JP2007199135A - Photosensitive composition, photosensitive composition for blue-violet laser, image-forming base material using the same, image-forming material and image-forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having high sensitivity to lamp exposure and to laser light, particularly ultraviolet to blue-violet laser light, and excellent in chemical resistance and adhesion to a substrate, which is particularly a photosensitive composition suitable for use as a solder resist or a dry film and for use in direct drawing particularly with ultraviolet to blue-violet laser light, an image-forming base material using the same, an image-forming material and an image-forming method. <P>SOLUTION: The photosensitive composition contains (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiation system and (C) an alkali-soluble resin, wherein the photopolymerization initiation system (B) contains (b1) an oxime initiator having a specific structure and (b2) a benzophenone compound containing a sulfur atom. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention includes a printed circuit board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, a photo spacer, a rib material, a protective film, a conductor circuit in an organic electroluminescence, an electrode processing substrate, etc. A photosensitive composition used for etching resist, plating resist, solder resist, dry film, coverlay, etc. for the formation of, especially for dry film and solder resist, and especially from ultraviolet to blue-violet laser light The present invention relates to a photosensitive composition suitable for use in direct drawing by an image forming apparatus, an image forming material using the same, an image forming material, and an image forming method.

Conventionally, for forming printed circuit boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, photo spacers, rib resists, organic electroluminescence, etc. A technique called lithography is widely used.
In the lithography method, usually, (1) a dry film resist material (a photosensitive composition coating solution is applied on a temporary support film and dried to form a photosensitive composition layer, and the surface of the photosensitive composition layer is coated). A photosensitive image-forming material produced by laminating an image-forming material covered with a film) on a substrate to be processed, or (2) applying a photosensitive composition coating solution directly onto the substrate to be processed and drying it. An image forming material prepared by forming a photosensitive composition layer and covering the surface of the photosensitive composition layer with a protective layer as necessary is used.

  Then, image formation is performed according to the following procedures (1) to (3). (1) Image exposure of the photosensitive composition layer on a to-be-processed substrate is carried out through the mask film in which the circuit and the electrode pattern were drawn. (2) The temporary support film or the protective layer is peeled off, and a resist image corresponding to the circuit pattern is formed by developing using a difference in solubility between the exposed portion and the unexposed portion in the developer. (3) Form the circuit or electrode pattern drawn on the mask film on the substrate by removing the resist image after etching, plating, or soldering the substrate to be processed using the resist image as a resist. .

On the other hand, in recent years, a laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using laser light as an exposure light source is not only productive, but also resolution and positional accuracy. As a result, the use of laser light has been actively studied in the lithography method.
By the way, various light sources from the ultraviolet to the infrared region are known as laser light. As laser light that can be used for image exposure, argon ions are used from the viewpoint of output, stability, photosensitive ability, cost, and the like. Lasers, helium neon lasers, YAG lasers, and semiconductor lasers that emit light in the visible to infrared region are the mainstays. For example, an argon ion laser having a wavelength of 488 nm and an FD-YAG laser having a wavelength of 532 nm were used. Lithography has already been put into practical use.

  However, the conventional photosensitive composition still cannot be said to have sufficient sensitivity in the direct drawing method using laser light. In addition, due to significant progress in laser technology in recent years, semiconductor lasers that can oscillate stably in the blue-violet region can be used, but the output is lower than other visible regions, etc. At present, the sensitivity, developability, and the like of the corresponding photosensitive composition have not reached a level at which they can be put into practical use not only in the direct drawing method but also in the lithography method.

  In order to improve the sensitivity of the photosensitive composition, the developability, and the durability of the image formed thereby, for example, an α, β-unsaturated monocarboxylic acid adduct of an epoxy resin can be used. A photosensitive composition containing an alkali-soluble modified epoxy acrylate resin to which a polyvalent carboxylic acid or an anhydride thereof is added, and the photosensitive composition is laminated on a substrate as a dry film resist material, Alternatively, an image forming method in which an image forming material for a photoresist formed by applying the composition coating liquid on a substrate and drying to form a photosensitive composition layer is exposed to a high-pressure mercury lamp, a visible laser, or an infrared laser and developed. Etc. are known. In addition, an alkali obtained by adding a polyvalent carboxylic acid or its anhydride to an α, β-unsaturated monocarboxylic acid adduct of a specific oxime compound and inorganic fine particles or epoxy resin for the purpose of improving sensitivity and resolution. A composition containing a soluble modified epoxy acrylate resin has been proposed (see, for example, Patent Documents 1 to 6). Further, for the purpose of improving surface curability (chemical resistance), a curable composition containing a compound having an oxime ester group and a benzophenone compound containing a sulfur atom is disclosed (Patent Document 7).

However, the photosensitive composition still leaves room for improvement in sensitivity and developability, and has insufficient heat resistance as a resist material to be obtained and adhesion to a substrate. In particular, the sensitivity of the photosensitive composition corresponding to the blue-violet semiconductor laser was insufficient. Furthermore, the problem of chemical resistance in the case of using the solder resist still has room for improvement, and it has not been sufficient for practical use.
JP-A-5-204150 JP 2000-147767 A JP 2001-228611 A JP 2002-105112 A JP 2002-107926 A JP 2003-280193 A JP 2005-182004 A

  The present invention has been made in view of the above-described prior art. Accordingly, the present invention is highly sensitive to laser light, particularly ultraviolet to blue-violet laser light as well as lamp exposure, and is also resistant to chemicals. And a photosensitive composition excellent in adhesion to a substrate, and particularly suitable for use as a solder resist or dry film, and particularly for direct drawing with ultraviolet to blue-violet laser light, It is another object of the present invention to provide an image forming material, an image forming material, and an image forming method using the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors, among oxime ester photopolymerization initiators having a specific structure (hereinafter sometimes referred to as “oxime initiators”), ultraviolet to blue. Those having high sensitivity to purple light have been found to be generally poorly soluble in solvents. Therefore, among the above oxime initiators, those which are hardly soluble are refined to have an average particle size smaller than that of the conventional oxime initiator. In addition, when these small-grain oxime initiators are further combined with a benzophenone compound having a sulfur atom, the photosensitive composition containing them is not only highly sensitive to ultraviolet to blue-violet laser light. The present inventors have found that the chemical resistance and the adhesion to the substrate are remarkably excellent. Further, among oxime initiators, those having high sensitivity to blue-violet light and being soluble in a solvent are found, and the photosensitive composition containing this is similarly combined with a benzophenone compound having a sulfur atom. As a result of coexistence, it was found that sensitivity, chemical resistance, and adhesion to the substrate were excellent. That is, this invention exists in the several invention shown below.
(1) A photosensitive composition containing (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiation system, and (C) an alkali-soluble resin, wherein (B) the photopolymerization initiation system is (b1 ) A photosensitive composition comprising a compound represented by the following general formula (1) or (2), and (b2) a benzophenone compound containing a sulfur atom.

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring together with R ¹ ′, and the linking group is an alkylene group having 1 to 10 carbon atoms that may have a substituent, — (CH═CH) _n —, — ( C [identical to] C) _n - or a combination thereof (n is an integer of 0 to 3), R ^2a are each optionally substituted alkanoyl group having 2 to 12 carbon atoms, 3 carbon 5 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 benzoyl group, C1-C20 heteroaryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 And R1 ′ represents an optional substituent containing an aromatic ring or a heteroaromatic ring.):

(In the formula, R ^1b is a phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms, each of which may be substituted. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number Represents an amino group having 0 to 20 or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1b forms a ring together with R 1 ′. The linking group may be a C 1-10 alkylene group which may have a substituent, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof ( n is an integer of 0 to 3), and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms. A phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyxycarbonylalkanoyl group having 3 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R1 ′ represents an aromatic ring or a heteroaromatic ring. Any optional substituents are included.)
(2) An image-forming material comprising a layer of the photosensitive composition as described in (1) above on a temporary support film.
(3) An image forming material, wherein the image forming material according to (2) is laminated on the substrate to be processed on the photosensitive composition layer side.
(4) An image forming method, wherein the photosensitive composition layer of the image forming material according to (3) is subjected to scanning exposure with a laser beam having a wavelength of 340 to 430 nm, and developed to reveal an image. .

  According to the present invention, it has high sensitivity to laser light, and is excellent in chemical resistance and adhesion to a substrate, particularly for solder resist or dry film, and direct drawing by ultraviolet to blue-violet laser light. It is possible to provide a photosensitive composition suitable for use in the present invention, and an image forming material, an image forming material, and an image forming method using the same.

The constituent features of the present invention described below are representative examples of embodiments of the present invention and are not specified in these contents.
[1] Photosensitive composition
The photosensitive composition of the present invention contains (A) an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiation system, and (C) an alkali-soluble resin as essential components, and (B ) It is essential that the photopolymerization initiation system contains (b1) an oxime initiator having a specific structure, and (b2) a benzophenone compound containing a sulfur atom.
Moreover, the photosensitive composition of this invention may contain the component other than the above further as needed.

  The constituent components of the photosensitive composition of the present invention are described in detail below. In the present invention, “(meth) acryl” means “acryl” and / or “methacryl”.

[1-1] (A) Ethylenically unsaturated group-containing compound
The ethylenically unsaturated group-containing compound of component (A) constituting the photosensitive composition of the present invention is a photopolymerization initiator of component (B) described later when the photosensitive composition is irradiated with actinic rays. Is a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule that undergoes addition polymerization by the action of a photopolymerization initiation system including

  The ethylenically unsaturated group-containing compound in the present invention may be a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and development of the exposed and non-exposed areas associated therewith. From the viewpoint that the difference in liquid solubility can be expanded, it is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group. Compounds are particularly preferred.

Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.
Examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylate compounds and poly Examples include urethane (meth) acrylates with isocyanate compounds, and epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds.

  Examples of the esters 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 reactants with aliphatic polyhydroxy compounds such as ethylene oxide adduct, propylene oxide adduct, diethanolamine, triethanolamine, etc. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylol pro Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane 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 hexa (meth) acrylate, and similar crotonates, Dipentae having a skeleton with multiple ring-opening additions of crotonate, maleate, itaconate, citraconate, and caprolactan Suritoru (meth) acrylate compound (e.g. Nippon Kayaku Co., Ltd. DPCA-30, DPCA-60, DPCA-120, etc.) and the like.

  Further, as the esters thereof, a reaction product of the unsaturated carboxylic acid as described above with an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adduct, specifically Are, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and unsaturated carboxylic acids such as those described above and tris ( Reaction products with heterocyclic polyhydroxy compounds such as 2-hydroxyethyl) isocyanurate, specifically, for example, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, etc. Also, unsaturated carboxylic acid and A reaction product of a polyvalent carboxylic acid and a polyhydroxy compound, specifically, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, a condensate of (meth) acrylic acid, maleic acid and diethylene glycol, Examples include condensates of (meth) acrylic acid, terephthalic acid, and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  The (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 formula (IVa) or (IVb). Those are preferred.

[In the formulas (IVa) and (IVb), R ⁵¹ represents a hydrogen atom or a methyl group, n is an integer of 1 to 25, and m is 1, 2, or 3. ]
Here, n is preferably 1 to 10, and particularly preferably 1 to 4, and specific examples thereof include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) Examples include acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

In addition, examples of the urethane (meth) acrylates include a reaction product of a hydroxy (meth) acrylate compound and a polyisocyanate compound.
As said hydroxy (meth) acrylate compound, the following are mentioned, for example.
Hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate,
Tetramethylolethane tri (meth) acrylate.
Examples of the polyisocyanate compound include the following.
Fatty acids such as hexamethylene diisocyanate, aliphatic polyisocyanates such as 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate Aromatic polyisocyanates such as cyclic polyisocyanate, 4,4′-diphenylmethane diisocyanate, tris (isocyanatephenyl) thiophosphate, and heterocyclic polyisocyanates such as isocyanurate.
Especially, as urethane (meth) acrylates, the compound which has 4 or more urethane bond [-NH-CO-O-] and 4 or more (meth) acryloyloxy group in 1 molecule is preferable. Examples of the compound include the following.

(I-1) A compound obtained by reacting a compound having 4 or more hydroxyl groups in one molecule with a diisocyanate compound.
Examples of the “compound having 4 or more hydroxyl groups in one molecule” include pentaerythritol and polyglycerin. Examples of the diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate.

(I-2) A compound obtained by reacting a compound having two or more hydroxyl groups in one molecule with a compound having three or more isocyanate groups in one molecule.
Examples of the compound having two or more hydroxyl groups in one molecule include ethylene glycol.
Examples of the compound having three or more isocyanate groups in one molecule include the following.
“Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, and the like “Duranate P-301-75E”, “A” Adduct types such as “Duranate E-402-90T” and “Duranate E-405-80T”.

(I-3) A compound having 4 or more, preferably 6 or more isocyanate groups in one molecule. For example, the compound obtained by superposing | polymerizing or copolymerizing isocyanate ethyl (meth) acrylate etc. is mentioned.
More specifically, for example, “Duranate ME20-100” (i) manufactured by Asahi Kasei Kogyo Co., Ltd. and one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule. It can be obtained by reacting the compound (ii) having it.
Examples of (ii) include pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  Here, the weight average molecular weight of the compound (i) is preferably 500 to 200,000, and particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is preferably 600 to 150,000. Further, it preferably has 6 or more urethane bonds, particularly preferably 8 or more, more preferably 6 or more (meth) acryloyloxy groups, and particularly preferably 8 or more.

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

  In the present invention, among the urethane (meth) acrylates, those represented by the following general formula (V) are particularly preferable.

[In the formula (V), Ra represents a group having a repeating structure of an alkyleneoxy group or an aryleneoxy group and 4 to 20 oxy groups capable of bonding to Rb, and Rb and Rc are each independently carbon. An alkylene group having a number of 1 to 10, Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups, and Ra, Rb, Rc and Rd 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, as the repeating structure of the alkyleneoxy group of Ra in the formula (V), for example, those derived from propylenetriol, glycerin, pentaerythritol and the like, and as the repeating structure of the aryleneoxy group, for example, pyrogallol , 1,3,5-benzenetriol and the like. Moreover, it is preferable that the carbon number of the alkylene group of Rb and Rc is respectively independently 1-5, and it is preferable that the (meth) acryloyloxy group in Rd is 1-7. Further, x is preferably 4 to 15, y is 1 to 10, and z is 1 to 10.

  Furthermore, as Ra, the following formula [wherein, k is an integer of 2 to 10. And Rb and Rc are each independently a dimethylene group, a monomethyldimethylene group or a trimethylene group, and Rd is particularly preferably represented by the following formula: .

  Moreover, as the epoxy (meth) acrylates, specifically, for example, (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, (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) trimethylol Aliphatic polyepoxy compounds such as propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy Aromatic compounds such as brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ethers And a reaction product with a polyepoxy compound such as a heterocyclic polyepoxy compound such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

In addition to the above, other ethylenically unsaturated group-containing compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate. Thioether bond-containing compounds in which the ether bond of an ether bond-containing ethylenically unsaturated compound is sulfurized with phosphorous pentasulfide to convert it to a thioether bond to improve the crosslinking rate, and for example, Japanese Patent No. 3164407 and The polyfunctional (meth) acrylate compound described in JP-A-9-100111 and the like, and silica sol having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.), methyl ethyl ketone-dispersed organo Silica sol (manufactured by Nissan Chemical Co., Ltd.) MEK-ST "), methyl isobutyl ketone-dispersed organosilica sol (" MIBK-ST "manufactured by Nissan Chemical Co., Ltd.)] and the like] using an isocyanate group or a mercapto group-containing silane coupling agent. Examples thereof include compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding an unsaturated compound with a silica sol via a silane coupling agent.

The above ethylenically unsaturated compounds may be used alone or in combination of two or more. In the present invention, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferred as the ethylenically unsaturated compound of component (A) above, and ester (meth) is preferred. Acrylates are particularly preferred, and among their ester (meth) acrylates, they contain polyoxyalkylene groups such as polyethylene glycol, polypropylene glycol, or polyethylene oxide adducts of bisphenol A, and contain two or more (meth) acryloyloxy groups. Particularly preferred are ester (meth) acrylates.

[1-2] (B) Photopolymerization initiation system
It is essential that the photopolymerization initiation system of the component (B) constituting the photosensitive composition of the present invention contains (b1) an oxime initiator having a specific structure, and (b2) a benzophenone compound containing a sulfur atom. To do. In addition, other photopolymerization initiation system components can be used in combination as long as the objects and effects of the present invention are not impaired.

[1-2-1] (b1) Oxime Initiator Having Specific Structure (b1) The oxime initiator having a specific structure according to the present invention is a radical, when the photosensitive composition is irradiated with actinic rays. It is an active compound that generates an active species such as an acid or a base and brings the ethylenically unsaturated compound of the component (A) into polymerization.
When the oxime initiator having the specific structure (b1) according to the present invention is hardly soluble in a solvent, the average particle diameter is preferably 0.001 μm or more and 150 μm or less. Moreover, when using for an ultraviolet to blue-violet semiconductor laser, it is preferable to have an absorption maximum in a wavelength range of 340 to 430 nm.

[1-2-1-1] (b1) Structure of oxime initiator having a specific structure
The oxime initiator according to the photosensitive composition of the present invention is characterized by being represented by the following general formula (1) or (2).

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. 20 phenoxycarbonylalkyl groups, C1-C20 heteroaryloxycarbonylalkyl groups or heteroarylthioalkyl groups, C0-20
Or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring together with R1 ′, and each linking group may have a substituent. An alkylene group of 1 to 10,-(CH = CH) _n -,-(C≡C) _n -or a combination thereof (n is an integer of 0 to 3), and R ^2a may be substituted. Good C2-C12 alkanoyl group, C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 benzoyl group, C1-C20 heteroaryloyl group, carbon A C2-C10 alkoxycarbonyl group or a C7-20 phenoxycarbonyl group is shown, R1 'shows the arbitrary substituents containing an aromatic ring or a heteroaromatic ring. )

In general formula (1), R ^1a is preferably an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or a phenoxycarbonylalkyl having 8 to 20 carbon atoms. A group or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1a may form a ring together with R ¹ ′, and the linking group may have a substituent, each having 1 to 1 carbon atoms. 10 alkylene groups, — (CH═CH) _n —, — (C≡C) _n —, or a combination thereof (n is an integer of 0 to 3), and R ^2a has 2 carbon atoms that may be substituted. R12 'shows the arbitrary substituents containing an aromatic ring or a heteroaromatic ring.

