KR20070065889A - Photosensitive composition, image-forming base material, image-forming material, and image-forming method - Google Patents

Abstract

Disclosed is a photosensitive composition which is highly sensitive to laser light, particularly to laser light from ultraviolet to blue-violet, and is excellent in long-term storage stability and adhesion to a substrate. The photosensitive composition is suitably used as a solder resist or a dry film, and in particular it is suitable for direct drawing wherein laser light from ultraviolet to blue-violet is used. Also disclosed are an image-forming base material using such a photosensitive composition, an image-forming material and an image-forming method. Specifically disclosed is a photosensitive composition containing an ethylenically unsaturated group-containing compound (A), a photopolymerization initiator (B) and an alkali-soluble resin (C) which is characterized in that the photopolymerization initiator (B) contains a photopolymerization initiator having a specific structure and an average particle diameter of not less than 0.001 mum and not more than 150 mum.

Description

Photosensitive composition, image forming material, image forming material, and image forming method {PHOTOSENSITIVE COMPOSITION, IMAGE-FORMING BASE MATERIAL, IMAGE-FORMING MATERIAL, AND IMAGE-FORMING METHOD}

INDUSTRIAL APPLICABILITY The present invention provides a printed circuit board, a liquid crystal display device, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, a photo spacer, a lip resist, an organic circuit in an organic electroluminescence, or the like, and the formation of an electrode processing substrate. It relates to a photosensitive composition used for etching resist, plating resist, solder resist, dry film, coverlay and the like. Moreover, especially for a dry film and a soldering resist, it is related with the photosensitive composition suitable for use for direct drawing by ultraviolet-violet laser light, and the image forming material, image forming material, and image forming method using the same. .

BACKGROUND ART Conventionally, formation of printed circuit boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, photo spacers, lip resists, organic electroluminescence, and the like for the formation of conductor circuits and electrode processed substrates, etc. The lithography method is widely used.

In the lithography method, (1) a dry film resist material (an image forming material in which a coating liquid of a photosensitive composition is applied and dried on a temporary support film to form a photosensitive composition layer, and the surface of the photosensitive composition layer is covered with a coating film), and the like. The photosensitive image forming material produced by laminating on the substrate to be processed or (2) the coating liquid of the photosensitive composition directly on the substrate to be processed and dried to form a photosensitive composition layer, if necessary, the surface of the photosensitive composition layer The image forming material produced by covering with a protective layer is used.

And image formation is performed in order of the following (1)-(3). (1) The photosensitive composition layer on a to-be-processed substrate is image-exposed 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 developed using the difference in solubility in the developing solution of the exposed portion and the non-exposed portion to form a resist image corresponding to the circuit pattern. (3) After the substrate to be processed is subjected to etching processing, plating processing, soldering, or the like using the resist image as a resist, a circuit or an electrode pattern drawn on the mask film is formed on the substrate by removing the resist image.

On the other hand, in recent years, by using laser light for an exposure light source, the laser direct drawing method of forming an image directly from digital information such as a computer without using a mask film can improve not only productivity but also resolution and position accuracy. Attention has been drawn to the fact that the use of the laser light has been actively studied in the lithography method.

By the way, although the laser light is known various light sources from the ultraviolet to the infrared region, laser light that can be used for image exposure, such as argon ion laser, helium neon laser, in terms of output, stability, photosensitive ability and cost, The main focus is to emit light in the infrared region from visible light such as YAG laser and semiconductor laser. For example, the lithographic method using an argon ion laser of wavelength 488 nm and an FD-YAG laser of wavelength 532 nm has already reached practical use.

However, the conventional photosensitive composition cannot be said to have sufficient sensitivity yet in the direct drawing method by a laser beam. In addition, recent advances in laser technology have made it possible to use semiconductor lasers capable of stably oscillating in the blue-violet region. However, the output power of the semiconductor laser is lower than that of other visible regions, and the sensitivity and development of the corresponding photosensitive composition are also low. It is a reality that sex and the like have not reached practical levels not only in the direct drawing method but also in the lithography method.

