precursor, and 10% by mass or less of a silane coupling agent. May be.

[2] Component blending amount in photosensitive composition <(A) Photopolymerizable monomer>
The content of the photopolymerizable monomer (A) in the photosensitive composition of the present invention is usually 80% by mass or less, preferably 70% or less, and usually 20% by mass with respect to the total solid content in the photosensitive composition. As mentioned above, Preferably it is 30 mass% or more. The higher the monomer content, the greater the crosslink density and the better the compression shape. However, when the content of the polymerizable monomer is in the above range or more, the development solubility tends to deteriorate.

<(B) Binder resin>
(B) The blending ratio of (A) photopolymerizable monomer to binder resin is usually 10/1 to 1/10, preferably 5 as the value of (binder resin) / (photopolymerizable monomer) (mass ratio). / 1 to 1/5. The smaller the mass ratio, the greater the crosslink density and the better the compression shape. However, when the mass ratio exceeds the above range, the development solubility tends to deteriorate.

Moreover, it is preferable that content of (A) photopolymerizable monomer is 30 mass% or more with respect to the total content of (A) photopolymerizable monomer and (B) binder resin, and is 50 mass% or more. More preferably, the mass is usually 70% or less. By setting it to the lower limit value or more, the crosslinking density increases and the total deformation amount tends to decrease.
(B) When (B-1) specific ethylenically unsaturated compound is used as the binder resin, the content of (B-1) specific ethylenically unsaturated compound in the photosensitive composition of the present invention is photosensitive. It is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably 50% by mass with respect to the total solid content in the composition. It is below mass%. A higher content of the specific ethylenically unsaturated compound is preferable because the total deformation amount of the cured product described later can be increased. However, when the content exceeds the above range, the development solubility tends to deteriorate.

  (B) When (B-2) ethylenically unsaturated group-containing resin is used as the binder resin, the content of (B-2) ethylenically unsaturated group-containing resin in the photosensitive composition of the present invention is: It is 20 mass% or more normally with respect to the total solid in a photosensitive composition, Preferably it is 25 mass% or more, and is 70 mass% or less normally, Preferably it is 60 mass% or less. If the content of these resins is too much or too little, the developability, curability and mechanical properties of the cured product tend to be lowered.

<(C) Photopolymerization initiator>
(C) Content of a photoinitiator is 0.1 mass% or more normally with respect to the total solid in the photosensitive composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 0.00. It is 7 mass% or more, and is 30 mass% or less normally, Preferably it is 20 mass% or less, More preferably, it is 20 mass% or less. If the content of the photopolymerization initiator is too small, the sensitivity may be lowered. On the other hand, if the content is too large, the solubility of the unexposed portion in the developer may be lowered, leading to poor development.

  Further, (C-1) hexaarylbiimidazole compound represented by general formula (1-1) and general formula (1-2) and (C-2) acylphosphine oxide compound represented by general formula (2) The mass ratio C-2 / C-1 is 0.5 or more and 15 or less, preferably 1 or more and 10 or less, and more preferably 2 or more and 8 or less. If C-2 / C-1 is too small, surface hardening tends to be too large and tends to show a forward taper. If it is too large, light transmission is weakened due to light absorption of C-1 to the inside, and internal hardening is weakened. There is a tendency to show reverse taper.

  In addition, the content of the hexaarylbiimidazole compound represented by (C-1) general formula (1-1) and general formula (1-2) in the (C) photopolymerization initiator is 0.05 mass. % Or more, more preferably 0.75% by mass or more, further preferably 0.1% by mass or more, and preferably 10% by mass or less, preferably 5% by mass or less. More preferably, it is more preferably 2% by mass or less. If it is less than the lower limit value, the surface tends to be uncured, and if it exceeds the upper limit value, the inside tends to be uncured.

  Further, the content of the acylphosphine oxide compound represented by (C-2) general formula (2) in the (C) photopolymerization initiator is preferably 0.1% by mass or more, 0.5 More preferably, it is preferably at least 1% by mass, more preferably at least 10% by mass, preferably at most 10% by mass, more preferably at most 3% by mass. More preferably. If it is less than the lower limit value, it tends to be hardened, and if it exceeds the upper limit value, the inside tends to be hardened.