(In the formula, R ^1b is a phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms, each of which may be substituted. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number Represents an amino group having 0 to 20 or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1b forms a ring together with R 1 ′. The linking group may be a C 1-10 alkylene group which may have a substituent, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof ( n is an integer of 0 to 3), and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms. A phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyxycarbonylalkanoyl group having 3 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R1 ′ represents an aromatic ring or a heteroaromatic ring. Any optional substituents are included.)

In general formula (2), Preferably, R ^<1b > shows a C1-C20 alkyl group, R ^<2b> is the C1-C20 heteroaryl group each substituted, C3-C3, respectively. 20 represents an alkoxycarbonylalkanoyl group, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R1 ′ represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

  Among the oxime ester compounds represented by the general formula (1) or (2), preferred compounds are those represented by the general formula (3) or (4).

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded together to form a divalent or trivalent linking group, linking groups each substituent alkylene group having 1 to 10 carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( Is an integer of 0 to 3), R ^2a are each optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, 7 carbon atoms Represents a benzoyl group having 20 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, and 1 to 1 carbon atoms 20 Heteroaryloyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxyoxycarbonylalkanoyl group, C2-C12 alkoxycarbonyl group or or phenoxycarbonyl group having a carbon number of ^{7~20, -OR 8, -SR 9,} -SOR 9, shows a -SO ₂ R ⁹ or -NR ¹⁰ R ^11,
And at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is —OR ⁸ , —SR ⁹ or —NR ^10.
R ¹¹ is shown. However, R ⁸ is a hydrogen atom, carbon atoms which may each be substituted 1-12
Alkyl group, alkanoyl group having 2 to 8 carbon atoms, alkenyl group having 3 to 12 carbon atoms, alkenoyl group having 3 to 20 carbon atoms, phenyl group having 6 to 20 carbon atoms, — (CH ₂ CH ₂ O) _m H (M
Represents an integer of 1 to 20), or a trialkylsilyl group having 3 to 15 carbon atoms, and R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or 2 to 8 carbon atoms. An alkanoyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a phenyl group having 6 to 20 carbon atoms or a trialkylsilyl group having 3 to 15 carbon atoms, R ¹⁰ and R ¹¹ Are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a carbon atom having 6 to 20 carbon atoms. Represents a phenyl group, R ^{3 to} R ⁷ may be bonded to each other and may form a ring structure together with R ¹ ; )

In general formula (3), R ^1a is preferably an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or a phenoxycarbonylalkyl having 8 to 20 carbon atoms. A group or an aminoalkyl group having 1 to 20 carbon atoms, and R
^1a may form a ring together with R ³ or R ⁷ , in which case R ¹ and R ³ or / and R ⁷ are bonded together to form a divalent or trivalent linking group, The groups each have an optionally substituted alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — (C
≡C) _n -or a combination thereof (n is an integer of 0 to 3), R ^2a represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 3 to 12 carbon atoms, or phenyl having 6 to 20 carbon atoms. group, heteroarylthio acryloyl group having 1 to 20 carbon atoms, indicates -SR ⁹ or -NR ¹⁰ R ^11, and at least one of ^{R 3, R 4, R 5} , R 6 and R ^7, -SR ⁹ or an -NR ¹⁰ R ^11. However, R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or a cyclohexane having 3 to 15 carbon atoms. An alkyl group or a phenyl group having 6 to 20 carbon atoms, wherein R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or a carbon number having 2 to 4 carbon atoms; hydroxyl alkyl group, an alkenyl group or a phenyl group having 6 to 20 carbon atoms having 3 to 5 carbon atoms, R ³
˜R ⁷ may be bonded to each other and may form a ring structure together with R ¹ .

(In the formula, R ^1b is a phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms, each of which may be substituted. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number A 0-20 amino group or a C1-C20 aminoalkyl group is shown, and R ^1b together with R ³ or R ⁷ In this case, R ^1b and R ³ or / and R ⁷ may be bonded to each other to form a divalent or trivalent linking group, and each of the linking groups has a substituent. A C1-C10 alkylene group,-(CH = CH) _n -,-(C
≡C) _n -or a combination thereof (n is an integer of 0 to 3), and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms or heteroarylalkanoyl having 1 to 20 carbon atoms. Group, a C3-C20 alkoxycarbonylalkanoyl group, a C8-C20 phenoxycarbonylalkanoyl group, a C3-C20 heteroaryloxyoxycarbonylalkanoyl group, or a C2-C10 aminocarbonyl group , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as in the general formula (3). )

In general formula (4), R ^1b is preferably an ^optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms. , A heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other
A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms,
An alkenoyl group having 3 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, -SR ⁹ or -NR ¹⁰ R ¹¹ , and R ³ , R ⁴ , R ^At least one of ⁵ , R ⁶ and R ⁷ represents —SR ⁹ or —NR ¹⁰ R ¹¹ . However, R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or a cyclohexane having 3 to 15 carbon atoms. An alkyl group or a phenyl group having 6 to 20 carbon atoms, wherein R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or a carbon number having 2 to 4 carbon atoms; A hydroxylalkyl group, an alkenyl group having 3 to 5 carbon atoms or a phenyl group having 6 to 20 carbon atoms), R ^{3 to} R ⁷ may be bonded to each other and may form a ring structure together with R ^1b .
Further preferred oxime ester compounds are compounds represented by any one of the following general formulas (5) to (7).

(In the formula, R ^1a and R ^2a have the same meaning as in the general formula (3), and R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁵ are each substituted with a hydrogen atom or a halogen atom. An alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group or benzoyl group having 7 to 20 carbon atoms, or —NR ¹⁰ R ¹¹ ; R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be bonded to each other to form a ring structure, L ¹ is a direct bond or a ketone group, and L ² is a sulfide bond or —N ( R ¹⁶ ) —, wherein R ¹⁶ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms. Alkenoyl group, C5-C8 cycloalkyl group, C6-C20 Phenyl group, C3-C20 heteroaryl group, C7-C20 benzyl group or C7-C12 benzoyl group, C2-C12 alkanoyl group, C3-C20 heteroarylloyl Group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxyoxycarbonylalkyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms or a phenoxycarbonyl group Represents a trialkylsilyl group having 3 to 15 carbon atoms or a hydroxylalkyl group having 2 to 4 carbon atoms, and is bonded to R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ to form a ring structure. May be.)

Preferably, R ^1a is an optionally substituted alkenyl group having 2 to 15 carbon atoms, a heteroarylalkyl group having 1 to 10 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or 8 to 20 carbon atoms. Phenoxycarbonylalkyl group, C1-C15 heteroarylthioalkyl group, C2-C12 dialkylamino group, C1-C15 dialkylaminoalkyl group, C3-C15 N-acyloxy-N An acylaminoalkyl group, or an alkylene group having 1 to 15 carbon atoms, which R ^1a and R ³ or / and R ⁷ may be bonded to each other and may have a substituent, — (CH═CH) _n -Or a combination thereof.

More preferably, the alkenyl group having 2 to 12 carbon atoms, the alkoxycarbonylalkyl group having 3 to 12 carbon atoms, the phenoxycarbonylalkyl group having 8 to 20 carbon atoms, and the heteroaryl having 1 to 10 carbon atoms, each of which may be substituted. A ruthioalkyl group, an amino group having 2 to 8 carbon atoms, or an alkylene group having 1 to 10 carbon atoms that R ^1a and R ³ or / and R ⁷ may be bonded to each other, This is a case where-(CH = CH) _n -or a combination thereof is formed. In addition, although n is an integer of 0-3 in the above, 1 or 2 is preferable.

Preferably, R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 12 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and a benzoyl group having 7 to 15 carbon atoms. , A heteroarylloyl group having 1 to 15 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms, a dialkylaminocarbonyl group having 3 to 12 carbon atoms, or phenyl having 7 to 15 carbon atoms An aminocarbonyl group is shown.

Preferably, R ³ , R ⁶ , R ⁷ and R ^{12 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkenyl groups, C2-C12 alkenoyl groups, C5-C8 cycloalkyl groups, C6-C12 phenyl groups, C3-C20 heteroaryl groups, C7-C12 Benzoyl group, C2-C12 alkanoyl group, C3-C20 heteroaryloyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 A heteroaryloxyxycarbonylalkanoyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, carbon A heteroaryloxyoxycarbonylalkyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, or —OR ⁸ or —NR ¹⁰ R ¹¹ , R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ may be bonded to each other and may form a ring structure together with R ^1a .

Preferably, R ¹⁶ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, and a cycloalkyl group having 5 to 8 carbon atoms. A phenyl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a benzyl group having 7 to 12 carbon atoms, a benzoyl group having 7 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, and a carbon number Heteroarylloyl group having 3 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxyoxycarbonylalkyl group having 3 to 20 carbon atoms, 2 to 12 carbon atoms An alkoxycarbonyl group or phenoxycarbonyl group, a trialkylsilyl group having 3 to 15 carbon atoms, or a hydroxylalkyl group having 2 to 4 carbon atoms. It is. Here, R < ³ >, R < ⁶ >, R < ⁷ >, R < ¹² > -R < ¹⁶ > may combine with each other and form a ring structure with R ^<1a> .

However, R ⁸ is a hydrogen atom, each optionally substituted alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, alkenoyl of 3 to 20 carbon atoms group, a phenyl group having 6 to 12 carbon _{atoms, - (CH 2 CH 2 O} ) m H (m is from 1 to 20
Or an alkyl group having 1 to 5 carbon atoms, preferably a trialkylsilyl group having 3 to 15 carbon atoms, and R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or 2 to 2 carbon atoms. 8 represents an alkanoyl group, an alkenyl group having 3 to 12 carbon atoms, or a phenyl group having 6 to 12 carbon atoms, wherein R ¹⁰ and R ¹¹ are each independently a hydrogen atom, and each optionally substituted 1 to 1 carbon atom. 12 represents an alkyl group having 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or a phenyl group having 6 to 20 carbon atoms.

(In the formula, R ^1b and R ^2b have the same ^{meanings as} in the general formula (4), and R ³ , R ⁶ , R ⁷ , R ¹²
To R ^{15, L 1,} and ^{L 2} have the same meanings as in the general formula (5). )
Preferably, R ^1b is an optionally substituted phenyl group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl group having 2 to 15 carbon atoms. A benzoyl group having 7 to 15 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms or a phenoxycarbonyl group having 7 to 12 carbon atoms, an amide group having 1 to 15 carbon atoms, a nitro group, and an alkenyl group having 2 to 15 carbon atoms , A C1-C10 heteroarylalkyl group, a C3-C20 alkoxycarbonylalkyl group, a C1-C15 heteroarylthioalkyl group, a C2-C12 dialkylamino group, a C1-C15 Or a dialkylaminoalkyl group having 3 to 15 carbon atoms, or R ^1a and R ³ or / and R ⁷ are This is a case where they are bonded to each other to form an alkylene group having 1 to 15 carbon atoms which may have a substituent, — (CH═CH) _n — or a combination thereof.

More preferably, each optionally substituted phenyl group having 6 to 15 carbon atoms, alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, carbon number 7-12 benzoyl group, C2-C12 alkoxycarbonyl group or C7-C12 phenoxycarbonyl group, C1-C10 amide group, nitro group, C2-C12 alkenyl group, carbon number An alkoxycarbonylalkyl group having 3 to 12 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroarylthioalkyl group having 1 to 10 carbon atoms, an amino group having 2 to 8 carbon atoms, R ^1b and R ³ or / And R ⁷ may be bonded to each other and each may have a substituent, a C 1-10 alkylene group, — (CH═CH) _n — or a combination thereof This is the case of forming a gutter. In the above, n is 0 to 0.
Although it is an integer of 3, 1 or 2 is preferable.

Preferably, R ^2b is an optionally substituted heteroaryl group having 1 to 15 carbon atoms, a heteroarylalkanoyl group having 1 to 15 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 15 carbon atoms, or 8 to 8 carbon atoms. A phenoxycarbonylalkanoyl group having 15 carbon atoms, a heteroaryloxycarbonylcarbonylalkanoyl group having 3 to 15 carbon atoms, and an aminocarbonyl group having 2 to 10 carbon atoms. Preferred ^{R 3, R 6, R 7} , R 12 ~R 15, L 1, and ^{L 2, R 3, R 6, R} 7 in the general formula ^{(5), R 12 ~R 15} , L 1, And the same preferable range of L ² .

(Wherein, R ^1a has the same meaning as in the general formula respectively (4), R ² represents an R ^2b in R ^2a and formula (4) in the above general formula (3), R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, or 6 to 20 carbon atoms. A phenyl group, a C 7-20 benzyl group or a benzoyl group, or —NR ¹⁰ R ¹¹ , R ³ , R ⁶ , R ⁷ , R ¹²
˜R ¹⁶ may be bonded to each other to form a ring structure, and at least one of R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁶ may be substituted. It includes at least one selected from the group consisting of a heteroarylalkyl group, a heteroarylalkanoyl group or a heteroaryloyl group, and a trialkylsilyl group having 3 to 15 carbon atoms. L ¹ and L ² have the same meaning as in the general formula (5). )

In the chemical formulas representing the oxime ester compound of the present invention, R ^1a , R ^1a , R ^2a , R ^2b , R ^{2 to} R ¹⁶ may each independently represent a fluorine atom,
Halogen atoms such as chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; cyano group; any organic group and the like. Examples of the arbitrary organic group include methyl group, ethyl group and n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group, n-heptyl group, n-octyl group, t-octyl group, etc. 18 linear or branched alkyl groups; C 3-18 cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group; 2 carbon atoms such as vinyl group, propenyl group, hexenyl group -18 linear or branched alkenyl group; cyclopentenyl group, cyclohexenyl group and other C3-C18 cycloalkenyl group; methoxy group, eth Si group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyloxy group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as oxy group and t-octyloxy group; methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t A linear or branched alkylthio group having 1 to 18 carbon atoms such as -butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, t-octylthio group; Aryl groups having 6 to 18 carbon atoms such as tolyl group, xylyl group and mesityl group; a 7 to 18 carbon atoms such as benzyl group and phenethyl group; Alkyl group; linear or branched alkenyloxy group having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group and hexenyloxy group; linear chain having 2 to 18 carbon atoms such as vinylthio group, propenylthio group and hexenylthio group Or a branched alkenylthio group; an acyl group represented by —COR ¹⁷ ; a carboxyl group; an acyloxy group represented by —OCOR ¹⁸ ; an amino group represented by —NR ¹⁹ R ²⁰ ; an acylamino represented by —NHCOR ^21. A carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; a carboxylic acid ester group represented by —COOR ²⁵ ; a sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; -SO ₃ sulfonic acid ester group represented by R ^28; 2-thienyl, 2-pyridyl group, a furyl group, an oxazolyl group, Benzokisazori Group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, a saturated or unsaturated heterocyclic group such as a tetrahydrothiophene dioxide group, and a trialkylsilyl group such as a trimethylsilyl group.

In addition, examples of the substituent of the present invention include a substituent such as ═N—OC (═O) R ² . As such compounds, R ^1a and R ^1b are substituted with ═N—OC (═O) R ² , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and 2 carbon atoms. It may be a -20 alkanoyl group, a benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, or an amide group having 1 to 20 carbon atoms.

  In the above, a plurality of substituents may be bonded to each other to form a ring, and the formed ring may be a saturated or unsaturated aromatic ring or heterocyclic ring, and each ring further has a substituent. And the substituent may further form a ring.

R ^{17 to} R ²⁸ each represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. These positional relationships are not particularly limited, and when they have a plurality of substituents, they may be the same or different.

  As mentioned above, although the compound shown by General formula (5)-(7) was explained in full detail, it is as follows when a preferable compound is put together in the combination of each substituent.

In General Formula (5), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, or carbon. R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded to each other to form 2 A valent or trivalent linking group, each of which may have a substituent, an alkylene group having 1 to 10 carbon atoms,-(CH = CH) _n -,-(C≡C
) _N- or a combination thereof (n is an integer of 0 to 3), R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 benzyl group or benzoyl group, or —NR ¹⁰ R ¹¹ , R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ may be bonded to each other to form a ring structure, and L ¹ is directly A compound which is a bond or a ketone group, and L ² is a sulfide bond or —N (R ¹⁶ ) —.

In General Formula (6), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted heteroarylalkanoyl group having 1 to 20 carbon atoms, An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ are A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, or benzoyl Group, or —NR ¹⁰ R ¹¹ , R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ may be bonded to each other to form a ring structure, and L ¹ is a direct bond or a ketone group , ^2, sulfide bond or -N (R ¹⁶⁾ -, compound.

In General Formula (7), R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or 8 to 8 carbon atoms. 20 phenoxycarbonylalkyl groups or aminoalkyl groups having 1 to 20 carbon atoms, or R ^1a may form a ring together with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded to each other to form a divalent or trivalent linking group, and each of the linking groups has an optionally substituted alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, -(C≡C) _n- , or a combination thereof (n is an integer of 0 to 3), and each R ² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, having 1 to 20 carbon atoms Heteroarylalkanoyl , Alkoxycarbonyl alkanoyl group having 3 to 20 carbon atoms or an aminocarbonyl group phenoxycarbonyl alkanoyl group or a C2-10 having 8 to 20 carbon ^{atoms, R 3, R 6, R} 7, R 12 ~R 15 is , A hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, or A benzoyl group, or —NR ¹⁰ R ¹¹ , R ³ , R ⁶ , R ⁷ , R ^{12 to} R ¹⁵ may be bonded to each other to form a ring structure, and R ³ , R ⁶ , R ⁷ , R ¹² in at least one of carbon atoms, which may each be substituted 1-20 of to R ¹⁵ heteroarylalkyl group, the heteroaryl alkanoyl group or heteroarylene acryloyl group and having 3 to 15 carbon atoms Comprises at least one selected from the group consisting of trialkyl silyl group, L ¹ is a direct bond or a ketone group, L ² is a sulfide bond or -N (R ¹⁶⁾ -, compound.

  In addition, a preferable oxime ester compound is a compound represented by the following general formula (8) or (9).