About the said subject, for the purpose of improving the sensitivity, developability, and durability of the image formed by it, for example, a polyhydric carboxylic acid or the like in the (alpha), (beta)-unsaturated monocarboxylic acid adduct of an epoxy resin, The photosensitive composition containing alkali-soluble modified epoxy acrylate resin which added the anhydride is known. Further, the photosensitive composition is laminated on a substrate as a dry film resist material, or the image forming material for photoresist in which the composition coating liquid is applied on a substrate and dried to form a photosensitive composition layer is formed of a high pressure mercury lamp or a visible laser, Or the image forming method which exposes by a infrared laser and develops is known. Furthermore, alkali-soluble modified epoxy acryl which added polyhydric carboxylic acid or its anhydride to the (alpha), (beta)-unsaturated monocarboxylic acid adduct of a specific oxime compound, an inorganic fine particle, or an epoxy resin for the purpose of improving a sensitivity or resolution. The composition which contained the rate resin is proposed (for example, refer patent documents 1-6).

However, while the said photosensitive composition still has room for improvement in sensitivity and developability, heat resistance as a resist material obtained, adhesiveness with respect to a board | substrate, etc. were also inadequate. In particular, the sensitivity of the photosensitive composition corresponding to the blue violet semiconductor laser was insufficient.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-204150

Patent Document 2: Japanese Unexamined Patent Publication No. 2000-147767

Patent Document 3: Japanese Unexamined Patent Publication No. 2001-228611

Patent Document 4: Japanese Unexamined Patent Publication No. 2002-105112

Patent Document 5: Japanese Unexamined Patent Publication No. 2002-107926

Patent Document 6: Japanese Unexamined Patent Publication No. 2003-280193

Disclosure of the Invention

Problems to be Solved by the Invention

This invention is made | formed in view of the above-mentioned prior art, As a photosensitive composition which is highly sensitive with respect to a laser beam, especially the ultraviolet-violet laser beam, and is excellent in time-lapse storage stability and adhesiveness with respect to a board | substrate, Especially For the purpose of providing a photosensitive composition suitable for use in direct drawing by blue-violet laser light, and especially for solder resist or dry film, and an image forming material, an image forming material, and an image forming method using the same. do.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it is generally a solvent which is highly sensitive to an ultraviolet-ray light from ultraviolet among the oxime ester system photoinitiators (henceforth a "oxime initiator") which has a specific structure. I found out that it was poorly soluble in. Therefore, by making these poorly soluble oxime initiators finer and making the average particle diameter smaller than before, the photosensitive composition containing them is highly sensitive to ultraviolet-violet laser light from ultraviolet and excellent in storage stability and adhesion to the substrate. Figured out. In addition, it was found that the oxime initiator had high sensitivity to blue-violet light and was soluble in a solvent, and found that the photosensitive composition containing the same was also excellent in sensitivity, time-lapse storage stability, and adhesion to the substrate.

That is, this invention consists of the summary shown below.

(1) As a photosensitive composition containing (A) an ethylenically unsaturated group containing compound, (B) photoinitiator, and (C) alkali-soluble resin, (B) photoinitiator has a structure of following General formula (I), Moreover, the photosensitive composition containing an average particle diameter of 0.001 micrometer or more and 150 micrometers or less is characterized by the photosensitive composition (Hereinafter, it may be called "the 1st photosensitive composition of this invention.").

[Formula 1]

(In formula, R <^2> may respectively be a C2-C20 alkanoyl group, a C3-C25 alkenoyl group, a C3-C8 cycloalkanoyl group, a C7-C20 benzoyl group, and C2-C20. An alkoxycarbonyl group of 10, a phenoxycarbonyl group of 7 to 20 carbon atoms, a heteroaryl group of 1 to 20 carbon atoms, a heteroaryloyl group of 1 to 20 carbon atoms, or an aminocarbonyl group of 1 to 20 carbon atoms, respectively. Arbitrary substituents.)