  In addition, when (C) another photopolymerization initiator is contained as the photopolymerization initiator, the content thereof in (C) the photopolymerization initiator is preferably 5% by mass or more, and 7% by mass. More preferably, it is more preferably 10% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 50% by mass or less. Further preferred. If the upper limit is exceeded, the effects of (C-1) and (C-2) tend to be inhibited.

  Moreover, as a compounding ratio of the photopolymerization initiator system to the ethylenically unsaturated compound described later, the value of (ethylenically unsaturated compound) / (photopolymerization initiator system) (mass ratio) is usually 1/1 to 100. / 1, preferably 2/1 to 50/1. If the blending ratio deviates from the above range, adhesion and curability may be lowered. The ethylenically unsaturated compound is a radically polymerizable compound that undergoes addition polymerization by the action of the above-mentioned photopolymerization initiator system when the photosensitive composition is irradiated with actinic rays, and may be crosslinked or cured in some cases. It means an alkali-soluble resin having at least one ethylenically unsaturated bond in the molecule.

<(D) Sensitizer>
(C) When using (D) sensitizer with a photoinitiator, content of a sensitizer is preferably 0.02 mass with respect to the total solid content in the photosensitive colored resin composition of the present invention. %, Usually 10% by mass or less, preferably 5% by mass or less, and the sensitizer is 0.1 to 50% by mass, particularly 0.1 to 40% by mass with respect to the photopolymerization initiator. It is preferable to use it.

  If the blending ratio of the photopolymerization initiator system component consisting of a photopolymerization initiator and a sensitizer is extremely low, the sensitivity to exposure light may be reduced. Solubility may be reduced, leading to poor development.

<(E) Silane coupling agent>
The content of the silane coupling agent is usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, based on the total solid content in the photosensitive composition.

<(F) Other ingredients>
(F-1) Thermally polymerizable initiator The content of the thermally polymerizable initiator is preferably 0.1 to 40% by mass, and preferably 0.2 to 20% by mass with respect to the total amount of the photosensitive composition. More preferably. When there are too few components, the curability as a photosensitive composition tends to be insufficient, and when there are too many components, background staining tends to occur during development.

(F-2) Epoxy Compound In the photosensitive composition of the present invention, the content ratio of the epoxy compound is preferably 1 to 70% by mass, and 5 to 50% by mass with respect to the total amount of the photosensitive composition. More preferably. If the amount is less than the above range, the curability as the photosensitive composition tends to be insufficient. On the other hand, if the range is exceeded, problems such as defective omission of non-image areas tend to occur during development.

(F-3) Epoxy Curing Agent In the photosensitive composition of the present invention, the content of the epoxy curing agent is 1 mass relative to the total amount of the photosensitive composition from the viewpoint of temporal stability as the photosensitive composition. % Or less is preferable, and 0.7% by mass or less is more preferable.

(F-4) Amino compound In the photosensitive composition of the present invention, the content ratio of the amino compound is usually 40% by mass or less and preferably 30% by mass or less with respect to the total amount of the photosensitive composition. The content is more preferably 20% by mass or less, and particularly preferably 10% by mass or less. Moreover, it is 0.5 mass% or more normally, and it is preferable that it is 1 mass% or more. If the content is too high, coloring and storage stability of the photosensitive composition may be deteriorated or pattern formability may be deteriorated. If the content is too low, the above-described curability and the effect of improving adhesion to the substrate can be obtained. There may not be. In particular, when the curing rate is expected, the content is usually 10% by mass or less, and preferably 5% by mass or less.

(F-5) Polymerization accelerator In the photosensitive composition of the present invention, the content ratio of the polymerization accelerator is preferably 20% by mass or less, and preferably 10% by mass or less based on the total amount of the photosensitive composition. Is more preferable.
(F-6) Inorganic filler The inorganic filler is preferably 70% by mass or less, and more preferably 50% by mass or less, based on the total amount of the photosensitive composition of the present invention.

(F-7) Surfactant When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, based on the total solid content in the photosensitive composition. More preferably, it is 0.01-0.5 mass%, Most preferably, it is 0.03-0.3 mass%. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case.

(F-8) Sensitizing dye In the photosensitive composition of the present invention, the content of the sensitizing dye is preferably 0.01 to 20% by mass relative to the total amount of the photosensitive composition. More preferably, it is 1-10 mass%. If it is less than the above range, the photocurability as the photosensitive composition tends to be insufficient, while if it exceeds the above range, background staining tends to occur during development.