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring together with Ar ₁ , and each of the linking groups thereof may have a substituent, an alkylene group having 1 to 10 carbon atoms, — (CH═CH) _n —, — ( C≡C) _n — or a combination thereof (n is an integer of 0 to 3), R ^2a has the same meaning as in the general formula (1), and Ar ₁ may have a substituent. Represents an aromatic ring, a heteroaromatic ring, a condensed aromatic ring or a condensed heteroaromatic ring, and p represents an integer of 2 to 5.)

In the general formula (8), R ^1a is preferably an optionally substituted alkenyl group having 2 to 25 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or a phenoxycarbonylalkyl having 8 to 20 carbon atoms. Group or a C1-C20 aminoalkyl group is shown. Also, R ^1a may form a ring together with Ar _1, in which case, R ^1a and Ar ₁ is bonded together form a divalent or trivalent linking group each other, the linkage is respectively substituted An alkylene group having 1 to 10 carbon atoms which may have a group, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof (n is an integer of 0 to 3), R ^2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms.

(In the formula, R ^1b is a phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms, each of which may be substituted. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number 0-20 amino group, or an amino alkyl group having 1 to 20 carbon atoms, also R ^1b is, form a ring with Ar ₁ At best, the linkage is respectively substituent may number 1 to 10 alkylene carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( n is an integer of 0 to 3), R ^2b has the same meaning as in the general formula (2), and Ar ₁ is an aromatic ring, heteroaromatic ring, condensed aromatic ring or condensed ring which may have a substituent. Represents a heteroaromatic ring, and p represents an integer of 2 to 5.)

In the general formula (9), preferably, R ^1b is an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ^2b is an optionally substituted heteroaryl having 1 to 20 carbon atoms. Group, a C1-C20 heteroarylalkanoyl group, a C3-C20 alkoxycarbonylalkanoyl group, a C8-C20 phenoxycarbonylalkanoyl group, or a C2-C10 aminocarbonyl group.

Ar ₁ is a part necessary for the compound of the present invention to absorb light, and is 200 nm.
As described above, a compound having absorption at 200 to 500 nm, more preferably 250 to 500 nm is preferably used. Specifically, Ar ₁ is an aromatic ring composed of a benzene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, an indene ring and a condensed ring thereof, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, A thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazane ring, a triazole ring, a pyran ring, a thiadizole ring, an oxadiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a condensed ring thereof, Further examples include condensed rings composed of aromatic and heterocyclic rings such as acridine ring, phenanthridine ring, xanthene ring, carbazole ring, phenazine ring, phenothiazine ring, phenoxazine ring, and benzothiazole ring.

p corresponds to the number of substitutable hydrogen atoms present in Ar ₁ selected from the above aromatic ring, heteroaromatic ring, condensed aromatic ring or condensed heteroaromatic ring, and is usually 2 to 5, preferably 2 to
A range of 3 is selected.
Next, specific examples of preferred compounds of the present invention are shown below.

As described above, the oxime initiator according to the present invention includes a compound known per se, and can be appropriately used, for example, from the compounds described in Patent Documents 1 to 6 described above.
In addition, (b1) oxime initiator which comprises the photosensitive composition of this invention is 10-100 weight% with respect to the whole photoinitiator combined with the arbitrary photoinitiators mentioned later, Preferably it is 50-. It is contained at 100% by weight, more preferably 80-100% by weight. If the amount of the oxime initiator is too small, the sensitivity tends to decrease.

[1-2-1-2] (b1) Average particle diameter of an oxime initiator having a specific structure
The oxime initiator having the specific structure includes compounds known in Patent Documents 1 to 6. In the present invention, the oxime initiator has an average particle size of 0.001 μm or more, preferably 0.01 μm or more, 150 μm or less, preferably 50 μm or less, more preferably 10 μm or less, particularly preferably 5 μm or less, particularly preferably. Is 2 μm or less, the sensitivity of the photosensitive composition is remarkably improved. This is presumably because a sufficient amount of the oxime initiator was uniformly dispersed in the photosensitive composition, so that the light absorption efficiency was increased and the composition was uniformly exposed. Moreover, it is excellent also in the point which can suppress precipitation and crystallization of the oxime initiator over time of the photosensitive composition. That is, the range of the average particle size is premised on that the oxime initiator is hardly soluble in the solvent. This is because the oxime initiator having a particle size is not present in the composition when soluble. The “average particle size” defined in the present application means a weight average particle size or a number average particle size, and can be measured by a known measurement method. The definition of the average particle size in the present invention is based on the technical idea of atomizing the oxime initiator, and in the range of the average particle size, it is a measured value by either the weight average particle size or the number average particle size. Can also achieve the object of the present invention.
The lower limit of the average particle size of the oxime initiator is usually 0.001 μm, preferably 0.01 μm.

In the present invention, the method for adjusting the average particle size of the oxime initiator to 0.001 μm or more and 150 μm or less is not particularly limited. For example, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a picomill, It is preferable to sufficiently disperse using a homogenizer or the like. In the dispersion treatment, a coating liquid, an organic binder having a dispersion function, or a surfactant such as nonion, cation, or anion, or a polymer dispersant is appropriately used as described in JP-A-2005-128483. It is preferable to perform the treatment in a system used together. Among these, a sand grinder is preferable as the dispersion treatment.
As the dispersing beads, glass beads or zirconia beads having an average particle diameter of usually 0.1 to 8 mm, preferably 0.2 to 2 mm are used.
Moreover, dispersion temperature (air temperature) is 0-100 degreeC normally, Preferably, it is the range of room temperature-80 degreeC. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the dispersion solution and the size of the sand grinder.

[1-2-1-3] (b1) Wavelength range of the absorption maximum of the oxime initiator having a specific structure
When the oxime initiator constituting the photosensitive composition of the present invention is used for an ultraviolet to blue-violet semiconductor laser, it is 340 nm or more, preferably 345 nm or more, more preferably 350 nm or more, particularly preferably 355 nm or more, and 430 nm. Hereinafter, those having an absorption maximum in a wavelength region of preferably 415 nm or less are preferable. When the absorption maximum is too close to the long wavelength side, it becomes easier to be exposed to light under yellow light and the safe light property is lowered, or when the transparency of the photosensitive composition layer is increased so as not to be exposed under yellow light. Sensitivity decreases because it becomes difficult to absorb blue-violet laser light. If the absorption maximum is too close to the short wavelength side, the irradiated light energy cannot be used efficiently for the photopolymerization reaction, resulting in low sensitivity. Among the oxime initiators, those having the above-mentioned absorption maximum are generally poorly soluble in a solvent. For example, the above-mentioned (X-20), (X-22), (X-28), etc. Those having a phenyl group having a plurality of alkyl groups or alkyloxyl groups introduced as a substituent, or those having a phenyl group having a long-chain alkyl group or an alkoxy group introduced as a substituent, etc. are soluble. There is. Such an oxime initiator is preferable because it has excellent compatibility with the photosensitive composition and does not have a problem of crystal precipitation with time.
The absorption maximum of the oxime initiator can be easily determined by, for example, measuring a solution obtained by dissolving the photopolymerization initiator in a tetrahydrofuran solvent so as to have a concentration of about 10 ⁻⁵ mol with a normal ultraviolet or visible light absorption spectrum meter. Desired.

[1-2-2] (b2) A benzophenone compound containing a sulfur atom The (b2) benzophenone compound containing a sulfur atom according to the present invention not only acts as a photosensitizer, but also exhibits the oxime of (b1). In combination with an initiator, especially in solder resist applications, it has the effect of increasing chemical resistance in addition to improving sensitivity, resolution, and solubility (developability) of the non-image area of the photosensitive layer in the developer. Have.
Examples of the benzophenone compound containing a sulfur atom used in the present invention include 4-
A benzoyl diphenyl sulfide compound is mentioned. The benzene ring to which the 4-benzoyl group of this compound is bonded may be substituted with one or two substituents selected from a chlorine atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, and an ethoxy group. The benzene ring to which the benzoyl group is not bonded may be substituted with one substituent selected from a chlorine atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, and an ethoxy group. Specific examples of 4-benzoyldiphenyl sulfide compounds include 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide (Kayacure BMS manufactured by Nippon Kayaku Co., Ltd.), 4-benzoyl-4′-ethyldiphenyl sulfide, 4 -Benzoyl-4'-propyldiphenyl sulfide, 4-o-methylbenzoyl diphenyl sulfide, 4-p-methylbenzoyl diphenyl sulfide, 4-m-methylbenzoyl diphenyl sulfide, 4-m, m'-dimethylbenzoyl diphenyl sulfide, 4 -o-chlorobenzoyl diphenyl sulfide, 4-p-chlorobenzoyl diphenyl sulfide, 4-pt-butylbenzoyl diphenyl sulfide, 4-m-methoxybenzoyl diphenyl sulfide, and the like.
The benzophenone compound containing a sulfur atom can be used alone or in combination of two or more.

[1-2-3] (B) Optional component of photopolymerization initiation system
The photopolymerization initiation system of the component (B) constituting the photosensitive composition of the present invention can be used in combination with one or more other photopolymerization initiators, sensitizers and the like, if necessary.

[1-2-3-1] Other photopolymerization initiator Examples of the one or more other photopolymerization initiators include acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, Hexaarylbiimidazoles, titanocenes, halogenated hydrocarbon derivatives, organoborates, organic peroxides, onium salts, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, coating solvents Soluble oxime ester compounds and the like.
Examples of the 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 the xylbenzenes 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 hexaarylbiimidazoles include 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (o-chlorophenyl). -4,4 ', 5,5'-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'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5 Examples include 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 halogen atom are more preferable. It is particularly preferred that the benzene ring bonded to the ', 5,5'-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

Examples of the titanocenes include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadienyl titanium bis. (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,4)
6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl) , Di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadi And enyltitanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl]. Among these, a titanium compound having a dicyclopentadienyl structure and a biphenyl structure is preferable, and a compound in which the o-position of the biphenyl ring is substituted with a halogen atom is particularly preferable.

  Examples of the halogenated hydrocarbon derivatives include halomethylated s-triazine derivatives, such as 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloro). Methyl) -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, -Bis (trichloromethyl) -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 (trichloro) Methyl) -s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4 6-bis (trichloromethyl) -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 Halomethylated s-triazine derivatives such as -4,6-bis (tribromomethyl) -s-triazine, among others, bis (trihalomethyl) ) -S- triazine are preferred.

Examples of the organic borates include organic boron ammonium complexes, organic boron phosphonium complexes, organic boron sulfonium complexes, organic boron oxosulfonium complexes, organic boron iodonium complexes, and organic boron transition metal coordination complexes. 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 -Tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron Anions and alkyl-triphenyl boron anions such as n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion are preferred, and examples of counter cations include ammonium cation, phosphonium cation, sulfonium cation, Onium compounds such as iodonium cations are preferred, and organic ammonium cations such as tetraalkylammonium are particularly preferred.
Examples of the organic oxide include t-butylbenzoic acid peroxide ester, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.

  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. Hexafluoroarsenate, dicyclohexyliodonium tetrafluoroborate, icyclohexyl salt such as dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenyls Honiumu 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 -Naphtylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, bis (sulfonyl) methane compounds such as phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenyl) Sulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, phenyl Carbonyl (sulfonyl) methane compounds such as carbonyl (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, Carbonyl (sulfonyl) diazomethane such as nylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane Compounds and the like.

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 sulfonamides thereof. For example, N-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide and the like, and triarylmethanols thereof include, for example, triphenylmethanol, tri (4-chlorophenyl) methanol and the like. , Respectively.
Examples of the oxime ester compound include oxime ester compounds described in JP 2000-80068 A. Specifically, for example, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  Among the photopolymerization initiators that can be used in combination, in the present invention, α-aminoacetophenone derivatives as acetophenones are preferred, and those represented by the following general formula (VI) are particularly preferred.

[In the formula (VI), R ³² represents an alkyl group which may have a substituent, an allyl group which may have a substituent, or a phenyl group which may have a substituent; R ³³ represents an alkyl group which may have a substituent, or an allyl group which may have a substituent, and R ³⁴ and R ³⁵ may each independently have a substituent. A good alkyl group, an allyl group which may have a substituent, or a phenyl group which may have a substituent, wherein R ³⁴ and R ³⁵ are linked to each other, or R ³⁴ or R ³⁵ And R ³² or R ³³ may be linked to each other to form a cyclic structure, and the benzene ring may have a substituent. ]
Here, as the alkyl group of R ³² , R ³³ , R ³⁴ , and R ^{35 in} the general formula (VI), those having 1 to 15 carbon atoms, particularly 1 to 10 carbon atoms are preferable. Examples of the substituent in the alkyl group, allyl group, and phenyl group include an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acetoxyalkoxy group, an alkoxyalkoxy group, an alkylcarbonylalkyl group, an alkylthio group, a haloalkyl group, A phenyl group, a halogen atom, etc. are mentioned. Further, R ³⁴ and R ³⁵ are connected to each other, or R ³⁴ or R ³⁵ and R ³² or R ³³ are connected to each other, and the formed cyclic structure includes pyrrolidine, piperidine, piperazine, morpholine. Oxazolidine, pyridine and the like.

  In addition, examples of the substituent in the benzene ring include alkyl groups, hydroxy groups, alkoxy groups, allyloxy groups, phenoxy groups, benzoyl groups, silyloxy groups, mercapto groups, alkylthio groups, allylthio groups, cycloalkylthio groups, benzylthio groups, phenylthio groups, Examples include an alkylsulfonyl group, a phenylsulfonyl group, an alkylsulfinyl group, an alkylamino group, an allylamino group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, and a halogen atom, and the benzene ring forms a condensed ring. As the condensed ring, fluorenone, dibenzosuberone, indoline, quinoxaline, carbazole, phenazine, acridanone, benzodioxole, benzofuran, xanthene, xanthone, phenoxazine, Nzochiazoru, phenothiazines, and the like.

  Specific examples of the α-aminoacetophenone derivative represented by the general formula (VI) above include the following compounds when classified according to the basic skeleton of the compound and exemplified for each carbon number. Particularly preferred are R32 and R33 each independently a methyl group, an ethyl group, or a benzyl group, and R34 and R35 are each a methyl group or a morpholino group that is linked to each other to form a cyclic structure. And a compound in which the benzene ring is unsubstituted or has a methylthio group, a dimethylamino group, or a morpholino group as a substituent, particularly preferably a morpholino group only in the p-position.

  As propan-1-one classified into 3 carbon atoms of the basic skeleton of the general formula (VI), 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylphenyl) -propan-1-one 1-phenyl-2-dimethylamino-2-methyl-3- (4-methoxyphenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (3,4-dimethoxy Phenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylthiophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl- 3- (4-fluorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (2-chlorophenyl) -propan-1-one, 1-phenyl- -Dimethylamino-2-methyl-3- (4-chlorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-bromophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-benzoylphenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-benzyl-propan-1-one, 1,3 -Diphenyl-2-dimethylamino-2-benzyl-propan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-fluorophenyl) 2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-benzoylphenyl) -2-dimethylamino-2-benzyl-prop 1-one, 1- (4-methylthiophenyl) -2-morpholino-2-methyl-propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- ( 4-methylphenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-methoxyphenyl) -propan-1-one, 1- (4- Methylthiophenyl) -2-dimethylamino-2-methyl-3- (3,4-dimethoxyphenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-Fluorophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (2-chlorophenyl) -propan-1-one 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-chlorophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl -3- (4-bromophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-benzoylphenyl) -propan-1-one, , 3-bis (4-methylthiophenyl) -2-dimethylamino-2-methyl-propan-1-one, 1- (4-butylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane -1-one, 1- (4-cyclohexylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-benzylthiol Nyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-dimethylamino) Phenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (2-chloropentenyl) -propan-1-one 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane-1 -One, 1- (N-methylindoline-5-yl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (N-butylphenoxy) 2-yl) -2-morpholino-2-benzyl-- propan 1-one, and the like.