(2) A photosensitive composition for blue violet laser containing (A) an ethylenically unsaturated group-containing compound, (B) photopolymerization initiator, and (C) alkali-soluble resin, wherein the photosensitive composition for blue violet laser has a wavelength region of 345 to 430 nm. A blue violet laser having a maximum peak of spectral sensitivity and (B) the photopolymerization initiator having an absorption maximum in a wavelength region of 340 to 430 nm and containing a photopolymerization initiator having the structure of the general formula (I). Photosensitive composition for (Hereinafter, it may be called "the 2nd photosensitive composition of this invention.").

(3) The image forming material in which the layer of the photosensitive composition of said (1) and / or the photosensitive composition for blue-violet laser of said (2) is formed on a temporary support film.

(4) The image forming material in which the image forming material as described in said (3) is laminated | stacked on the to-be-processed substrate at the photosensitive composition layer side.

(5) An image forming method in which the photosensitive composition layer of the image forming material according to (4) is subjected to scanning exposure using a laser beam having a wavelength of 340 to 430 nm, and subjected to development to display an image.

Effects of the Invention

According to the present invention, while being highly sensitive to laser light, it is excellent in storage stability over time and adhesion to the substrate, and is particularly suitable for solder resist or dry film, and also for direct drawing by ultraviolet light from ultraviolet light. Suitable photosensitive compositions, and image forming materials, image forming materials, and image forming methods using the same can be provided.

To practice the invention  Best form for

The structural requirements of the present invention described below are representative examples of the embodiments of the present invention and are not specified in these contents.

[1] photosensitive compositions

The 1st photosensitive composition of this invention contains (A) ethylenically unsaturated group containing compound, (B) photoinitiator, and (C) alkali-soluble resin as an essential component, and (B) photoinitiator as a component. Has the specific structure mentioned later, and it is essential to contain the photoinitiator whose average particle diameter is 0.001 micrometer or more and 150 micrometers or less. The 2nd photosensitive composition of this invention has the specific structure which (B) photoinitiator mentions later, and makes it essential to contain the photoinitiator which has absorption maximum in the wavelength range of 340-430 nm. And you may contain the component of that excepting the above.

Below, the spectral sensitivity characteristic and the component of the photosensitive composition of this invention are demonstrated in detail. In addition, in this invention, "(meth) acryl" shall mean "acryl" or / and "methacryl".

[1-1] (A) Ethylenic unsaturated group-containing compound

The ethylenically unsaturated group-containing compound, which is the component (A) constituting the photosensitive composition of the present invention, acts upon the action of the photopolymerization initiator containing the photopolymerization initiator, which is component (B) described later, when the photosensitive composition is irradiated with active light. It is a compound which has at least 1 radically polymerizable ethylenically unsaturated bond in a molecule | numerator which add-polymerizes and bridge | crosslinks and hardens according to the case.

The ethylenically unsaturated group-containing compound in the present invention may be a compound having one or more ethylenically unsaturated bonds in a molecule, but polymerizable, crosslinkable, and the difference in developer solubility of exposed and non-exposed portions can be increased. It is preferable that it is a compound which has two or more ethylenically unsaturated bonds in a molecule | numerator from the point which can be used. Moreover, the acrylate compound whose unsaturated bond originates in a (meth) acryloyloxy group is especially preferable.

As a compound which has one or more ethylenically unsaturated bonds in a molecule | numerator, For example, unsaturated carboxylic acids, such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, a citraconic acid, or its alkyl Ester, (meth) acrylonitrile, (meth) acrylamide, styrene, etc. are mentioned.

As a compound which has two or more ethylenically unsaturated bonds in a molecule | numerator, For example, ester of unsaturated carboxylic acid and a polyhydroxy compound, (meth) acryloyloxy group containing phosphate, hydroxy (meth) acrylate compound And urethane (meth) acrylates of polyisocyanate compounds, epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds, and the like.