(F-9) Coloring material The proportion of the coloring material in the total solid content of the photosensitive composition is usually selected in the range of 1 to 70% by mass when used for a color filter or a black matrix. be able to. In this range, 10 to 70% by mass is more preferable, and 20 to 60% by mass is particularly preferable. When the ratio of the color material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when the liquid crystal cell is formed. On the other hand, if the ratio of the color material is too large, sufficient image formability may not be obtained. On the other hand, when used as a spacer or the like, the proportion of the coloring material in the total solid content in the photosensitive composition is usually 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass. It is as follows.

(F-10) Pigment derivative The addition amount of the pigment derivative is usually 0.1 to 30% by mass, preferably 0.1 to 20% by mass or less, more preferably 0.1 to 10% by mass, further based on the pigment. Preferably it is 0.1-5 mass% or less.
(F-11) Dispersant and / or dispersion aid The content of the pigment dispersant is usually 50% by mass or less, preferably 30% by mass or less, in the solid content of the photosensitive coloring composition.

(F-12) Solid content The total solid content in the photosensitive composition of this invention is 10 mass% or more normally 80 mass% or less. Moreover, when using the photosensitive composition of this invention as a spacer use, in order to form a film thickness of 30-50 micrometers, 30-70 mass% is preferable for the total solid in a photosensitive composition, and film thickness 2 In order to form .about.30 .mu.m, the total solid content in the photosensitive composition is preferably 10 to 30% by mass.

[3] Manufacturing method of photosensitive composition Next, an example of the manufacturing method of the photosensitive composition of this invention is demonstrated.
First, necessary components as composition components are added and mixed to obtain a uniform solution. In the manufacturing process, fine dust is often mixed with the photosensitive solution. Therefore, the obtained photosensitive composition is preferably filtered with a filter or the like.

When the photosensitive composition of the present invention further contains a pigment as a coloring material, the coloring material is usually subjected to a dispersion treatment using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like in advance. Is preferred. Since the color material is finely divided by the dispersion treatment, the coating characteristics of the resist are improved.
In the dispersion treatment, the treatment is preferably carried out in a system in which a pigment and a solvent or an organic binder having a dispersion function, or the above-described pigment dispersant are further used in combination. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. Also, dispersion treatment with a solution in which all components to be blended as a photosensitive composition are mixed at the same time is not preferable because a highly reactive component may be denatured due to heat generated during dispersion.

  In the case of dispersing with a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to 8 mm are preferably used. The conditions for the dispersion are usually that the temperature is from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (coloring material, solvent, dispersant) and the size of the sand grinder. The standard of dispersion is to control the gloss of the ink so that the 20 ° gloss value of the photosensitive composition is in the range of 100 to 200. If the gloss of the photosensitive composition is low, the dispersion treatment is not sufficient and rough pigment particles often remain, which is insufficient in terms of developability, adhesion, resolution, and the like. Further, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

[4] Method for forming cured product A cured product can be obtained by curing the photosensitive composition of the present invention. The photosensitive composition of the present invention includes 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 and a coverlay film in organic electroluminescence, and various types of electrons. Forming cured products such as insulation coating layers of components, and forming cured products such as color filter pixels, black matrices, overcoats, ribs, and spacers used in image display devices such as liquid crystal displays and organic EL displays Although it can be used by a known method in each application, the case where it is used as a spacer will be described below.

(Use as spacer)
Usually, a photosensitive composition dissolved or dispersed in a solvent is supplied into a film or pattern by a method such as coating on a substrate on which a spacer is to be provided, and the solvent is dried and then supplied into a film. If necessary, pattern formation is performed by a method such as photolithography in which exposure and development are performed as necessary. Thereafter, if necessary, spacers are formed on the substrate by performing additional exposure or thermosetting treatment.