As butan-1-one classified into 4 carbon atoms of the basic skeleton of the general formula (VI), 1-phenyl-2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylphenyl) 2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,5-dimethyl-4 -Methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,4-dimethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3 , 4,5-trimethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-hydroxyphenyl) -2-dimethylamino-2-
Benzyl-butan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-allyloxyphenyl) -2-dimethyl Amino-2-benzyl-butan-1-one, 1- (4-ethoxycarbonylmethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (1,1,2- Trimethylpropyldimethylsilyloxy) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1 − (4-Chlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,4-dichlorophenyl) -2-dimethylamino-2-benzene Zyl-butan-1-one, 1- (3,4-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,5-dichlorophenyl) -2-dimethylamino-2- Benzyl-butan-1-one, 1- (4-bromophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-mercaptophenyl) -2-dimethylamino-2-benzyl- Butan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylthiophenyl) -2-dibutylamino-2-benzyl-butane 1-one, 1- (4-methylthiophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butan-1-one, 1- [4- (2-methoxyethylthio) Enyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-octylthiophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylsulfonylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (4-Methylphenylsulfonyl) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-benzenesulfonylphenyl) -2-dimethylamino-2-benzyl-butane-1 -One, 1- (4-methylsulfinylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-aminophenyl) -2-di Methylamino-2-benzyl-butan-1-one, 1- (4-methylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2- Dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-methylbenzyl) -butan-1-one, 1- (4-dimethylamino Phenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -butane-1 -One, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (1-chlorohexenylmethyl) -butan-1-one, 1- (4-dimethylamino Phenyl) -2-dimethylamino-2- (2-pinen-10-yl) -butan-1-one, 1- (4-dimethylamino-2-methylphenyl) -2-dimethylamino-2-benzyl-butane -1-one, 1- (4-dimethylamino-3-ethylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-diethylaminophenyl) -2-dimethylamino-2- Benzyl-butan-1-one, 1- (4-isopropylaminophenyl) -2-dimethylamino-2-butyl-butan-1-one, 1- [4- (2-methoxyethylamino) phenyl] -2- Dimethylamino-2-benzyl-butan-1-one, 1- [4- (3-methoxypropylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one 1- (4-acetylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (N-acetylmethylamino) phenyl] -2-dimethylamino-2-benzyl-butane -1-one, 1- [4- (N-acetyl-3-methoxypropylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-piperidinophenyl) − 2-Dimethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2- Dimethylamino-2- (3,4-dimethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-ethylbenzyl) -buta 1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2 -(4-Butylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-isobutylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) ) -2-Dimethylamino-2- (4-dodecylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-hydroxymethylbenzyl) -butane-1- ON, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-acetoxyethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl)- 2-dimethylamino-2- (4-methoxybenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-butoxybenzyl) -butan-1-one, -(4-morpholinophenyl) -2-dimethylamino-2- [4- (2-hydroxyethoxy) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [ 4- (2-methoxyethoxy) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- (2-methoxyethoxy) ethoxy) benzyl]- Butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- (2-methoxyethoxy) ethoxycarbonyl) benzyl] -butane- 1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- (2- (2-methoxyethoxy) ethoxycarbonyl) ethyl) benzyl] -butan-1-one, 1 -(4-morpholinophenyl) -2-dimethylamino-2- [4- (2-bromoethyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4 -(2-diethylaminoethyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-trifluoroacetate, 1- (4-morpholino Phenyl) -2-dimethylamino-2-benzyl-butan-1-one-dodecylbenzenesulfonate, 1- (4-morpholinophenyl) -2-dimethyl Amino-2-benzyl-butan-1-one-p-toluenesulfonate, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-camphorsulfonate, 1- (4-morpholino Phenyl) -2-diethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butan-1-one, 1- ( 4-morpholinophenyl) -2-butylmethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-isopropylbenzyl) -butane-1- ON, 1- (4-morpholinophenyl) -2-dibutylamino-2-benzyl-butan-1-one, 1- (4-morpholinopheny ) -2-Benzylmethylamino-2-benzyl-butan-1-one, 1- (3-chloro-4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4 -(2,6-dimethylmorpholin-4-yl) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,4-dimethyl-1,2,3,4-tetrahydroquinoxaline -6-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (N-butylcarbazol-3-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,3-benzodioxol-5-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,3-dihydrobenzofuran-5-yl) -2-dimethyl Amino-2 Benzyl-butan-1-one, 1- (xanthen-2-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,3-dihydro-2,3-dimethylbenzothiazole- 5-yl) -2-dimethylamino-2-benzyl-butan-1-one, 2- (2-dimethylamino-2-benzyl-butanoyl) -fluorenone, 2- (2-dimethylamino-2-benzyl-butanoyl) ) -Dibenzosuberone, 3,6-di (2-dimethylamino-2-benzyl-butanoyl) -9-butyl-carbazole and the like.

  As pentan-1-one classified into carbon number 5 of the basic skeleton of the general formula (VI), 1- (4-morpholinophenyl) -2-dimethylamino-2-allyl-pentan-1-one, 1- ( 4-morpholinophenyl) -2-dimethylamino-2-benzyl-pentan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (2-isopropylbenzyl) -pentan-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-isobutylbenzyl) -pentan-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4- Butoxybenzyl) -pentan-1-one and the like.

Furthermore, as penten-1-one, 1-phenyl-2-dimethylamino-2-methyl-4-penten-1-one, 1-phenyl-2-dimethylamino-2-ethyl-4-penten-1-one 1-phenyl-2-dimethylamino-2-benzyl-4-penten-1-one, 1-phenyl-2-morpholino-2-methyl-4-penten-1-one, 1-phenyl-2-morpholino- 2-Benzyl-4-penten-1-one, 1,2-diphenyl-2-morpholino-4-penten-1-one, 1- (4-methylphenyl) -2-morpholino-2-methyl-4-pentene -1-one, 1- (4-dodecylphenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-ethyl-4- Penten-1-one, 1- (4-methoxyphenyl) -2-dibutylamino-2-methyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-piperidino-2-ethyl-4 -Penten-1-one, 1- (4-methoxyphenyl) -2-oxazolidino-2-methyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-morpholino-2-ethyl-4 -Penten-1-one, 1- (4-methoxyphenyl) -2-morpholino-2-phenyl-4-penten-1-one, 1- (3,4-dimethoxyphenyl) -2-morpholino-2-ethyl -4-penten-1-one, 1- [4- (2-methoxyethoxy) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (2-methoxyethoxy) Feni ] -2-morpholino-2-ethyl-4-penten-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-Isopropyloxyphenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-butyloxyphenyl) -2-morpholino-2-ethyl-4-penten-1-one 1- [4- (2-allyloxyethoxy) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (2-allyloxyethoxy) phenyl] -2-morpholino 2-ethyl-4-penten-1-one, 1- (4-trimethylsilyloxyphenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-fluoropheny L) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4 -Fluorophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- ( 4-fluorophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one 1- (4-fluorophenyl) -2-morpholino-2-ethyl-5-methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-benzyl-4-pentene -1- ON, 1- (3,4-dichlorophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (3,5-dichloro-4-methoxyphenyl) -2-morpholino-2- Methyl-4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2- Ethyl-4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2-tert-butyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethylamino 2-methyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-methylthiophenyl) -2- Dimethylamino 2-phenyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-methylthiophenyl) -2- Piperidino-2-ethyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-methylthiophenyl) -2- Morpholino-2-ethyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-methylthiophenyl) ) -2-morpholino-2-phenyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-benzyl-4-penten-1-one, 1- (4-ethyl) Thiophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-isopropylthiophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4- Allylthiophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-methyl-4-pentene-1- ON, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-ethyl-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2- Morpholino-2-propyl-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-tert-butyl-4-penten-1-one, 1- [ 4 (2-Methoxycarbonylethylthio) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- (4-methylsulfonylphenyl) -2-dimethylamino-2-ethyl-4-pentene- 1-one, 1- (4-butylsulfinylphenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- [4- (4-methylphenylthio) phenyl] -2-morpholino- 2-ethyl-4-penten-1-one, 1- [4- (4-methylphenylsulfonyl) phenyl] -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- ( 4-chlorophenylthiophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2 Methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-dimethyl Amino-2-benzyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-methylphenylamino-2-ethyl-4-penten-1-one, 1- (4-dimethylaminophenyl) ) -2- (pyrrolidin-1-yl) -2-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-Dimethylaminophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-be Zyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2- (2,6-dimethylmorpholin-4-yl) -2-ethyl-4-penten-1-one, 1- (4 -Diethylaminophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- [4-bis (2-methoxyethyl) aminophenyl] -2-morpholino-2-methyl-4-pentene- 1-one, 1- (4-butylaminophenyl) -2-dibutylamino-2-methyl-4-penten-1-one, 1- (4-butylaminophenyl) -2-morpholino-2-methyl-4 -Penten-1-one, 1- (4-dibutylaminophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-diallylaminophenyl) -2-morpholino-2 Methyl-4-penten-1-one, 1- [4- (pyrrolidin-1-yl) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- (4-piperidinophenyl) ) -2-piperidino-2-methyl-4-penten-1-one, 1- [4- (piperazin-1-yl) phenyl] -2-dimethylamino-2-ethyl-4-penten-1-one, 1- [4- (4-Methylpiperazin-1-yl) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (N-methylpiperazin-1-yl) phenyl ] -2- (N-methylpiperazin-1-yl) -2-methyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-methyl-4-pentene-1 -One, 1- (4-morpholino Enyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-isopropyl-4-penten-1-one, 1- (4 -Morpholinophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-diethylamino-2-ethyl-4-penten-1-one, 1- ( 4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2-methyl-4- Penten-1-one, 1- (4-morpholinophenyl) -2-allylmethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-di Rylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl)- 2- (piperazin-1-yl) -2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- ( 4-morpholinophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-penten-1-one-dodecylbenzenesulfonate 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholin 2-benzyl-4-penten-1-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2-morpholin-2-methyl-4-penten-1-one, 1 -[4- (2,6-dimethylmorpholin-4-yl) phenyl] -2- (2,6-dimethylmorpholin-4-yl) -2-ethyl-4-penten-1-one, 1- (N -Butylindoline-5-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (1,4-dibutyl-1,2,3,4-tetrahydroquinoxalin-6-yl)- 2-morpholino-2-ethyl-4-penten-1-one, 1- (N-butylcarbazol-3-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (5 10-dibutyl-5,10-dihydrophena -6-yl) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (1,3-benzodioxol-5-yl) -2-morpholino-2-methyl-4 -Penten-1-one, 1- (benzofuran-3-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (benzofuran-6-yl) -2-morpholino-2-ethyl -4-penten-1-one, 1- (2,3-dihydrobenzofuran-5-yl) -2-morpholino-2-methyl-4-penten-1-one, 1- (N-methylphenothiazine-2- Yl) -2-dimethylamino-2-allyl-4-penten-1-one, 3,6-di (2-morpholino-2-methyl-4-pentenoyl) -carbazole, 2- (2-dimethylamino-2) -Allyl-4-pentenoy ) -Acridanone, 2- (2-morpholino-2-methyl-4-pentenoyl) -xanthone, 2- (4-morpholinobenzoyl) -2-ethyl-N-methyl-1,2,3,6-tetrahydropyridine, etc. Is mentioned.

  As hexane-1-one classified into carbon number 6 of the basic skeleton of the general formula (VI), 1- (4-methylthiophenyl) -2-morpholino-2-allyl-hexane-1-one, 1- (4 -Morpholinophenyl) -2-dimethylamino-2-benzyl-hexane-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-4,5,5-trimethyl-hexane-1- ON, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-butylbenzyl) -hexane-1-one, 1- (4-morpholinophenyl) -2-dioctylamino-2- (4 -Methylbenzyl) -hexane-1-one and the like.

Further, as hexen-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-hexen-1-one, 1- (4-dimethylaminophenyl) -2- Dimethylamino-2,4,5-trimethyl-4-hexen-1-one, 1-
(4-Dimethylaminophenyl) -2-morpholino-2-ethyl-4-hexen-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-hexene-
1-one etc. are mentioned.

1- (4-dimethylaminophenyl) -2-dimethylamino-2- [4- (2-methoxy) benzyl] as heptan-1-one classified into 7 carbon atoms of the basic skeleton of the general formula (VI) -Heptan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-heptan-1-one and the like.
Further, as hepta-1,6-diene, 4-benzoyl-4-dimethylamino-hepta-1,6-diene, 4- (4-methoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-methoxybenzoyl) -4-morpholino-hepta-1,6-diene, 4- (3,4-dimethoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4- Phenoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-fluorobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-fluorobenzoyl) -4- Morpholino-hepta-1,6-diene, 4- (4-methylthiobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-methylthiobenzoyl) -4 Morpholino-hepta-1,6-diene, 4- (4-dimethylaminobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-dimethylaminobenzoyl) -4-morpholino-hepta-1 , 6-diene, 4- (4-morpholinobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-morpholinobenzoyl) -4-morpholino-hepta-1,6-diene, etc. It is done.

As octan-1-one classified into 8 carbon atoms of the basic skeleton of the general formula (VI), 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-octane-1-one, 1- ( 4-morpholinophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -octan-1-one and the like.
In the photosensitive composition of the present invention, the content ratio of the other photopolymerization initiator is usually 0 to 90% by weight, preferably 0 to 50% by weight, more preferably 0 to 0% by weight with respect to the whole photopolymerization initiator. Contains 20% by weight.

[1-2-3-2] Other sensitizing dyes
The photosensitive composition of the present invention preferably contains a sensitizing dye component for the purpose of improving the sensitivity of the composition, and the sensitizing dye has an absorption maximum in the ultraviolet to blue-violet region having a wavelength of 340 to 430 nm. Among them, dialkylaminobenzene compounds are preferable, among which dialkylaminobenzene compounds, pyromethene compounds, trihydroxypyrimidine derivatives, and the like can be given.

The preferred dialkylaminobenzene compounds include, in particular, dialkylaminobenzophenone compounds, dialkylaminobenzene compounds 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 benzene rings. Dialkylaminobenzene compounds having a substituent containing a sulfonylimino group at the carbon atom in the p-position with respect to the amino group above, and dialkylaminobenzene compounds having a carbostyryl skeleton are preferred.

As the dialkylaminobenzophenone compound, those represented by the following general formula (VII) are preferable.

[In the formula (VII), R ⁶² , R ⁶³ , R ⁶⁶ and R ⁶⁷ each independently represents an alkyl group which may have a substituent, R ⁶⁴ , R ⁶⁵ , R ⁶⁸ , and R ⁶⁹ independently represents an alkyl group which may have a substituent, or a hydrogen atom, and R ⁶² and R ⁶³ , R ⁶² and R ⁶⁴ , R ⁶³ and R ⁶⁵ , R ⁶⁶ and R ⁶⁷ , R ⁶⁶ and R ⁶⁸ , and R ⁶⁷ and R ⁶⁹ may each independently form a nitrogen-containing heterocycle. ]
Here, the carbon number of the alkyl group of R ⁶² , R ⁶³ , R ⁶⁶ , and R ⁶⁷ in formula (VII), and
When R ⁶⁴ , R ⁶⁵ , R ⁶⁸ , and R ⁶⁹ are alkyl groups, the number of carbon atoms is preferably 1-6.

Further, when forming a nitrogen-containing heterocyclic ring, it is preferably a 5- or 6-membered ring, and R ⁶² and R ⁶⁴ , R ⁶³ and R ⁶⁵ , R ⁶⁶ and R ⁶⁸ , or R ⁶⁷ and R ⁶⁹ are 6-membered rings. It is preferable that R ⁶² and R ⁶³ and R ⁶⁴ and R ⁶⁵ , and / or R ⁶⁶ and R ⁶⁷ , R ⁶⁸ and R ⁶⁹ form a julolidine ring. Is 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 (VII) include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and compounds having the following structure. 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 compound represented by the following general formula (VIII) is preferable.

[In the formula (VIII), R ⁷⁰ and R ⁷¹ each independently represents an alkyl group which may have a substituent, and R ⁷² and R ⁷³ each independently have a substituent. R ⁷⁰ and R ⁷¹ , R ⁷⁰ and R ⁷² , and R ⁷¹ and R ⁷³ may each independently form a nitrogen-containing heterocyclic ring, , Oxygen atom, sulfur atom, dialkylmethylene group, imino group,
Or the benzene ring which shows an alkylimino group and is condensed to a heterocyclic ring may have a substituent. ]
Here, the number of carbon atoms of the alkyl group of R ⁷⁰ and R ⁷¹ in formula (VIII) and the number of carbon atoms when R ⁷² and R ⁷³ are an alkyl group are preferably 1 to 6, and when forming a nitrogen heterocycle is preferably a 5- or 6-membered ring, is preferably R ⁷⁰ and R ^72, R ⁷¹ and R ⁷³ form a tetrahydroquinoline ring of 6-membered ring, and R ⁷⁰ R ⁷¹ , R ⁷² and R ⁷³ particularly preferably form a julolidine ring. 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. In addition, when X is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when X is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.
That's right.

Specific examples of the compound represented by the general formula (VIII) 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, and And compounds having the following structure.

Examples of the dialkylaminobenzene compound other than the compound represented by the general formula (VIII) 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.

Further, as the dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom with respect to the amino group on the benzene ring, those represented by the following general formula (VI) are preferable.

[In the formula (IX), R ⁷⁴ and R ⁷⁵ each independently represents an optionally substituted alkyl group, and R ⁷⁶ and R ⁷⁷ each independently represent a substituent. It indicates also alkyl group, or a hydrogen atom, R ⁷⁴ and R ^76, R ⁷⁴ and R ^76, and each, independently of R ⁷⁵ and R ^77, may form a nitrogen-containing heterocycle, R ⁷⁸ Represents a monovalent group or a hydrogen atom, and R ⁷⁹ represents a monovalent group. ]
Here, the carbon number of the alkyl group of R ⁷⁴ and R ⁷⁵ in formula (IX) and the carbon number when R ⁷⁶ and R ⁷⁷ are an alkyl group are preferably 1 to 6, and When forming a nitrogen heterocycle, it is preferably a 5- or 6-membered ring, but R ⁷⁶ and R ⁷⁷ are preferably hydrogen atoms.

Examples of the monovalent group of R ⁷⁸ and R ⁷⁹ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkenyloxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, Aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino group, acylamino group, carbamate group, sulfonamido group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio Group, imino group, cyano group, heterocyclic group and the like. Of these, R ⁷⁸ is preferably a hydrogen atom, and R ⁷⁹ is preferably an aryl group.
Moreover, as a dialkylaminobenzene type compound which formed the carbostyryl skeleton, what is represented by the following general formula (X) is preferable.

[In the formula (X), R ⁸⁰ , R ⁸¹ and R ⁸⁴ each independently represents an alkyl group which may have a substituent, and R ⁸² and R ⁸³ each independently represents a substituent. An alkyl group which may have, or a hydrogen atom, R ⁸⁰ and R ⁸¹ , R ⁸⁰ and R ⁸² , and R ⁸¹ and R ⁸³ may each independently form a nitrogen-containing heterocycle; R ⁸⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ]
Here, the carbon number of the alkyl group of R ⁸⁰ , R ⁸¹ , and R ⁸⁴ in formula (X), and R ⁸² ,
R ^83, and the number of carbon atoms when R ⁸⁵ is an alkyl group is preferably from 1 to 6, also in the case of forming a nitrogen-containing heterocyclic ring, but is preferably in the range 5 or 6-membered ring, R ⁸² And R ⁸³ is preferably a hydrogen atom. R ⁸⁵ is preferably a phenyl group.

As the above-mentioned sensitizing dye, in the present invention, the dialkylaminobenzophenone compound represented by the general formula (VII) and the amino group on the benzene ring represented by the general formula (IX) are p −. A dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the carbon atom at the position or a dialkylaminobenzene compound having a carbostyril skeleton represented by the general formula (X) is particularly preferred.
In the photosensitive composition of the present invention, the content of the other sensitizing dye is usually 0 to 90% by weight, preferably 0 to 50% by weight, more preferably 0 to 20% by weight, based on the entire sensitizer. % Content.