Examples of the esters include unsaturated carboxylic acids as described above, ethylene glycol, polyethylene glycol (additional number 2 to 14), propylene glycol, polypropylene glycol (additional number 2 to 14), trimethylene glycol, tetra Reactants of aliphatic polyhydroxy compounds such as methylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamines and triethanolamines; Can be mentioned. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropane tree (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 the like, and Plural ring opening parts of the same crotonate, isocrotonate, maleate, itaconate, citraconate, and caprolactane The dipentaerythritol (meth) acrylate type compound (for example, DPCA-30, DPCA-60, DPCA-120, etc. by Nippon Kayaku Co., Ltd.) which have added skeleton etc. are mentioned.

Moreover, as said ester, the reaction product of the above-mentioned unsaturated carboxylic acid, aromatic polyhydroxy compounds, such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A, or these ethylene oxide adducts, Specifically, Bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc. are mentioned, for example. Moreover, the reaction product of such unsaturated carboxylic acid and heterocyclic polyhydroxy compounds, such as tris (2-hydroxyethyl) isocyanurate, Specifically, for example, tris (2-hydroxyethyl) iso Di (meth) acrylate of a cyanurate, a tri (meth) acrylate, etc. are mentioned. Moreover, the reactant of unsaturated carboxylic acid, polyhydric carboxylic acid, and a polyhydroxy compound, specifically, the condensate of (meth) acrylic acid, phthalic acid, and ethylene glycol, the condensation of (meth) acrylic acid, maleic acid, and diethylene glycol, for example Water, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, and condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin; and the like.

Moreover, as said (meth) acryloyloxy-group containing phosphate, it will not specifically limit, if it is a phosphate compound containing a (meth) acryloyloxy group. Especially, it is preferable to represent with the following general formula (IVa) or (IVb).

[Formula 2]

[In 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, it is preferable that n is 1-10, especially 1-4. As these specific examples, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, etc. are mentioned, for example, These may each be used independently and may be used as a mixture.

Moreover, as said urethane (meth) acrylates, the reactant of a hydroxy (meth) acrylate compound and a polyisocyanate compound, etc. are mentioned, for example. As said hydroxy (meth) acrylate compound, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylol ethane tri (meth) acrylate, etc. are mentioned, for example. As said polyisocyanate compound, For example, aliphatic polyisocyanate, such as hexamethylene diisocyanate and 1,8- diisocyanate-4-isocyanate methyl octane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4'- Alicyclic polyisocyanates such as methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate and tris (isocyanatephenyl) thiophosphate, iso Heterocyclic polyisocyanate, such as cyanurate, is mentioned.

Especially, as urethane (meth) acrylates, the compound which has four or more urethane bond [-NH-CO-O-] and four or more (meth) acryloyloxy groups in 1 molecule is preferable. Examples of the compound include the following ones.

(i-1) A compound obtained by reacting a diisocyanate compound with a compound having four or more hydroxyl groups in one molecule.

As said "compound which has four or more hydroxyl groups in 1 molecule", pentaerythritol, polyglycerol, etc. are mentioned, for example. As said diisocyanate compound, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, etc. are mentioned, for example.

(i-2) It is a compound obtained by making the compound which has 3 or more isocyanate groups in 1 molecule react with the compound which has 2 or more hydroxyl groups in 1 molecule.

As a compound which has two or more hydroxyl groups in 1 molecule, ethylene glycol etc. are mentioned, for example.

As a compound which has three or more isocyanate groups in 1 molecule, For example, "Duranate 24A-100", "Duranate 22A-75PX", "Duranate 21S-75E", "Duranate 18H" by Asahi Kasei Kogyo Co., Ltd. And an adduct type such as "Duranate P-301-75E", "Duranate E-402-90T", and "Duranate E-405-80T".

(i-3) As a compound which has four or more, preferably 6 or more isocyanate groups in 1 molecule, the compound obtained by superposing | polymerizing or copolymerizing isocyanate ethyl (meth) acrylate etc. is mentioned, for example.

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) acryloyl jade in one molecule. It can obtain by making compound (ii) which has a timing react.

As the compound (ii), for example, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acryl The rate etc. are mentioned.