[4-1] Substrate The substrate on which the spacer is provided may be a metal plate itself such as copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, etc., but usually, for example, epoxy resin, polyimide Resin, bismaleimide resin, unsaturated polyester resin, phenolic resin, melamine resin and other thermosetting resins, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, Resin such as thermoplastic resin such as fluorine resin, paper, glass, inorganic substance such as alumina, silica, barium sulfate, calcium carbonate, or glass cloth base epoxy resin, glass nonwoven fabric base epoxy resin, paper base epoxy Composite materials such as resin, paper base phenolic resin, thermosetting resin sheet Etc., and the metal or the metal such as indium tin oxide, indium oxide, tin oxide, zinc oxide, indium zinc oxide, indium oxide doped tin oxide on the surface of the insulating support having a thickness of about 0.02 to 10 mm A metal-clad laminate in which a conductive layer having a thickness of about 1 to 100 μm is formed by heating, pressure laminating a metal foil such as an oxide, or sputtering, vapor deposition or plating of a metal is preferably used. . Also preferred are organic films such as polyimide on TFT arrays or other cured films.

[4-2] Solvent The solvent used to dissolve or disperse the photosensitive composition is sufficient if it has sufficient solubility or dispersibility with respect to the components used and gives good coating properties. Although there is no particular limitation, for example, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanol acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, 3-methoxy-1-butyl alcohol Propylene glycol solvents such as rupropylene glycol diacetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, Ester solvents such as methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketone solvents such as cyclohexanone, methyl amyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone And high polar solvents such as these, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons to these. The use ratio of the solvent is usually in the range of about 1 to 20 times by mass ratio with respect to the total amount of each component of the photosensitive composition.

[4-3] Supplying Method to Substrate The photosensitive composition of the present invention is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred. The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually in the range of 0.5 to 100 μm, preferably 1 to 80 μm, particularly preferably 1 to 50 m. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method or a printing method.

[4-4] Drying method Drying after supplying the photosensitive composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 130 ° C., preferably 50 to 110 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.

[4-5] Exposure Method Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive composition and irradiating an ultraviolet or visible light source through this mask pattern. Further, a scanning exposure method using a laser beam may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed in a deoxygenated atmosphere or on the photopolymerizable layer in order to prevent the sensitivity of the photopolymerizable layer from being reduced by oxygen. . The light source used for said exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[4-6] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and, if necessary, a surfactant, or an organic solvent. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), co The organic alkaline compound such emissions and the like. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
[4-7] Additional exposure and thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above-described exposure method, if necessary, or may be subjected to thermosetting treatment. It is particularly preferable to perform a thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. In the present invention, preferable treatment conditions for forming a cured product having mechanical properties include, for example, a heat curing treatment at 200 to 250 ° C., particularly 220 to 230 ° C., and 20 to 30 minutes.

[4-8] Physical Properties of Spacer A cured product obtained by curing the photosensitive composition of the present invention is useful as a spacer as described above, and can be particularly suitably used as a thick film spacer. The thickness of the thick spacer is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, further preferably 30 μm or more, and usually 60 μm or less.

  In the spacer formed using the cured product according to the present invention, the ratio (Top) / (Bottom) × 100% of the maximum width of the upper surface to the maximum width of the lower surface is preferably 70% or more, and 80% or more. More preferably, it is 90% or more, more preferably 130% or less, more preferably 120% or less, and further preferably 110% or less. There exists a tendency which can be made into a perpendicular | vertical shape by setting it as the said range.

Further, the spacer formed using the cured product according to the present invention preferably has an elastic recovery rate of 70% or more, more preferably 80% or more, further preferably 90% or more, usually 100% or less. There exists a tendency which can make it difficult to deform | transform by setting it as the said lower limit or more. The elastic recovery rate can be measured by a microcompression apparatus.
In addition, when the spacer according to the present invention is used as a photo spacer or column spacer for an image display device, it is preferable that the variation in thickness of each spacer is small, and the variation in the thickness of the spacer according to the present invention provided in the image display device is 10%. Or less, more preferably 7% or less, and even more preferably 5% or less. By setting it to the upper limit value or less, a liquid crystal layer having a uniform thickness tends to be formed.

  The spacer formed using the cured product according to the present invention preferably has a transmittance at a wavelength of 400 nm to 650 nm of 80% or more, more preferably 85% or more, and further preferably 90% or more. . When it is at least the lower limit value, the transmittance in the visible light region tends to be good. The transmittance can be measured with an ultraviolet-visible spectrophotometer.

[5] Use of the photosensitive composition of the present invention A cured product obtained by curing the photosensitive composition of the present invention is a printed wiring board, a liquid crystal display element, a plasma display, a large-scale integrated circuit, a thin transistor, a semiconductor package, Color filter pixels used in image display devices such as liquid crystal displays and organic EL displays as cured products such as color resists, solder resist films and coverlay films in organic electroluminescence, and insulating coating layers of various electronic components It is useful as a cured product of black matrix, overcoat, ribs and spacers.