[1-3] (C) Alkali-soluble resin
Examples of the alkali-soluble resin (C) constituting the photosensitive composition of the present invention include phenolic hydroxyl group-containing resins and carboxyl group-containing resins. For example, a phenolic resin such as a polyvinylphenol resin, a novolak resin, a resol resin, or the like, a carboxyl group-containing vinyl resin, or a carboxyl group-containing epoxy resin is preferable. Among these, a carboxyl group-containing vinyl resin or a carboxyl group-containing epoxy resin is preferable. Is more preferable. In particular, when the image-forming material coated with the photosensitive composition of the present invention is used as a single-layer image-forming material that does not use an overcoat, the reduction in sensitivity due to oxygen in the air is suppressed, and the heat resistance and chemical resistance are improved. For these purposes, a carboxyl group-containing epoxy resin is particularly preferred. Hereinafter, a carboxyl group-containing vinyl resin and a carboxyl group-containing epoxy resin as the preferred component (C) will be described in detail.

[1-3-1] Carboxyl group-containing vinyl resin
Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, -(Meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate, etc. And copolymers with other vinyl compounds. These carboxyl group-containing vinyl resins preferably have an acid value of 50 to 300 KOH · mg / g, and particularly preferably 100 to 250 KOH · mg / g. Moreover, it is preferable that the weight average molecular weight of polystyrene conversion is 10,000-200,000, and it is especially preferable that it is 20,000-100,000.

  Among these, the carboxyl group-containing vinyl resin contained in the photosensitive composition of the present invention includes structural repeating units derived from ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and styrenes. The copolymer is preferably a copolymer, and as the copolymer, 10 to 50% by weight, 15 to 50% by weight of structural repeating units derived from ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and styrenes, respectively. Preferably in a proportion of -80 wt% and 1-40 wt%, more preferably in a proportion of 15-50 wt%, 15-80 wt% and 1-15 wt%, respectively, It is particularly preferred to include 15 to 35 wt%, 30 to 80 wt%, and 5 to 15 wt%.

  Here, specific examples of the styrene monomer in the copolymer include α-substituted alkylstyrenes such as styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, and m-methyl. Nuclear substituted alkyl styrene such as styrene, p-methyl styrene, 2,5-dimethyl styrene, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, dihydroxy styrene, etc., nuclear substituted hydroxy styrene, p-chlorostyrene, p -Nuclear substituted halogenated styrenes such as bromostyrene and dibromostyrene, and the like. Specific examples of acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, n-butyl (meth) acrylate, i-butyl Le (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate. Here, the carbon number of (meth) acrylic acid is preferably an alkyl ester having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and glycidyl. Examples thereof include substituted alkyl esters such as (meth) acrylate, benzyl (meth) acrylate, aminoethyl (meth) acrylate, and N, N-dimethylaminoethyl (meth) acrylate.

  In addition, as the copolymer, in addition to the structural repeating unit derived from each monomer of the styrene monomer, (meth) acrylic acid ester monomer, and (meth) acrylic acid, For example, unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N- Derived from other copolymerizable monomers such as (meth) acrylic acid derivatives such as dimethyl (meth) acrylamide and N, N-dimethylaminoethyl (meth) acrylamide, and vinyl compounds such as vinyl acetate and vinyl chloride. A constitutional repeating unit may be contained. The content of constituent repeating units derived from these other monomers is preferably 10 mol% or less of the entire copolymer.

Other carboxyl group-containing vinyl resins include carboxyl group-containing vinyl resins having an ethylenically unsaturated bond in the side chain. Examples of the carboxyl group-containing vinyl resin include the following.
(I) A reaction product obtained by reacting a carboxyl group-containing polymer with an aliphatic epoxy group-containing unsaturated compound or an alicyclic epoxy group-containing unsaturated compound.
Examples of the aliphatic epoxy group-containing unsaturated compound include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, and monoalkyl monoitaconate. Examples include glycidyl ester, monoalkyl monoglycidyl fumarate, and monoalkyl monoglycidyl maleate.
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 proportion of the aliphatic epoxy group-containing unsaturated compound or alicyclic epoxy group-containing unsaturated compound to be reacted is usually 5 to 90 mol%, preferably 30 to 70, based on the carboxyl group of the carboxyl group-containing polymer. Mol%.
(Ii) A reaction product obtained by copolymerizing a compound having two or more unsaturated groups and an unsaturated carboxylic acid such as (meth) acrylic acid, or an unsaturated carboxylic acid ester.
Examples of the compound having two or more unsaturated groups include allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, and 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.
The ratio with which the unsaturated carboxylic acid is reacted is usually 10 to 90 mol%, preferably 30 to 80 mol%, based on the entire compound having an unsaturated group.

An acrylic resin having an ethylenic double bond in the side chain of the carboxyl group-containing vinyl resin is also preferable. By using such an acrylic resin, the photosensitive composition of the present invention is used as a colored resin composition for a color filter. When used, the photocurability is improved, so that the resolution of the color filter and the adhesion between the pixel and the substrate can be further improved.
As a method for introducing an ethylenic double bond into the side chain of an acrylic resin, for example, the method described in Japanese Patent Publication No. 50-34443, Japanese Patent Publication No. 50-34444, etc.,
(1) A method of reacting a carboxyl group of an acrylic resin with a compound having both a glycidyl group, an epoxycyclohexyl group, and a (meth) acryloyl group
(2) A method of reacting acrylic acid chloride or the like with the hydroxyl group of the acrylic resin
Etc.

  Specifically, an acrylic resin having a carboxyl group or a hydroxyl group is added to glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3, By reacting compounds such as 4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic acid chloride, and (meth) allyl chloride, an acrylic resin having an ethylenic double bond group in the side chain can be obtained. it can. Especially, what made the alicyclic epoxy compound like (3,4-epoxycyclohexyl) methyl (meth) acrylate react with acrylic resin which has a carboxyl group and a hydroxyl group is preferable.

[1-3-2] Carboxyl group-containing epoxy resin
Specifically, the unsaturated group- and carboxyl group-containing epoxy resin is formed, for example, by ring-opening addition of a carboxyl group of an α, β-unsaturated monocarboxylic acid to an epoxy group of a polyepoxy compound or an epoxy resin. An ethylenically unsaturated bond is added via an ester bond (—COO—), and an ester bond formed by reacting the resulting hydroxyl group with a carboxyl group of a polyvalent carboxylic acid or its anhydride. And the remaining carboxyl group added.

  Here, examples of the epoxy resin include those obtained by reaction addition of epichlorohydrin, epibromohydrin, hydroxymethyl epoxy, etc. to the phenol group of the phenolic hydroxyl group-containing resin with an alkali or an acid catalyst. Specific examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and trisphenol epoxy resin. Of these, phenol novolac epoxy resins, cresol novolac epoxy resins, biphenol fluorenediglycidyl ether and epoxy resins having repeating units thereof are particularly preferred.

  Examples of the α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and pentaerythritol tri (meth) acrylate anhydride. Acid adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (Meth) acrylate tetrahydrophthalic anhydride adduct, reaction product of (meth) acrylic acid and ε-caprolactone and the like, and (meth) acrylic acid is particularly preferable.

  Specific examples of the polyvalent carboxylic acid or anhydride thereof include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, and 4-methyltetrahydrophthalic acid. 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid Examples thereof include acids and anhydrides thereof, among which maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and tetrahydrophthalic anhydride is particularly preferable.

  Among the above, in the present invention, the epoxy resin is a phenol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, from the viewpoints of sensitivity, resolution, and adhesion to a substrate as a photosensitive composition. Cresol novolak epoxy resin, trisphenol novolak resin, bisphenol A novolak resin, polycondensation resin of triphenol and epichlorohydrin, biphenol fluorenediglycidyl ether and epoxy resin having its repeating unit, α, β-unsaturated It is particularly preferable that the monocarboxylic acid is (meth) acrylic acid and the polyvalent carboxylic acid or anhydride thereof is tetrahydrophthalic anhydride or succinic anhydride. Specifically, for example, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct is added to biphenol fluorene glycidyl ether and then tetrahydrophthalic anhydride is further subjected to ring-opening addition. “Pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct” has a structure in which a (meth) acrylate group is partially added.

Moreover, what has an acid value of 20-200 mg * KOH / g is preferable, and it is still more preferable that it is 30-180 mg * KOH / g. Moreover, the thing whose weight average molecular weights by a gel permeation chromatography are 2,000-200,000 is preferable, and it is still more preferable that it is 3,000-150,000.
The unsaturated group- and carboxyl group-containing epoxy resin in the present invention can be produced by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate. Next, tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, or quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride The reaction is carried out in the presence of a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or methyl hydroquinone in the presence of a catalyst such as a phosphorus compound such as triphenylphosphine or a stibine such as triphenylstibine. In the reaction, the α, β-unsaturated monocarboxylic acid is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to one chemical equivalent of the epoxy group of the epoxy resin. The addition reaction is usually carried out at a temperature of 60 to 150 ° C, preferably 80 to 120 ° C. Subsequently, the polyvalent carboxylic acid or its anhydride is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents per 1 chemical equivalent of the hydroxyl group produced in the reaction. In addition, it can be produced by a method such as continuing the reaction under the above conditions.

Specific examples of the structural repeating unit of the unsaturated group and carboxyl group-containing epoxy resin as the component (C) are shown below.

Furthermore, the unsaturated group and carboxyl group-containing epoxy resin as the component (C) is a urethane bond in order to impart flexibility to the resulting resist in applications where folding resistance is required, such as flexible wiring boards. Siloxane bonds or polyacrylonitrile-butadiene structures may be introduced.
As a method for introducing the urethane bond, for example, as described in JP-A No. 2003-155320, a polyfunctional isocyanate such as isophorone diisocyanate is reacted with an epoxy resin and an α, β-unsaturated monocarboxylic acid. The method of introduce | transducing the urethane bond obtained by making it react is mentioned. In addition, the compound obtained by the above method may further include a carboxylic acid having two hydroxyl groups in the molecule such as 2-dimethylolpropionic acid, an unsaturated group-containing carboxylic acid, or a unit price or a polyvalent compound. An acid anhydride may be reacted.
Examples of the resin into which the urethane bond is introduced include a urethane-modified resin of bisphenol A or bisphenol F. Specifically, "UXE3002" (acid value 100), "UXE3009" (acid value 60), etc. by Nippon Kayaku Co., Ltd. are mentioned.
Examples of the method for introducing the siloxane bond include a method in which the epoxy group of the epoxy resin also reacts with mono- or diaminosiloxane, mono- or dimercaptodimethylsiloxane, and the like. Further, the compound obtained by the above method may be further reacted with an unsaturated group-containing carboxylic acid, or a unit price or a polyhydric acid anhydride, if necessary.
Examples of the method for introducing the polyacrylonitrile-butadiene structure include a method in which an epoxy group of an epoxy resin is reacted with an acrylonitrile-butadiene copolymer having both ends modified with a carboxylic acid. Thereby, rubber characteristics can be imparted. Further, the compound obtained by the above method may be further reacted with an unsaturated group-containing carboxylic acid, or a unit price or a polyhydric acid anhydride, if necessary.

[1-3-3] Other preferred resins
Other preferable alkali-soluble resins as component (C) include polyvinylphenol resins, novolak resins and other phenolic hydroxyl group-containing resins.
Examples of the polyvinylphenol resin include p-hydroxy (α-methyl) styrene [where “(α-methyl) styrene” means “styrene” and / or “α-methylstyrene”. To do. And a copolymer of (α-methyl) styrene.

  Examples of the novolak resin and other phenolic hydroxyl group-containing resins include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4′-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4 -At least one of phenols such as benzenetriol, phloroglucinol, triphenolmethane, etc. under an alkali or acid catalyst, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propion Aldehydes such as aldehyde, benzaldehyde, furfural, etc., or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, epoxy compounds having a leaving group such as epichlorohydrin, epibromohydrin, hydroxymethyl epoxy, dicyclopentadiene And those obtained by polycondensation with at least one kind of unsaturated polycyclic hydrocarbons.

These phenolic hydroxyl group-containing resins preferably have a weight average molecular weight of 1,500 to 50,000.
In the present invention, the alkali-soluble resin as component (C) further contains an alkali-soluble resin other than the alkali-soluble resins described in [1-3-1] to [1-3-3]. As the alkali-soluble resin, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide and the like alone Or a copolymer, and a polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. Is preferred.

  Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and styrene. , Α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, Examples thereof include a copolymer with a vinyl compound such as vinyl acetate.

  Among these, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% of styrene, 10-70 mol% of (meth) acrylate, 10-60 mol% of (meth) acrylic acid. A copolymer consisting of 5 to 25 mol% of styrene, 20 to 60 mol% of (meth) acrylate, and 15 to 55 mol% of (meth) acrylic acid is particularly preferable. These carboxyl group-containing vinyl resins preferably have an acid value of 30 to 250 mg · KOH / g and a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000.

Furthermore, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are suitable. Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate is added to the carboxyl group-containing polymer. , Α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Group epoxy group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1. ] Dec-2-yl] oxymethyl (meth) acrylate-containing alicyclic epoxy group-containing unsaturated compound, 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer Reaction products obtained by reacting, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, Compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1- Propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) The ratio of the compound having two or more unsaturated groups such as chloramide and the unsaturated carboxylic acid such as (meth) acrylic acid or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned.

Further, as an alkali-soluble resin other than the unsaturated group and carboxyl group-containing epoxy resin, an acrylonitrile-butadiene copolymer resin in which both ends are modified with a carboxylic acid for applications such as flexible wiring boards that require folding resistance. And dimethylsiloxane resin whose both ends are epoxy-modified. Furthermore, for example, a hydroxyl group of a hydroxyl group-containing (meth) acrylate such as pentaerythritol triacrylate or a hydroxyl group of a phenol resin such as a phenol novolac resin and a number of isophorone diisocyanates described in JP-A-10-142791, etc. Examples thereof include a phenol resin into which a urethane bond obtained by reacting with a functional isocyanate is introduced.

In the photosensitive composition of the present invention, the ethylenically unsaturated compound of the component (A) is usually 1% by weight or more, preferably 5% by weight or more, based on the total amount of the photosensitive composition. It is usually 70% by weight or less, preferably 50% by weight or less.
The oxime initiator as the component (b1) is usually 0.001% by weight or more, preferably 0.01% by weight or more, and usually 50% by weight or less, preferably 20%, based on the total amount of the photosensitive composition. % By weight or less.
The benzophenone compound containing a sulfur atom as the component (b2) is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 20% by weight or less, preferably 10% by weight or less.
Each content ratio of the alkali-soluble resin of the component (C) is usually 5% by weight or more, preferably 10% by weight or more, and usually 70% by weight or less, preferably 50% by weight or less.
When there are too few each said components, it will become a tendency for the sensitivity as a composition, photocurability, etc. to be inferior. On the other hand, when there are too many said components, the tackiness as a composition becomes inadequate, or there exists a tendency for the problem that a background stain | pollution | contamination arises at the time of image development generate | occur | produces.

[1-4] Other ingredients
The photosensitive composition of the present invention may further contain the following components in addition to the components other than those described above.
[1-4-1] (D) Epoxy compound
In addition to the components (A) to (C), the photosensitive composition of the present invention further contains an epoxy compound as the component (D) for the purpose of improving the strength and heat resistance of the photocured film. preferable. As the epoxy compound, constituting a repeating unit of a so-called 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 A polyglycidylamine compound obtained by reacting a polyamine compound and epichlorohydrin, such as a compound ranging from a low molecular weight substance to a high molecular weight substance, is preferred.

  Examples of the epoxy compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and diglycidyl ether type epoxy of bis (3,5-dimethyl-4-hydroxyphenyl). , Diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide-added bisphenol A, and epoxy resin constituting these repeating units Polyglycidyl ether compounds such as diglycidyl ester type epoxy of hexahydrophthalic acid, diglycidyl ester type epoxy of phthalic acid, etc. Compounds, polyglycidylamine compounds such as diglycidylamine-type epoxy of bis (4-aminophenyl) methane, and epoxy resins that are precursors of carboxyl group-containing epoxy resins described in [1-3-2]. .

  Further, for example, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples thereof include oxetane derivatives such as 1,4-benzenecarboxylic acid bis [(3-ethyl-3-axetanyl) methyl] ester, phenol novolac oxetane, and cresol novolac oxetane.

In addition, a copolymer of a vinyl polymer having an epoxy group in the side chain and another vinyl compound that can be copolymerized may be used.
Examples of the vinyl polymer having an epoxy group in the side chain include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, Aliphatic epoxy group-containing unsaturated compounds such as itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2, Alicyclic epoxy group-containing unsaturated compounds such as 3-epoxycyclopentylmethyl (meth) acrylate and 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] oxymethyl (meth) acrylate And the like.
Examples of other copolymerizable vinyl compounds include styrene, α-methylstyrene, and dicyclopentanyl (meth) acrylate described in JP-A No. 2001-89533.

Moreover, a crystalline epoxy compound having a melting point of 50 ° C. or higher can be included as necessary for the purpose of further improving the strength of the photocured film, improving heat resistance, and the like.
The melting point of the crystalline epoxy compound is preferably 60 to 160 ° C, particularly preferably 70 to 150 ° C. The compound preferably has 9 to 30 carbon atoms, particularly preferably 10 to 25 carbon atoms, preferably 1 to 5 functional groups, and particularly preferably 2 to 3 functional groups.

Specific examples of such crystalline epoxy compounds include triglycidyl isocyanurate, which is a triglycidylamine-type epoxy compound obtained by reaction of isocyanuric acid and epichlorohydrin, and reaction of biphenol derivatives with epichlorohydrin. Examples of the resulting diglycidyl ether type epoxy include bixylenol diglycidyl ether, bixylenol full orange glycidyl ether, and biphenol full orange glycidyl ether.
Further, instead of or in combination with the above crystalline epoxy compound, a crystalline epoxy compound having a higher melting point can be used. Crystalline epoxy generally has advantages such as improved film strength, improved humidity resistance, and improved sensitivity over amorphous epoxy, but is easily melted due to heat generated by dispersion during dispersion. Accordingly, a crystalline epoxy having a melting point of usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 195 ° C. or higher is preferable because melting and dissolution during dispersion can be prevented.
Examples of such a high melting crystalline epoxy compound include tetraglycidyl xylyl ethane and tetraglycidyl phenylol ethane, which are tetraglycidyl ether type epoxies obtained by a reaction of a tetraphenol derivative and epichlorohydrin.

  In the photosensitive composition of the present invention, the content of the epoxy compound as the component (D) is preferably 0.5 to 70% by weight, and 2 to 50% by weight with respect to the total amount of the photosensitive composition. More preferably. If the content of the component (D) is too small, the strength of the resulting cured product tends to be insufficient. On the other hand, when there is too much content of (D) component, it will become the tendency for image formability to fall.