Here, it is preferable that it is 500-200,000, and, as for the weight average molecular weight of the said compound (i), it is especially preferable that it is 1,000-150,000. Moreover, it is preferable that the molecular weight of urethane (meth) acrylates as mentioned above is 600-150,000. Moreover, it is preferable to have six or more urethane bonds, and it is especially preferable to have eight or more urethane bonds. Moreover, it is preferable to have 6 or more (meth) acryloyloxy groups, and it is especially preferable to have 8 or more.

On the other hand, such urethane (meth) acrylates have, for example, a molar ratio of the compound (i) and the compound (ii) between the former isocyanate group and the latter hydroxyl group in an organic solvent such as toluene or ethyl acetate. It can be manufactured by the method of making it into the ratio of -10/1, and making it react at 10-150 degreeC for 5 minutes-about 3 hours using catalysts, such as n-butyl dilaurate as needed.

In this invention, it is especially preferable that it is represented by the following general formula (V) among the said urethane (meth) acrylates.

[Formula 3]

[In Formula (V), Ra represents the group which has a repeating structure of an alkyleneoxy group or an aryleneoxy group, and has 4-20 oxy groups which can couple | bond with Rb, and Rb and Rc are respectively independently C1-C1 An alkylene group of 10, Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups, Ra, Rb, Rc, and Rd may have a substituent, x is an integer of 4 to 20, y is an integer of 0-15, z is an integer of 1-15.]

Here, as a repeating structure of the alkyleneoxy group of Ra in Formula (V), what originates in propylene triol, glycerin, pentaerythritol, etc., for example, As a repeating structure of an aryleneoxy group, it is fatigue, for example Those derived from galol, 1,3,5-benzenetriol, etc. can be illustrated, respectively. Moreover, it is preferable that carbon number of the alkylene group of Rb and Rc is 1-5 each independently, and it is preferable that the (meth) acryloyloxy group in Rd is 1-7. Moreover, it is preferable that x is 4-15, y is 1-10, and z is 1-10, respectively.

In addition, Ra is a 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. Moreover, as Rd, it is especially preferable that each is a following formula.

[Formula 4]

Moreover, as said epoxy (meth) acrylates, specifically, (meth) acrylic acid or the above-mentioned hydroxy (meth) acrylate compound, and (poly) ethylene glycol polyglycidyl ether, for example. , (Poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly Aliphatic polyepoxy compounds, such as hexamethylene glycol polyglycidyl ether, (poly) trimethylol propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, and (poly) sorbitol polyglycidyl ether, Rooms, such as a volac poly epoxy compound, a brominated phenol novolac poly epoxy compound, (o-, m-, p-) cresol novolac poly epoxy compound, a bisphenol A poly epoxy compound, and a bisphenol F poly epoxy compound Of polyepoxy compounds such as heterocyclic polyepoxy compounds, such as a group polyepoxy compound, sorbitan polyglycidyl ether, triglycidyl isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate Reactants and the like.

Moreover, as other ethylenically unsaturated group containing compound, For example, (meth) acrylamides, such as ethylenebis (meth) acrylamide, allyl ester, such as diallyl phthalate, and vinyl group containing compound, such as divinyl phthalate, etc. Logistics, thioether bond-containing compounds which improved the crosslinking rate by sulfiding ether bonds of ethylenically unsaturated compounds containing ether bonds with phosphorus penta sulfide and the like and converting them into thioether bonds, and Japanese Patent Nos. Polyfunctional (meth) acrylate compound described in Japanese Patent Application Laid-Open No. 9-100111, etc., and a 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 dispersion organosilica sol ("MEK-ST" by Nissan Chemical Co., Ltd.), methyl isobutyl ketone dispersion organosilica sol (made by Nissan Chemical Co., Ltd.) Of `` MIBK-ST '') and the like] to a ethylenically unsaturated compound such as a compound obtained by using an isocyanate group or a mercapto group-containing silane coupling agent to react with a silica sol through a silane coupling agent to bind The compound which improved the strength and heat resistance as a cargo, etc. are mentioned.