  Hereinafter, the photosensitive composition of the present invention will be described with reference to specific examples for spacers, but the present invention is not limited to the following examples unless it exceeds the gist.

[1] Synthesis of (B-1) 4.86 parts by mass of succinic anhydride and 100 parts by mass of commercially available dipentaerythritol pentaacrylate were added in the presence of 0.524 parts by mass of triethylamine and 0.0339 parts by mass of hydroquinone. By reacting at 85 ° C. for 6 hours, a polyfunctional acrylate mixture having an acid value of 94 composed of a polyfunctional acrylate having one carboxyl group and two or more acryloyl groups in one molecule and pentaerythritol tetraacrylate (ethylenic non-functional). A saturated group-containing carboxylic acid mixture AA1) was obtained.

  Next, 9.11 parts by mass of 2,2-bis [4- (oxiranylmethoxy) phenyl] propane (epoxy equivalent 185), 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) 0. 573 parts by mass and propylene glycol monomethyl ether acetate were added, and after stirring for 30 minutes, 2.3 parts by mass of triphenylphosphine was added and reacted at 78 to 83 ° C.

  The solution having a transparent viscosity was heated and stirred for 6 hours until the acid value reached 2.0 KOH · mg / g to obtain a colorless and transparent reaction product. Subsequently, propylene glycol monomethyl ether acetate was added to the obtained reaction product and dissolved, and then 6.91 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride was added, and the mixture was added at 85 to 90 ° C. for 4 hours. By reacting, compound (B-1) was obtained. The obtained compound had a weight average molecular weight of 3,000.

[2] Preparation of photosensitive composition Examples were prepared by diluting with propylene glycol monomethyl ether acetate so that the solid content was 60% at the blending ratio (parts by mass) shown in Table 1, and stirring each component until uniform. And the photosensitive composition of a comparative example was mix | blended.
The following symbols were used in the table.

A-1: Pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate PE-4A)
B-2: Acrylic copolymer resin 0.93 mol of acrylic acid was added to a copolymer resin containing tricyclodecane methacrylate / styrene / glycidyl methacrylate (molar ratio 0.02 / 0.05 / 0.93) as a constituent monomer. A resin obtained by reacting and adding tetrahydrophthalic anhydride in a molar ratio of 0.1. (Weight average molecular weight 9,000 Solid content acid value (KOHmg / g) 24.3)
C-1: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-biimidazole (manufactured by Kurokin Kasei Co., Ltd.)
C-2: IRG819 (manufactured by BASF, compound of the following structural formula)

C-3: Irg369 (manufactured by BASF)
D-1: 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-1: F559 (made by DIC)
E-2: Imidazolesilane (IM-1000 manufactured by Nikko Materials)

[3] Formation and Evaluation of Spacer A method for performance evaluation will be described below.
(Spacer formation)
A coating solution (said photosensitive composition) was applied onto the ITO film of a glass substrate having an ITO film formed on the surface using a spinner, and then heated and dried on a hot plate at 90 ° C. for 2 minutes to a thickness of 50 μm. The coating film was formed. A mask having a 20 μm opening (a circular opening having a diameter of 20 μm) is used for the obtained coating film, an exposure gap is 60 μm, an ultraviolet ray having an intensity at 365 nm of 64.8 mW / cm ² and an exposure amount of 400 mJ / It was exposed so as to be cm ^2. The ultraviolet irradiation at this time was performed under air. Next, spray development was performed with a 0.28% TMAH aqueous solution at 23 ° C. for twice the minimum development time, followed by washing with pure water for 1 minute. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions. By these operations, unnecessary portions were removed, and the substrate on which the spacer pattern was formed was cured by heating in an oven at 220 ° C. for 30 minutes to form a photospacer.

(Evaluation of spacer shape)
The shape of the spacer was observed from the side using an optical microscope and SEM (manufactured by Keyence Corporation). The side surface of the spacer is observed in a rectangular or trapezoidal shape, and the ratio of the length of the upper base to the length of the lower base (Top / Bottom) × 100% is shown in Table 1.
(Evaluation of spacer film slippage)
Using an optical microscope and SEM (manufactured by Keyence Corporation), the presence or absence of film reduction on the surface of the spacer was observed. The case where the upper surface was flat and uniform was evaluated as “◯”, the case where the upper surface was slightly rounded, “Δ”, and the case where the upper surface was arched as “X”.