[1-4-2] (E) Amino compound
In addition to the components (A) to (C), the photosensitive composition of the present invention further comprises a methylol group as a functional group and carbon for the purpose of improving the heat resistance and chemical resistance of the resulting cured product. It is preferable to contain an amino compound (E) component having at least two alkoxymethyl groups modified with alcohol condensation of 1 to 8, and as these amino compounds, for example, a melamine resin obtained by polycondensation of melamine and formaldehyde, 2 such as 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, or urea. A resin obtained by copolycondensation of a seed or more and formaldehyde, and Modified resins of the methylol groups of these resins were alcohol condensation degeneration and the like.

Specifically, as a melamine resin and its modified resin, “Cymel” (registered trademark) 300, 301, 303, 340, 736, 738, 370, 771, 3 of Mitsui Cytec Co., Ltd.
25, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nikarak” (registered trademark) MW- from Sanwa Chemical Co., Ltd. 100LM (old product name is E-2151), MX-750LM, MX-302, and benzoguanamine resin and modified resins thereof, “Cymel” (registered trademark) 1123, 1125, 1128, and glycoluril resin and its As modified resins, “Cymel” (registered trademark) 1170, 1171, 1174, 1172, and “Nicalac” (registered trademark) MX-270, and as urea resin and modified resins thereof, “UFR” manufactured by Mitsui Cytec Co., Ltd. (Registered Trademark) 65, 300, “Nikarak” (Registered Trademark) MX-290, etc. That.

As these amino compound (E) components, in the present invention, melamine resins and modified resins thereof are preferable, modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins of 80% or more are particularly preferable. .
In the photosensitive composition of the present invention, the content ratio of the amino compound as the component (E) is preferably 0.1 to 20% by weight with respect to the total amount of the photosensitive composition, and preferably 0.5 to 10%. More preferably, it is% by weight.

[1-4-3] (F) Epoxy curing agent
In addition to the components (A) to (C), the photosensitive composition of the present invention further contains an epoxy curing agent (F) component for the purpose of improving the photocurability and thermosetting of the composition. As the epoxy curing agent of the component (F), for example, oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3 -Ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, Polycarboxylic acids such as trimellitic acid and biphenyltetracarboxylic acid and their anhydrides, tributylphosphine, triphenylphosphine , Organic phosphines such as tris-2-cyanoethylphosphine, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- (2- Cyanoethyl) -2-phenylimidazole, imidazoles such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, dicyandiamide, benzylmethylamine, 4-methylbenzyl-N, N-dimethylamine, 4-methoxy Amine compounds such as benzyl-N, N-dimethylamine and 4-dimethylaminobenzyl-N, N-dimethylamine, 2,4,6-triamino-s-triazine, 2-vinyl-4,6-diamino-s -Triazine, 2-vinyl-4,6-diamino-s-to Amino-s-triazine such as azine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine / isocyanuric acid adduct Quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyltributylammonium chloride, phosphonium salts such as tri-n-butyl-2,5-dihydroxyphenyl-phosphonium bromide, hexadecyltributylphosphonium chloride, etc. Among them, those having a —NH— group are preferred, amine compounds and amino-s-triazines are preferred, and dicyandiamide and 2,4,6-triamino-s-triazine are particularly preferred. Moreover, benzoic acid compounds, such as 2,5-dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid, can also be mentioned.
In the photosensitive composition of the present invention, the content of the epoxy curing agent as the component (F) is 0.1% by weight with respect to the total amount of the photosensitive composition in terms of stability over time as the photosensitive composition. % Or less is preferable.

[1-4-4] (G) Thermal acid generator In addition to the components (A) to (C), the photosensitive composition of the present invention is further heated for the purpose of improving chemical resistance and adhesion. It may contain a compound (thermal acid generator) (G) component that generates an acid by action.
Examples of the thermal acid generator of component (G) include various onium salt compounds such as aromatic diazonium salts, diaryliodonium salts, triallylsulfonium salts, triallyl selenium salts, sulfonate esters, and halogen compounds. It is done.
Specific examples of the aromatic diazonium salt include chlorobenzenediazonium hexafluorophosphate, dimethylaminobenzenediazonium hexafluoroantimonate, naphthyldiazonium hexafluorophosphate, dimethylaminonaphthyldiazonium tetrafluoroborate and the like. Diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium triflate, 4,4′-di-t-butyl-diphenyliodonium triflate, 4 4,4′-di-t-butyl-diphenyliodonium tetrafluoroborate, 4,4′-di-t-butyl-diphenyliodonium hexafluorophosphate, and the like.

Monophenylsulfonium salts include benzyl-p-hydroxyphenylmethylsulfonium hexafluorophosphate, p-hydroxyphenyldimethylsulfonium hexafluoroantimonate, p-acetoxyphenyldimethylsulfonium hexafluoroantimonate, Examples thereof include benzyl-p-hydroxyphenylmethylsulfonium hexafluoroantimonate, monophenylsulfonium salt types such as compounds represented by the following general formula (10), and benzylphenylsulfonium salt types.

(In the formula, Z represents a phenyl group.)
Triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tri (p-chlorophenyl) sulfonium tetrafluoroborate, Tri (p-chlorophenyl) sulfonium hexafluorophosphate, tri (p-chlorophenyl) sulfonium hexafluoroantimonate, 4-t-butyltriphenylsulfonium hexafluorophosphate, and the following general formula (11 ) And the like.

  Triallyl selenium salts include triallyl selenium tetrafluoroborate, triallyl selenium hexafluorophosphate, triallyl selenium hexafluoroantimonate, di (chlorophenyl) phenyl selenium tetrafluoroborate, di (chlorophenyl) phenyl selenium hexafluoro Examples thereof include phosphate, di (chlorophenyl) phenyl selenium hexafluoroantimonate, and the like.

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

Among these thermal acid generators, a monophenylsulfonium salt type, a benzylphenylsulfonium salt type, or a compound represented by the above general formula (11) is preferable.
In the photosensitive composition of the present invention, the content ratio of the thermal acid generator as the component (G) is usually 0.1% by weight or more, preferably 0.5% by weight or more, based on the total amount of the photosensitive composition. It is usually 20% by weight or less, preferably 10% by weight or less.
[1-4-5] (H) Polymerization accelerator
In addition to the components (A) to (C), the photosensitive composition of the present invention may further contain a polymerization accelerator (H) component for the purpose of improving the photopolymerization initiation ability of the composition. The polymerization accelerator for the component (H) preferably contains an amino acid ester or a dipolar compound, and the amino acid ester or dipolar compound includes the following general formula (X1a) or (
Those represented by X1b) are preferred.

[In the formulas (X1a) and (X1b), R ²⁶ and R ²⁷ each independently has an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An optionally substituted heterocyclic group or a hydrogen atom, R ²⁸ and R ²⁹ each independently represents an optionally substituted alkyl group or a hydrogen atom, and R ³⁰ represents a substituent. 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 ³¹ may have a substituent. An alkyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent is shown, and s is an integer of 0 to 10. ]
Here, the alkyl groups represented by R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , and R ³¹ in formulas (X1a) and (X1b) preferably have 1 to 8 carbon atoms. More preferably, it is ~ 4. Examples of the alkenyl group for R ³⁰ include a vinyl group, an allyl group, and an isopropenyl group. Examples of the aryl group for R ²⁶ , R ²⁷ , R ³⁰ , and R ³¹ include a phenyl group and a naphthyl group. Examples of the heterocyclic group of R ²⁶ , R ²⁷ and R ³⁰ 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, among the amino acid esters or dipolar compounds represented by the above general formula (X1a) or (X1b), one of R ²⁶ and R ^{27 in} formula (X1a) is a hydrogen atom and the other is It is a phenyl group which may have a substituent, R ²⁸ and R ²⁹ are both hydrogen atoms, and R 30 may have an alkyl group which may have a substituent, or may have a substituent. An amino acid ester which is a phenyl group and s is 0, 1, or 2, or R ²⁶ and R ^{27 in} formula (X1b) are both hydrogen atoms, or one of them has a substituent A good alkyl group, R ²⁸ and R ²⁹ are both hydrogen atoms, R 31 is an optionally substituted alkyl group, or an optionally substituted phenyl group, and s 1 is 0 It is an amino acid bipolar ion compound that is 1, or 2. preferable. While the other is a phenyl group with a hydrogen atom in the general formula s is 0 in (X1a), R ²⁶ and R ^27, the ester of R ²⁸ and R ²⁹ are both hydrogen atoms N- phenylglycine, among others, R ³⁰ is N-phenylglycine benzyl ester which is a benzyl group, or, in the general formula (X1b), s is 0, R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are all hydrogen atoms, and R ³¹ is a phenyl group A dipolar ionic compound of N-phenylglycine is particularly preferred.

In the present invention, the polymerization accelerator of the component (H) may further contain a polymerization accelerator other than the ester of amino acid or the dipolar ion compound. Examples of the polymerization accelerator include 2- Mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate Mercapto group-containing compounds such as trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, etc. Thiol compounds, N, N-dialkylaminobenzoic acid esters, N-phenylglycine or its derivatives such as ammonium salts and sodium salts thereof, phenylalanine or its salts such as ammonium and sodium salts, derivatives such as esters, etc. Examples include amino acids having an aromatic ring or derivatives thereof.
In the photosensitive composition of the present invention, the content ratio of the polymerization accelerator of the component (H) is preferably 20% by weight or less, and preferably 1 to 10% by weight with respect to the total amount of the photosensitive composition. Is more preferable.

[1-4-5] (I) Inorganic filler
In addition to the components (A) to (C), the photosensitive composition of the present invention may further contain an inorganic filler (I) component for the purpose of improving the strength as a cured product. Well, as the inorganic filler of the component (I), for example, talc such as “ST-2000” and “BST” manufactured by Nippon Talc, silica such as “R972” and “R974” manufactured by Nippon Aerosil, alumina, soot Examples thereof include barium sulfate and magnesium oxide such as “B-30”, “BF-1”, and “BF-40” manufactured by Kagaku Co., Ltd. These inorganic fillers can be surface-treated with a silane coupling agent or the like as required. The average particle size is usually 0.005 μm or more, usually 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less.

  In the photosensitive composition of the present invention, the content of the inorganic filler as the component (I) is preferably 70% by weight or less, and preferably 1 to 50% by weight with respect to the total amount of the photosensitive composition. Is more preferable.

[1-4-6] (J) Color material
Moreover, the photosensitive composition of this invention may contain (J) coloring material further in addition to the said (A)-(C) component. (J) A coloring material means a coloring material, particularly when the photosensitive composition of the present invention is used as a color filter, a solder resist or other colored composition. 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, pigments of various colors 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. Specific examples of pigments that can be used are shown below by pigment numbers. Note that “CI” described below means a 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, 179, 181, 184, 185, 187, 188, 190, 93,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243, 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, 5345, 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, 173 174, 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: 345: 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, a black color material can also be used as the color material. 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.

  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 OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12345), 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)).

  Further, 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 and titanium black are 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, # 2340, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31 Degussa Corporation: Printex3, Printex3OP, Printex30, Printex30OP Printex40, Printex45, Print ex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack340, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S16 0, Color Black S170 manufactured by Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R , BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8 Colombian Carbon Co .: RAVEN11, RAVEN14, RAVEN15, RAVEN 6, Raven22 Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven590H, Raven1000, Raven1020, Raven1040, Raven1060U, Raven1080U, Raven1080U, Raven1080U, Raven1080U, Raven1080U RAVEN5750, RAVEN7000
Examples of titanium black include the following.

As a method for producing titanium black, a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials.
As an example of another black pigment, aniline black, an iron oxide black pigment, and organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment.
In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used as the pigment.

The above-mentioned 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.
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.

As the coloring material used in the photosensitive composition of the present invention, for example, in the case of use for a solder resist, it is preferable to use a coloring material containing no halogen atom.
In the case where the coloring material in the total solid content of the photosensitive composition of the present invention is an inorganic or organic pigment, the average particle size of the pigment is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm. The following are used in a dispersed manner. In the pigment dispersion, it is preferable to use a dispersing agent and / or a dispersion aid together in order to improve dispersibility and dispersion stability.
As the dispersant, a surfactant, a polymer dispersant, and the like are usually used, but a polymer dispersant is particularly preferable because it is excellent in dispersion stability over time. As the polymer dispersant, for example, a nitrogen atom-containing dispersant described in, for example, JP-A-2005-126673 is preferable, and as such a nitrogen atom-containing dispersant, for example, a urethane-based dispersant and a nitrogen atom are contained. Graft copolymer, AB block copolymer and / or BAB block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base Examples include coalescence. A dispersing agent may be used individually by 1 type, or may mix and use 2 or more types.
The proportion of the color material (J) in the total solid content of the photosensitive composition of the present invention is usually 1 to 70% by weight, preferably 10 to 70% by weight, and more preferably 20 to 60% by weight. If the content ratio of the color material is too small, the coloring power becomes low, the film thickness becomes too thick with respect to the color density, and adversely affects the gap control at the time of forming a liquid crystal cell. On the other hand, if the content ratio of the coloring material is too large, the dispersion stability is deteriorated and there is a risk that problems such as re-aggregation and thickening occur.

[1-4-7] (K) Surfactant
In addition to the components (A) to (C), the photosensitive composition of the present invention is further intended to improve applicability as a composition coating solution and developability of the photosensitive composition layer. Nonionic, anionic, cationic, amphoteric, and fluorine-based surfactant (K) components may be contained.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene. Fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters And polyoxyethylene sorbite fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.

Further, fluorine-based and silicone-based ones can be preferably used. As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable. Specifically, 1,1,2,2-tetra Fluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, Hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1, 1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1 2,2,3,3-hexafluorodecane and the like. These commercially available products include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafac F142D”, “Same F172”, “Same F173”, “Same” manufactured by Dainippon Ink & Chemicals, Inc. F183 "," F470 "," FC430 "manufactured by Sumitomo 3M Corporation," DFX-18 "manufactured by Neos Corporation, and the like.

  Examples of silicone-based surfactants include “Toray Silicone DC3PA”, “Same SH7PA”, “Same DC11PA”, “Short SH21PA”, “Short SH28PA”, “Short SH29PA”, “Short SH30PA” manufactured by Torre Silicone Co., Ltd. "SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-444 (4) (5) (6) (7) 6", "TSF" manufactured by Toshiba Silicone Co., Ltd. Commercial products such as “-4460”, “TSF-4452”, “KP341” manufactured by Silicone Co., Ltd., “BYK323”, “BYK330” manufactured by Big Chemie.

Of these, silicone surfactants are preferred, and polyether-modified silicone surfactants are more preferred.
Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special Examples thereof include polymer surfactants. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

Examples of commercially available products include alkyl sulfate salts such as “Emar 10” manufactured by Kao Corporation, and alkyl naphthalene sulfonates such as “Perex NB-L” manufactured by Kao Corporation. “Homogenol L-18”, “Homogenol L-100” manufactured by Kao Corporation and the like can be mentioned.
The cationic surfactants include quaternary ammonium salts, imidazoline derivatives, amine salts, and the like, and the amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids, and the like. Is mentioned. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include “Acetamine 24” manufactured by Kao Corporation for alkylamine salts, and “Cotamine 24P” and “Cotamin 86W” manufactured by Kao Corporation for quaternary ammonium salts.

Two or more kinds of surfactants may be combined. Silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer surfactant Examples include combinations of agents. Of these, silicone surfactants / fluorine surfactants are preferred. Examples of the silicone surfactant / fluorine surfactant combination include polyether-modified silicone surfactant / oligomer-type fluorine surfactant. Specifically, for example, “TSF4460” /
Neos "DFX-18", Big Chemie "BYK-300""BYK-330" / Seimi Chemical "S-393", Shin-Etsu Silicone "KP340" / Dainippon Ink "F-478""SH7PA" manufactured by Torre Silicone Co., Ltd., "DS-401" manufactured by Daikin Co., Ltd., "L-77" manufactured by Nihon Unicar Co., Ltd., and "FC4430" manufactured by Sumitomo 3M Co., Ltd.
In addition, the photosensitive composition of the present invention mainly has a contact angle θ (degrees) with respect to a clean glass surface of a droplet of the photosensitive composition and a surface tension σ (mN) by appropriately selecting the surfactant. / M)
Is preferably adjusted so as to satisfy the following formulas (1), (2), and (3). By satisfying any of the following formulas (1), (2), and (3), it is possible to prevent the occurrence of coating unevenness and drying unevenness.

θ ≦ 5 × (σ ₀ −σ) (1)
σ ≦ σ ₀ −1 (2)
θ ≦ 15 (3)

[In the above formula, σ ₀ is the surface tension (mN / m) of the solvent alone used in the photosensitive composition. ]
Further, the photosensitive composition of the present invention preferably satisfies the following formulas (1 ′), (2 ′), and (3 ′), and the following formulas (1 ″), (2 ″), and (3 '') is more preferable, the following formula (2 '''),
And (3 ′ ″) are particularly preferable.

θ ≦ 4 × (σ ₀ −σ) (1 ')
σ ≦ σ ₀ −1.5 (2 ')
θ ≦ 12 (3 ')

θ ≦ 3 × (σ ₀ −σ) (1 '')
σ ≦ σ ₀ -2 (2``)
θ ≦ 9 (3``)

σ ≦ σ ₀ -2 (2 ''')
θ ≦ 5 (3 ''')

In addition, the photosensitive composition of the present invention has a surface tension σ ′ (mN / m) when diluted until the solvent weight is doubled by the solvent used in the photosensitive composition in terms of leveling properties. And the surface tension σ (mN / m) before dilution preferably satisfy the following formula (4):
Is more preferable, and it is particularly preferable that the following formula (4 ″) is satisfied.

| Σ−σ ′ | ≦ 0. 4 (4)
| Σ−σ ′ | ≦ 0. 3 (4 ')
｜ σ−σ ′ | ≦ 0.2 (4 '')

  In the present invention, the contact angle and the surface tension are measured by the following methods, respectively, and the dilution method is as follows.

<Contact angle>
(I) The glass substrate for liquid crystal panel is cleaned with a cleaning agent and then subjected to light cleaning by UV ozone treatment. By the cleaning, the contact angle with pure water is 0 (zero), that is, a clean glass substrate that spreads out completely. Examples of the cleaning agent include a surfactant-containing type alkaline cleaning agent, and an inorganic alkali is preferable. Specific examples include “Sunwash TL-100” manufactured by Lion Corporation, “Semi-clean KG” manufactured by Yokohama Oil Co., Ltd., and the like. UV ozone treatment is performed with a low-pressure mercury lamp irradiation device (for example, “VUM” manufactured by Oak Manufacturing Co., Ltd.) at an illuminance of usually 1 to 100 mW / cm ² , preferably 5 to 20 mW / cm ² for 10 to 300 seconds, preferably 30 to 120. It is performed on condition of second.

(Ii) The static contact angle of the resin composition with respect to the glass substrate produced by (i) is measured at 23 ° C. using a contact angle measuring device by a droplet method. Here, the “static contact angle” refers to a contact angle under a condition in which a state change with time due to flow or the like does not occur. The droplet method is usually performed by measuring within 1 minute after forming a droplet, preferably by measuring within 5 to 20 seconds. As the contact angle measuring device, for example, a direct reading method, an image processing method, or the like is used. Examples of the direct reading contact angle measuring device include “CA-DT” manufactured by Kyowa Interface Science Co., Ltd. Examples of the image processing type contact angle measuring device include “MCA-2” manufactured by Kyowa Interface Science Co., Ltd. and “DSA100” manufactured by KRUSS.

<Surface tension>
A platinum plate whose surface is fully red hot with an alcohol lamp or the like and cleaned is prepared, and the static surface tension of the resin composition is measured at 23 ° C. using a surface tension meter by a flat plate method. Here, “static surface tension” refers to surface tension under conditions in which state change with time due to flow or the like does not occur. Examples of the surface tension meter include “CBVP-A3” manufactured by Kyowa Interface Science Co., Ltd. and “Sigma 700” manufactured by KSV Corporation.

<Dilution method>
At room temperature, the same solvent as that used in the resin composition is added dropwise to the resin composition in the beaker while stirring and diluted. Specifically, for example, a magnetic stirrer or the like is added dropwise and diluted for 10 to 30 minutes while stirring at about 30 to 120 rpm.
The photosensitive composition satisfying the above formulas (1), (2), (3), and (4) of the present invention is prepared by the above-mentioned (C) alkali-soluble resin, surfactant. It is important to achieve this by selecting the type, amount, combination, etc. of each component, such as solvent, and adjusting the balance between the hydrophilicity / hydrophobicity of the surfactant, lipophilicity / oleophobicity, and the molecular weight and the polarity of the solvent. It is. These adjustments are not simply inferred from the specific molecular structure of the surfactant, but are determined by whether or not the entire composition satisfies the above formula.
In the photosensitive composition of the present invention, the content ratio of the (K) surfactant component is preferably 10% by weight or less, preferably 0.001 to 5% by weight, based on the total amount of the photosensitive composition. Is more preferable.

[1-4-8] Other additives
Furthermore, the photosensitive composition of the present invention contains various additives such as hydropolymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, and the like. 2% by weight or less of the total amount, plasticizers such as dioctyl phthalate, didodecyl phthalate, and tricresyl phosphate are similarly 40% by weight or less, and sensitivity property improvers such as tertiary amines and thiols are also 10% by weight or less. The precursor is also 30% by weight or less, and a flame retardant such as a non-halogen condensed phosphate (specifically, for example, aromatic condensed phosphates “CR-733S”, “CR-741”, “CR— 747 "," PX-200 ", etc.) may also be contained in a proportion of 40% by weight or less.

[1-5] Spectral sensitivity characteristics and minimum exposure
The photosensitive composition of the present invention usually has a maximum spectral sensitivity peak in the wavelength region of 340 to 430 nm, preferably 350 to 430 nm, more preferably 355 to 430 nm, and particularly preferably 360 to 430 nm. When the maximum peak of spectral sensitivity is on the short wavelength side, the sensitivity to laser light having a wavelength of 340 to 430 nm tends to be inferior as a photosensitive composition. On the other hand, when the maximum peak of spectral sensitivity is on the long wavelength side, It tends to be inferior in safe light property.

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.
Specific measurement examples include the following.
A sample obtained by cutting the image forming material into a size of 50 × 60 mm is 330 using a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. Exposure is performed by irradiating light dispersed in a wavelength region of ˜650 nm for 10 seconds while setting the exposure wavelength linearly in the horizontal axis direction and logarithmically changing the exposure intensity in the vertical axis direction.

  Next, an image corresponding to the sensitivity of each exposure wavelength is obtained by spraying a 1% by weight sodium carbonate aqueous solution at 30 ° C. as a developing solution to a pressure of 0.15 MPa and spray development in a time twice as long as the minimum developing time. It is done. The exposure energy capable of forming an image is calculated from the image height, 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 read.

Further, the photosensitive composition of the present invention is preferably an image forming minimum exposure amount capable [S _410] is 50 mJ / cm ² or less at a wavelength of 410 nm, further preferably at 30 mJ / cm ² or less, 20 mJ / Cm ² or less is particularly preferable. If this minimum exposure amount [S ₄₁₀ ] is too large, the exposure time tends to be longer and the practicality tends to be lowered, depending on the exposure intensity of the laser light source. The lower limit of the minimum exposure amount [S ₄₁₀ ] is preferably as small as possible, but is usually 1 mJ / cm ² or more.

Further, the photosensitive composition of the present invention has a ratio [S ₄₁₀ / S ₄₅₀ ] of 0.1 to the minimum exposure amount [S ₄₅₀ (mJ / cm ² )] capable of forming an image at a wavelength of 450 nm of [S ₄₁₀ ]. Or less, more preferably 0.05 or less. If this ratio [S ₄₁₀ / S ₄₅₀ ] is too large, it tends to be difficult to achieve both the blue-violet laser sensitivity and the safe light property under a yellow lamp.

In addition, the photosensitive composition of the present invention has a minimum exposure amount capable of forming an image at a wavelength of 450 nm of a minimum exposure amount [S _450-650 (mJ / cm ² )] capable of forming an image at each wavelength of 450 nm to 650 nm. The ratio [S _450-650 / S ₄₅₀ ] to [S ₄₅₀ (mJ / cm ² )] is preferably more than 1. If this ratio [S _450-650 / S ₄₅₀ ] is less than the above range, it tends to be difficult to achieve both blue-violet laser sensitivity and safe light performance under a yellow lamp.

It should be noted that the minimum exposure capable of forming an image at a wavelength of 410 nm [S ₄₁₀ ], the minimum exposure capable of forming an image at a wavelength of 450 nm [S ₄₅₀ ], and the minimum exposure capable of forming an image at a wavelength exceeding 450 nm and not more than 650 nm. The amount [S _450-650 (mJ / cm ² )] is the exposure energy capable of forming an image calculated from the obtained image height in the measurement of the maximum peak of the spectral sensitivity using the spectral sensitivity measuring apparatus described above. This means the minimum exposure that can be formed under optimum development conditions determined by changing development conditions such as developer type, development temperature, development time, etc. Usually, a condition is employed in which an alkaline developer at a temperature of 25 to 40 ° C. and a pH of 11 to 14 is sprayed at a pressure of 0.1 to 0.5 MPa for 0.5 to 3 minutes.

[2] Image forming material, image forming material, and image forming method
The photosensitive composition of the present invention can be used to form the image forming material of the present invention. The image forming material is usually coated on a temporary support film as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent and dried, and if necessary, the surface of the formed photosensitive composition layer is coated. It is formed by covering with a film. Examples of such an image forming material include a dry film resist material.

The image forming material can be further used to form the image forming material of the present invention. There are usually two types of image forming materials. One is created by peeling the coating film on the photosensitive composition layer side of the image-forming material when it is covered with a coating film and laminating it on the substrate to be processed. The other is created by the following procedure. (1) A coating solution in which each component of the negative blue-violet laser-sensitive composition is dissolved or dispersed in an appropriate solvent; (2) directly coated on a substrate to be processed and dried; (3) A layer of the negative blue-violet laser photosensitive composition of the present invention is formed on the substrate to be processed.
Furthermore, the image forming material is suitably used in the following image forming method. That is, the photosensitive composition layer of the image forming material is scanned and exposed with a laser beam having a wavelength of 340 to 430 nm, for example, and developed to reveal an image.

[2-1] Image forming material and image forming material
As a temporary support film used for the image forming material of the present invention, particularly a dry film resist material, conventionally known films such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film are used. The temporary support film preferably has a film thickness of 10 to 30 μm, a haze value of 1.5% or less, and metal-containing particles such as antimony having a diameter of 10 μm or more or aggregates thereof of 10/10 cm ² or less. At that time, when those films have the solvent resistance and heat resistance necessary for the production of the image forming material, the photosensitive composition coating solution is directly applied onto the temporary support film. Then, the image forming material of the present invention can be produced by drying, and even if those films have low solvent resistance or heat resistance, for example, polytetrafluoroethylene film, release film, etc. First, a photosensitive composition layer is formed on a film having releasability, and a temporary support film having low solvent resistance and heat resistance is laminated on the layer, and then a film having releasability is formed. By peeling, the image forming material of the present invention can be produced.
Further, for the purpose of enhancing the transferability of the photosensitive layer, a thermosetting transfer layer such as an ethylene vinyl acetate copolymer having a thickness of usually 10 to 50 μm can be provided on a temporary support film such as a polyethylene terephthalate film. .

The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate Cellosolve solvents such as ethyl cellosolve 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, etc. Propylene glycol solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate Ester solvents such as ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, cyclohexanone, Examples thereof include ketone solvents such as methyl amyl ketone, highly polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons thereto. The use ratio of the solvent is usually in the range of about 1 to 20 times by weight with respect to the total amount of each component of the photocurable composition.

  As the coating method, conventionally known methods such as spin coating, wire bar coating, spray coating, dip coating, air knife coating, roll coating, blade coating, screen coating, and curtain coating can be used. . The coating amount at that time is preferably 5 μm or more, more preferably 10 μm or more, as a dry film thickness, from the viewpoint of image formation to be described later, and subsequent workability such as etching and plating. In terms of sensitivity and the like, the thickness is preferably 200 μm or less, and more preferably 100 μm or less. In addition, the drying temperature in that case is about 30-150 degreeC, for example, Preferably it is about 40-110 degreeC. The drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes.

When used as an image forming material as a dry film resist material or the like, the surface of the formed photosensitive composition layer is covered with a coating film until the image forming material is laminated on a substrate to be processed. It is preferable that a conventionally known film such as a polyethylene film, a polypropylene film, a polyester film, or a polytetrafluoroethylene film is used as the covering film. Specifically, for example, a 40 μm-thickness polyester film “S120” manufactured by Mitsubishi Polyester is preferably used. Further, the coated film preferably has a film thickness of 10 to 50 μm, fish eyes having a diameter of 80 μm or more and 10 pieces / m ² or less, and preferably has a center line average roughness (Ra) of 0.1 μm. .

  Further, when the photosensitive composition layer side of the image forming material is covered with a coating film, the coating film is peeled off and laminated by heating, pressurizing, or the like. The image-forming material of the present invention is produced by directly applying and drying the coating composition liquid. In that case, the substrate to be processed is etched, plated, or soldered using a negative image that has been exposed by developing and exposing the photosensitive composition layer formed thereon with a laser beam or the like. By doing so, patterns such as circuits and electrodes are formed on the surface, and may be a metal plate itself such as copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, Usually, for example, thermosetting resins such as epoxy resins, polyimide resins, bismaleimide resins, unsaturated polyester resins, phenol resins, melamine resins, saturated polyester resins, polycarbonate resins, polysulfone resins, acrylic resins, polyamide resins, polystyrene resins, Trees made of thermoplastic resins such as polyvinyl chloride resin, polyolefin resin, and fluorine resin , Paper, glass, and inorganic materials such as alumina, silica, barium sulfate, calcium carbonate, or composites of glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin, etc. A metal foil made of a material such as metal oxide such as indium oxide, tin oxide, indium oxide doped tin oxide is heated and pressure-bonded on the surface of an 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 laminating or by sputtering, vapor deposition, or plating a metal is preferably used.

  When the image forming material of the present invention is produced by directly applying and drying the photosensitive composition coating solution, the photosensitive composition formed on the substrate to be processed as described above. A solution of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, etc. on the photosensitive composition layer in order to prevent polymerization inhibiting action due to oxygen of the photosensitive composition on the physical layer. The protective layer may be formed by applying and drying.

  The photosensitive composition of the present invention constituting the photosensitive composition layer laminated on the substrate to be processed as described above is composed of the (A) component containing an ethylenically unsaturated group and the (B) component. It contains a photopolymerization initiator, the alkali-soluble resin of the component (C), and the components (D) to (I) used as necessary. The component (D) is preferably dispersed in the other components containing the components (A) to (C) in the form of fine particles in which particles having a particle diameter of 5 μm or less occupy 50% or more of the total particles. Particles having a diameter of 5 μm or less are preferably dispersed in the form of fine particles occupying 80% or more of the total particles, and particles having a particle diameter of 3 μm or less are particularly preferably dispersed in the form of fine particles occupying 80% or more of the total particles. preferable.

If the dispersion state of the component (D) is not in the form of fine particles, the stability over time as the photosensitive composition will be inferior, or the adhesion to the substrate will be inferior, and the object of the present invention cannot be achieved.
In the present invention, in order to disperse the component (D) in the form of fine particles as described above, for example, the component (D) is finely pulverized into the fine particles under mechanical shearing stress by a mill roll or the like, and then the other components. The component (D) may be dispersed together with the alkali-soluble resin of the component (C) and finely pulverized into the fine particles under mechanical shear stress by a mill roll or the like, and then the other components. In addition, it is preferable to adopt a method of dispersing in a coating solvent.

[2-2] Image forming method
And the said image forming material of this invention which has the photosensitive composition layer of this invention on a to-be-processed substrate peeled the temporary support film, when the photosensitive composition layer is formed with the said image forming material. After, or when the photosensitive composition layer is formed by directly applying and drying the photosensitive composition coating liquid and having the protective layer, the protective layer and the like are peeled off Thereafter, the photosensitive composition layer is subjected to scanning exposure using a laser beam as an exposure light source and then developed to form a negative image on the substrate to be processed.

  As the exposure light source, carbon arc lamp, mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, and laser such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, ruby laser, etc. Although a light source is mentioned, the light source which generate | occur | produces the laser beam of the ultraviolet region of the wavelength range of 340-430 nm to the ultraviolet to blue violet region is preferable, and it is still more preferable that the center wavelength is about 405 nm. Specific examples include an indium gallium nitride semiconductor laser that oscillates at a center wavelength of 405 nm.

  The scanning exposure method using a laser light source is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like. The output light intensity is preferably 1 to 100 mW, more preferably 3 to 70 mW, the oscillation wavelength is preferably 355 to 430 nm, more preferably 400 to 420 nm, and the beam spot diameter is preferably 2 to 30 μm, more preferably 4 Scan exposure is performed at a scanning speed of ˜20 μm, a scanning speed of preferably 50 to 500 m / second, more preferably 100 to 400 m / second, and a scanning density of preferably 2,000 dpi or more, more preferably 4,000 dpi or more.

  The development after the laser scanning exposure is preferably performed using an aqueous developer containing an alkali component and a surfactant. Examples of the alkali component include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, Inorganic alkali salts such as dibasic sodium phosphate, tribasic sodium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine Organic amine compounds and the like, and used at a concentration of about 0.1 to 5 wt%.

  Examples of the surfactant include the same surfactants as mentioned in the photosensitive composition, and among them, nonionic, anionic, or amphoteric surfactants are preferable. Betaine type compounds are preferred. The surfactant is preferably used at a concentration of 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, and particularly preferably 0.001 to 5% by weight.

Furthermore, the developing solution can contain an organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, if necessary. Further, the pH of the developer is preferably 9 to 14, and more preferably 11 to 14.
The development is usually about 10 to 50 ° C., more preferably 20 to 20 ° C., by a known development method such as immersing the image forming material in the developer or spraying the developer on the image forming material. It is performed at a temperature of about 40 ° C. for a time of about 5 seconds to 10 minutes. Further, after the development processing, in order to improve heat resistance and chemical resistance as a resist of a negative image formed as a cured product, for example, it is preferable to perform heat treatment at a temperature of about 140 to 160 ° C. for 10 minutes to 1 hour. . Further, if necessary, the entire surface exposure of 50 to 1000 mJ / cm ² can be performed using the exposure light source before the heat treatment.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[1] Examples 1 and 2 and Comparative Example 1
[1-1] Preparation of photosensitive image forming material for solder resist
[1-1-1] Example 1
Components other than the component (b1-1) listed in Table 1 below and 20 parts by weight of isobutyl methyl acetate (MIBK) solution were subjected to dispersion treatment with a paint shaker to obtain a photosensitive composition solution (PA1).
Next, a hardly soluble photopolymerization initiator dispersion solution of the following component (b1-1), a benzophenone compound (b2-1) containing a sulfur atom represented by the following formula of the component (b2), and a photosensitive composition solution (PA1) was mixed and stirred with an ultrasonic disperser for 10 minutes to obtain a coating solution.

Next, the above-prepared coating solution is applied onto a polyethylene terephthalate film (thickness 19 μm) as a temporary support film in an amount that gives a dry film thickness of 40 μm using a wire bar, and 5% in an oven at 80 ° C. A polyethylene film (thickness 25 μm) as a coating film was laminated on the photosensitive composition layer formed by drying for a minute to prepare a photosensitive image forming material.

[1-1-2] Example 2
In Example 1, a photosensitive image-forming material was prepared in the same manner except that the oxime initiator (b1-3) soluble in a solvent was used instead of the photopolymerization initiator (b1-1) component (see Table 1 below). ).
[1-1-3] Comparative Example 1
In Example 1, a photosensitive image forming material was prepared in the same manner except that the photopolymerization initiator (b1-2) was used instead of the photopolymerization initiator (b1-1) (see Table 1 below).