(Evaluation of spacer compression performance)
The elastic recovery rate of the photospacer was measured using a Fischer scope H-100 (manufactured by Fischer Instruments).
Table 1 shows the elastic recovery rate when a load of 500 mN was applied using a planar indenter (100 μm × 100 μm) having a square cross section.

(Evaluation of spacer adhesion)
Using an optical microscope, the size of the minimum contact mask size of the spacer was observed. Table 1 shows the minimum adhesion mask size.

  In Examples 1 to 3 in which C-1 was used as a photopolymerization initiator satisfying the general formula (1-1) and C-2 was used as a photopolymerization initiator satisfying the general formula (2), the shape of the spacer was vertical. Thus, there is almost no film reduction on the surface, and compression characteristics and adhesion are good. On the other hand, in Comparative Example 1 in which the photopolymerization initiator is only C-1, photocuring does not occur and no spacer is obtained, and in Comparative Example 2 in which the photopolymerization initiator is only C-2, surface curing is not satisfactory. It is enough. Further, in Comparative Example 3 in which the photopolymerization initiator is used in combination with C-2 and C-3, the surface curing is insufficient, and also in Comparative Example in which the photopolymerization initiator is only C2 and the sensitizer D1 is used in combination. In No. 4, since internal hardening is inadequate, adhesiveness is getting worse.

  The transmittance | permeability was measured for the produced evaluation sample of Example 3 using the visible ultraviolet spectrophotometer. The measurement results are shown in FIG. As shown in FIG. 1, it was confirmed that the spacer had a very high transparency and exceeded 90% transmittance in the visible region.

  From the above results, it can be seen that by using the photopolymerization initiator of the present invention, it is possible to form a photosensitive composition having good shape, film sliding, compression and adhesion when the spacer is formed.

Claims (11)

A photosensitive composition containing (A) a photopolymerizable monomer, (B) a binder resin, and (C) a photopolymerization initiator, wherein (C-1) A hexaarylbiimidazole compound represented by the formula (1-1) and / or the following general formula (1-2), and (C-2) an acylphosphine oxide compound represented by the following general formula (2) A photosensitive composition characterized by the above.

(In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxy group having 1 to 4 carbon atoms. Represents a group or a halogen atom, and m, n and l each independently represents an integer of 0 to 5.)

(In formula, R < ⁴ > -R < ⁸ > is respectively independently a hydrogen atom, the C1-C4 alkyl group which may have a substituent, or the C1-C4 which may have a substituent. Represents an alkoxy group, and R ⁹ and R ¹⁰ each independently have an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group having 1 to 10 carbon atoms, or Represents a benzoyl group which may have a substituent having 1 to 10 carbon atoms.) The photosensitive composition according to claim 1, wherein the acylphosphine oxide compound represented by the general formula (2) is a compound represented by the following structural formula.

  (C-1) Content (mass%) of the hexaarylbiimidazole compound represented by the general formula (1-1) and the general formula (1-2) in the photopolymerization initiator (C-1) and (C -2) C-2 / C-1, which is a ratio to the content (% by mass) of the acylphosphine oxide compound represented by the general formula (2), is 0.5 or more and 15 or less. The photosensitive resin composition of Claim 1 or 2.   (D) The photosensitive composition of any one of Claims 1-3 containing the compound which has a mercapto group as a sensitizer.   The photosensitive composition according to claim 4, wherein the compound having a mercapto group is 2-mercaptobenzothiazole and / or 2-mercaptobenzimidazole.   (E) The silane coupling agent which has an imidazole group as a silane coupling agent is contained, The photosensitive composition of any one of Claims 1-5 characterized by the above-mentioned.   The content of the (A) photopolymerizable monomer is 40% by mass or more based on the total content of the (A) photopolymerizable monomer and the (B) binder resin. The photosensitive composition of any one of 6.   Hardened | cured material formed by hardening | curing the photosensitive composition of any one of Claims 1-7.   A spacer comprising the cured product according to claim 8.   An image display device comprising the cured product according to claim 8.   An image display device comprising the spacer according to claim 9.

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