*) The content of (b1-1) (b1-2) (b1-3) indicates the amount of only the oxime initiator compound.
(A1) Dipentaerythritol hexaacrylate
(B1) 1- (4-Methylthiophenyl) -2-morpholino-2-methyl-propan-1-one
(B1-1) Photopolymerization initiator represented by the following formula (absorption maximum 383 nm), alkali-soluble resin (C1) and isobutyl methyl ketone (MIBK) (weight ratio 40:30:30 weight ratio) After that, a photopolymerization initiator dispersion liquid dispersed in an average particle size of 0.4 μm by performing a dispersion treatment with a sand grinder (RMH-03 type) manufactured by Imex Corporation.

In addition, the average particle diameter of the said photoinitiator was measured using the Nikkiso Co., Ltd. laser diffraction scattering type particle size distribution measuring apparatus (MT3300EX).
Also, the photopolymerization initiator dispersion is applied on a polyethylene terephthalate film (thickness 19 μm) as a temporary support film in an amount that gives a dry film thickness of 40 μm using a wire bar, and dried in an oven at 80 ° C. for 5 minutes. When the particle diameter of the photopolymerization initiator in the coating film was measured using a Nikon optical microscope “L-200” having a digital length measuring device, the coating sample thus prepared had a photopolymerization initiator of 70% or more. The particle size was 2 μm or less.
(B1-2) A photopolymerization initiator represented by the following formula and an alkali-soluble resin (C1) mixed at a weight ratio of 40:30, and then kneaded with a three-roll mill. Dispersion.

In addition, when the average particle diameter of the said photoinitiator was measured using the Nikkiso Co., Ltd. laser diffraction scattering type particle size distribution measuring apparatus (MT3300EX), it was impossible to measure because there were many precipitated particles having a particle diameter of 200 μm or more.
The above photopolymerization initiator dispersion was applied on a polyethylene terephthalate film (thickness 19 μm) as a temporary support film in an amount to give a dry film thickness of 40 μm using a wire bar, and dried in an oven at 80 ° C. for 5 minutes. When the particle diameter of the photopolymerization initiator in the coating film was measured with a Nikon optical microscope “L-200” having a digital length measuring device, the photopolymerization initiator was 70% or more. The particle size of was 170 μm or more.
(B1-3) Photopolymerization initiator represented by the following formula (absorption maximum 383 nm)

(C1) Isopropylene glycol of unsaturated group and carboxyl group-containing epoxy resin (acid value 100 KOH · mg / g, weight average molecular weight 5,000, “PR-300PG” manufactured by Showa Polymer Co., Ltd.) having the following constitutional repeating units Monomethyl ether acetate (PGMA) solution (solid content 63% by weight)
(C2) Isobutylmethyl of an unsaturated group and carboxyl group-containing epoxy resin (acid value 100 KOH · mg / g, weight average molecular weight 4,000, “Kayarad ZAR-1527” manufactured by Nippon Kayaku Co., Ltd.) having the following constitutional repeating unit Ketone (MIBK) solution (solid content: 70% by weight)

(D1) Cresol novolac type epoxy resin (weight average molecular weight 4,000, “180S70” manufactured by Japan Epoxy Resin Co., Ltd.)
(E1) Methanol-modified melamine compound (“Nikarak” (registered trademark) MW100LM from Sanwa Chemical Co., Ltd.)
(I1) Talc
(I2) Barium sulfate
(J1) Phthalocyanine blue
(K1) Surfactant "BYK330" manufactured by Big Chemical Company

[1-2] Creation of image forming material
The copper foil surface of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm thick copper foil is buffed with “Scotchlite SF” manufactured by Sumitomo 3M Limited. After washing with water and drying with an air stream, the surface is then preheated to 60 ° C. in an oven, and the photosensitive image-forming material obtained above is placed on the copper foil of the copper-clad laminate. While peeling the polyethylene film, using a hand-type roll laminator on the peeling surface, laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min on the copper-clad laminate. An image forming material on which a photosensitive composition layer was formed was produced.

[1-3] Laser exposure sensitivity
About the photosensitive composition layer of the obtained image forming material, the exposure sensitivity was measured by the method shown below. The results are shown in Table 1. That is, the photosensitive composition layer of the obtained image forming material is fixed on an aluminum cylinder having a diameter of 7 cm, and a laser having a center wavelength of 405 nm and a laser output of 5 mW while changing the rotation speed at 10 to 100 revolutions per minute. Using a light source (“NLHV500C” manufactured by Nichia Corporation), scanning exposure was performed with an image surface illuminance of 2 mW and a beam spot diameter of 20 μm while changing the beam scanning interval and scanning speed, and then 1 wt% sodium carbonate at 30 ° C. An aqueous solution was sprayed as a developing solution to a pressure of 0.15 MPa, and a negative image was revealed by spray development in a time twice as long as the minimum development time. With respect to the obtained image, an exposure amount required for reproducing a line width of 20 μm was obtained and set as sensitivity to a blue-violet laser.

[1-4] Maximum peak of spectral sensitivity
Furthermore, when the maximum peak of spectral sensitivity was measured by the method shown below, it was about 400 nm.
A sample obtained by cutting an image forming material into a size of 50 × 60 mm is used with a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. The light split in the wavelength range of 340 to 650 nm was exposed by irradiating for 10 seconds with the exposure wavelength linearly changing in the horizontal axis direction and the exposure intensity changing logarithmically in the vertical axis direction. By spraying a 1 wt% sodium carbonate aqueous solution at 30 ° C. as a developing solution to 0.15 MPa and spray developing in a time twice as long as the minimum developing time, an image corresponding to the sensitivity of each exposure wavelength is obtained, Calculate the exposure energy that can be formed from the image height, plot the wavelength on the horizontal axis, and the reciprocal of the exposure energy on the vertical axis. It took only.

[1-5] [S _410], [S ₄₁₀ / S _450], and [S _450-650 / S _450]
Further, when the minimum exposure amount [S ₄₁₀ (mJ / cm ² )] capable of forming an image at a wavelength of 410 nm was measured by the method shown below, it was as shown in Table 1. Further, the ratio [S ₄₁₀ / S ₄₅₀ ] of the minimum exposure amount [S ₄₁₀ ] capable of forming an image at a wavelength of ₄₁₀ nm to the minimum exposure amount [S ₄₅₀ (mJ / cm ² )] capable of forming an image at a wavelength of 450 nm, and the wavelength ratio 450nm exceeds 650nm minimum exposure amount capable of forming an image at each wavelength below [S _450-650 (mJ / cm ^2)] minimum exposure amount capable of forming an image at the wavelength 450nm of [S ₄₅₀ (mJ / cm ^2)] [S _450-650 / S ₄₅₀ ] was measured and evaluated according to the following criteria.
In the same manner as described above, the minimum exposure amount [S ₄₁₀ (mJ / cm ² )] capable of forming an image at a wavelength of 410 nm and an image at a wavelength of 450 nm when the exposure is performed while changing the wavelength in the wavelength region of 340 to 650 nm and development is performed. Minimum exposure amount that can be formed [S ₄₅₀ (mJ / cm ² )] and minimum exposure amount that can form an image at each wavelength of 450 nm to 650 nm or less [S _450-
650 (mJ / cm ² )] were calculated, and the ratios [S ₄₁₀ / S ₄₅₀ ] and [S _450-650 / S ₄₅₀ ] were calculated and evaluated according to the following criteria.

[1-5-1] evaluation criteria of the [S ₄₁₀ / S _450]
A: _S410 / _S450 is 0.03 or less.
B: _S410 / _S450 is more than 0.03 and less than or equal to 0.05.
C: S ₄₁₀ / S ₄₅₀ is more than 0.05 and 0.1 or less.
D: S ₄₁₀ / S ₄₅₀ exceeds 0.1.
[1-5-2] evaluation criteria of the [S _450-650 / S _450]
A: S _450-650 / S ₄₅₀ is more than 10.
B: S _450-650 / S ₄₅₀ is more than 5 and 10 or less.
C: S _450-650 / S ₄₅₀ is more than 1 and 5 or less.
D: S _450-650 / S ₄₅₀ is 1 or less.

[1-6] Safe light property under yellow light
Separately, with respect to the obtained photosensitive image forming material, the safelight property under a yellow light was evaluated by the method shown below.
In the measurement of the exposure sensitivity, the image forming material was allowed to stand for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, and 30 minutes under yellow light illumination (conditions in which light having a wavelength of about 470 nm or less was blocked). In the same manner as described above, scanning exposure and development processing were performed, and the standing time until the image changed compared to the above was obtained, and evaluated according to the following criteria.
A: More than 20 minutes
B: 10 minutes or more and less than 20 minutes
C: 1 minute or more and less than 10 minutes
D: Less than 1 minute

[1-7] Electroless nickel gold plating chemical resistance A 04 mm thick copper-clad glass epoxy substrate (EL170 manufactured by Mitsubishi Gas Chemical Co., Ltd.) subjected to surface chemical polishing treatment using a chemical polishing treatment agent CPE900 manufactured by Mitsubishi Gas Chemical Co., Ltd. An image forming material prepared by the same method as in Example 1 above was used for image formation, using a substrate obtained by immersion at 25 ° C. for 60 seconds using a 20-fold diluted solution of degreasing agent (ACL009) and further washing with water. Laser exposure was performed with the minimum exposure required, followed by development processing, and a thin line image having a width of 20 μm was formed on the copper substrate. Next, this substrate was subjected to an overheating effect treatment at 150 ° C. for 1 hour to obtain an image forming material in which the photosensitive layer fine wires were thermally cured.

  This image forming material is immersed in a 20-fold diluted aqueous solution of degreasing agent (ACL990) manufactured by Uemura Kogyo Co., Ltd. at 50 ° C. for 5 minutes, washed with water, further immersed in a 10% by weight sulfuric acid aqueous solution at 25 ° C. for 30 minutes, and washed with water. Thereafter, the sample was immersed in an aqueous solution containing 10% by weight of sodium persulfate and 1.8% by volume of sulfuric acid in 1 L, washed at 25 ° C. for 30 minutes, and further subjected to soft etching treatment. Subsequently, after being immersed in a 1.8% by volume sulfuric acid aqueous solution at 25 ° C. for 30 minutes, an electroless nickel plating catalyst (an aqueous solution containing 100 ml of KAT-450 made by Uemura Kogyo Co., Ltd. and 18 ml of sulfuric acid in 1 L) After immersion in water at 25 ° C. for 30 minutes, followed by washing with water, an electroless nickel plating solution (150 ml in 1 L, electroless nickel reagent NPR-M, 45 ml Nimden-NPR-A, 3 ml Nimden -An aqueous solution containing NPR-D) was immersed in water at 80 ° C for 18 minutes, washed with water, and a nickel plating layer having a thickness of 3 µm was formed. Subsequently, it is immersed in an electroless gold plating solution (50 ml of TKK-51 M20 manufactured by Uemura Kogyo Co., Ltd. and 1st gold cyanide potassium solution in 1 L) at 85 ° C. for 7 minutes and then washed with water to form a 0.03 μm thick gold plating layer I let you. Cellophane tape (manufactured by Nichiban Co., Ltd.) was adhered to the fine line resist portion of the plated image forming material thus obtained, the tape was peeled off, the proportion of the fine line resist adhered and transferred to the tape was measured, and the plating chemical resistance was evaluated. .

A: The fine line resist transferred to the peeled tape was less than 5% of the original resist.
It was.
B: The fine line resist transferred to the peeled tape was 5% or more and less than 20% with respect to the original resist.
C: The fine line resist transferred to the peeled tape is 20% to 50% of the original resist
Was less than.
D: The fine line resist transferred to the peeled tape was 50% or more of the original resist.

Further, in Examples 1 and 2 and Comparative Example 1, (b2-1) Photosensitivity obtained in the same manner as in Examples 1 and 2 and Comparative Example 1 except that the benzophenone compound containing a sulfur atom was excluded. When the above electroless nickel gold plating chemical resistance evaluation was performed on the image forming materials (referred to as Examples 1 ′ and 2 ′ and Comparative Example 1 ′), the evaluation was “D”.
In Example 1, in the above electroless nickel gold plating chemical resistance evaluation, instead of a copper-clad glass epoxy substrate, a glass plate “AN100” manufactured by Asahi Glass Co., Ltd. was used to deposit gold to a thickness of 10 nm. A similar effect can be expected even if the same evaluation as the above evaluation test is performed.

Claims (12)

(A) A photosensitive composition containing an ethylenically unsaturated group-containing compound, (B) a photopolymerization initiation system, and (C) an alkali-soluble resin, wherein (B) the photopolymerization initiation system is (b1) A photosensitive composition comprising a compound represented by formula (1) or (2), and (b2) a benzophenone compound containing a sulfur atom.

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring together with R ¹ ′, and the linking group is an alkylene group having 1 to 10 carbon atoms that may have a substituent, — (CH═CH) _n —, — ( C [identical to] C) _n - or a combination thereof (n is an integer of 0 to 3), R ^2a are each optionally substituted alkanoyl group having 2 to 12 carbon atoms, 3 carbon 5 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 benzoyl group, C1-C20 heteroaryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 And R1 ′ represents an optional substituent containing an aromatic ring or a heteroaromatic ring.):

(In the formula, R ^1b is a phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms, each of which may be substituted. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number Represents an amino group having 0 to 20 or an aminoalkyl group having 1 to 20 carbon atoms, and R ^1b forms a ring together with R 1 ′. The linking group may be a C 1-10 alkylene group which may have a substituent, — (CH═CH) _n —, — (C≡C) _n — or a combination thereof ( n is an integer of 0 to 3), and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms. A phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyoxycarbonylalkanoyl group having 3 to 20 carbon atoms, or an aminocarbonyl group having 2 to 10 carbon atoms, and R1 ′ is an aromatic ring or heterocycle
An optional substituent containing an aromatic ring is shown. )   The photosensitive composition according to claim 1, wherein the compound (b1) has an average particle size of 0.001 μm to 150 μm.   The photosensitive composition according to claim 1 or 2, wherein the compound (b1) has an absorption maximum in a wavelength range of 340 to 430 nm.   The photosensitive composition of any one of Claims 1 thru | or 3 which has the maximum peak of spectral sensitivity in the wavelength range of 340-430 nm. (B1) The photosensitive composition according to any one of claims 1 to 4, wherein the compound represented by the general formula (1) or (2) is a compound represented by the general formula (3) or (4). object.

Wherein R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and 8 to 8 carbon atoms. A phenoxycarbonylalkyl group having 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, an amino group having 0 to 20 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms, R ^1a may form a ring with R ³ or R ⁷ , in which case R ^1a and R ³ or / and R ⁷ are bonded together to form a divalent or trivalent linking group, linking groups each substituent alkylene group having 1 to 10 carbon atoms which may have _{a, - (CH = CH) n} -, - (C≡C) n - or a combination thereof ( Is an integer of 0 to 3), R ^2a are each optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, 7 carbon atoms Represents a benzoyl group having 20 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a phenoxycarbonyl group having 7 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms, a benzyl group having 7 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, and 1 to 1 carbon atoms 20 Heteroaryloyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxyoxycarbonylalkanoyl group, C2-C12 alkoxycarbonyl group or or phenoxycarbonyl group having a carbon number of ^{7~20, -OR 8, -SR 9,} -SOR 9, shows a -SO ₂ R ⁹ or -NR ¹⁰ R ^11,
And at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is —OR ⁸ , —SR ⁹ or —NR ^10.
R ¹¹ is shown. However, R ⁸ is a hydrogen atom, carbon atoms which may each be substituted 1-12
Alkyl group, alkanoyl group having 2 to 8 carbon atoms, alkenyl group having 3 to 12 carbon atoms, alkenoyl group having 3 to 20 carbon atoms, phenyl group having 6 to 20 carbon atoms, — (CH ₂ CH ₂ O) _m H (M
Represents an integer of 1 to 20), or a trialkylsilyl group having 3 to 15 carbon atoms, and R ⁹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or 2 to 8 carbon atoms. An alkanoyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a phenyl group having 6 to 20 carbon atoms or a trialkylsilyl group having 3 to 15 carbon atoms, R ¹⁰ and R ¹¹ Are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a hydroxyl alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a carbon atom having 6 to 20 carbon atoms. Represents a phenyl group, R ^{3 to} R ⁷ may be bonded to each other and may form a ring structure together with R ¹ ; ):

(In the formula, R ^1b is a phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms, each of which may be substituted. Group, benzoyl group having 7 to 20 carbon atoms, alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, amide group having 1 to 20 carbon atoms, nitro group, alkenyl group having 2 to 25 carbon atoms, 1 to carbon atoms 10 heteroarylalkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, carbon number A 0-20 amino group or a C1-C20 aminoalkyl group is shown, and R ^1b together with R ³ or R ⁷ In this case, R ^1b and R ³ or / and R ⁷ may be bonded to each other to form a divalent or trivalent linking group, and each of the linking groups has a substituent. A C1-C10 alkylene group,-(CH = CH) _n -,-(C
≡C) _n -or a combination thereof (n is an integer of 0 to 3), and R ^2b is an optionally substituted heteroaryl group having 1 to 20 carbon atoms or heteroarylalkanoyl having 1 to 20 carbon atoms. Group, a C3-C20 alkoxycarbonylalkanoyl group, a C8-C20 phenoxycarbonylalkanoyl group, a C3-C20 heteroaryloxyoxycarbonylalkanoyl group, or a C2-C10 aminocarbonyl group , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as in general formula (3). )   (C) The photosensitive composition according to any one of claims 1 to 5, wherein the alkali-soluble resin is a carboxyl group-containing epoxy resin and / or a carboxyl group-containing vinyl resin.   The alkali-soluble resin (C) is a carboxyl group-containing vinyl resin, and the content of each constituent repeating unit derived from ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and styrenes is The photosensitive composition according to any one of claims 1 to 5, which is 10 to 50% by weight, 15 to 80% by weight, and 1 to 40% by weight with respect to all the structural repeating units of the coalescence.   The photosensitive composition according to any one of claims 1 to 7, further comprising (I) an inorganic filler.   The photosensitive composition according to claim 1, further comprising (J) a coloring material.   An image-forming material comprising a layer of the photosensitive composition according to any one of claims 1 to 9 formed on a temporary support film.   An image forming material, wherein the image forming material according to claim 10 is laminated on the substrate to be processed on the photosensitive composition layer side. 12. An image forming method, wherein the photosensitive composition layer of the image forming material according to claim 11 is scanned and exposed with a laser beam having a wavelength of 340 to 430 nm, and developed to reveal an image.