The said ethylenically unsaturated group containing compound may be used independently, respectively and 2 or more types may be used together. In this invention, ester (meth) acrylates, (meth) acryloyloxy group containing phosphates, or urethane (meth) acrylates are preferable as an ethylenically unsaturated group containing compound which is the above (A) component, Ester (meth) acrylates are particularly preferable, and among these ester (meth) acrylates, polyoxyalkylene groups such as polyethylene glycol, polypropylene glycol, or polyethylene oxide adducts of bisphenol A are contained, and (meth) More preferred are ester (meth) acrylates containing two or more acryloyloxy groups.

[1-2] (B) Photopolymerization Initiator

[1-2-1] (B) essential components of a photopolymerization initiator

The photoinitiator which is (B) component which comprises the photosensitive composition of this invention generate | occur | produces active species, such as a radical, an acid, or a base, when the photosensitive composition is irradiated with actinic light, and is ethylenic which is said (A) component It is an active compound that leads to polymerization of an unsaturated group-containing compound. In the 1st photosensitive composition of this invention, it is essential to contain the photoinitiator which has a specific structure (General formula (I)) and is 0.001 micrometer-150 micrometers of average particle diameters. In the 2nd photosensitive composition of this invention, it is essential to contain the photoinitiator which has a specific structure mentioned later and has an absorption maximum in the wavelength range of 340-430 nm.

[1-2-1-1] (B) Average particle diameter of essential components of photopolymerization initiator

The photoinitiator which has the said "specific structure" contains the compound well-known in the said patent documents 1-6. In the present invention, the average particle diameter of the photopolymerization initiator is 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. Especially, since it is 2 micrometers or less, it becomes the thing excellent in the sensitivity of the photosensitive composition. It is considered that this is because a sufficient amount of the photopolymerization initiator is uniformly dispersed in the photosensitive composition, resulting in a high light absorption efficiency and a composition that is uniformly photosensitive. Moreover, it is also excellent in the point which can suppress the precipitation and crystallization of the photoinitiator in time progress of a photosensitive composition. That is, the 1st photosensitive composition of this invention presupposes that it is poorly soluble with respect to a solvent. This is because in solubility, a photopolymerization initiator having a particle diameter is not present in the composition. In addition, the average particle diameter prescribed | regulated by this invention means a weight average particle diameter or a number average particle diameter, and it can measure by a well-known measuring method. The measured value by any of a weight average particle diameter or a number average particle diameter can achieve the objective of this invention.

In this invention, the method for making the average particle diameter of the said photoinitiator into 0.001 micrometer or more and 150 micrometers or less is not specifically limited, For example, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, It is preferable to disperse | distribute using a pico mill, a homogenizer, etc. In the dispersion treatment, a coating liquid, an organic binder having a dispersing function, or a surfactant such as a nonionic, a cation or an anion, a polymer dispersant or the like is suitably used in combination as described in JP 2005-128483 A. It is preferable to process. Especially, a sand grinder is mentioned as a preferable dispersion process.

As the beads for dispersion, 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 (temperature) is 0-100 degreeC normally, Preferably it is the range of room temperature to 80 degreeC. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the dispersion solution, the device size of the sand grinder, and the like.

[1-2-1-2] Wavelength range of absorption maximum of essential components of photopolymerization initiator

As an absorption wavelength region of the said photoinitiator which comprises the photosensitive composition of this invention, when it is a blue violet semiconductor laser, 340 nm or more, Preferably it is 345 nm or more, More preferably, 350 nm or more, Especially preferably, 355 nm It is above, and it is preferable to have absorption maximum in 430 nm or less, Preferably it is 415 nm or less. When the absorption maximum is excessively biased toward the long wavelength side, it becomes easy to be exposed under the yellow light and the safety light is lowered, or when the transparency of the photosensitive composition layer is increased so as not to be exposed even under the yellow light, it becomes difficult to absorb the blue-violet laser light. Is lowered. On the other hand, if the absorption maximum is excessively biased toward the short wavelength side, the irradiated light energy cannot be used efficiently for the photopolymerization reaction, resulting in a reduction degree. The second photosensitive composition of the present invention is characterized in the wavelength range of absorption maximum described above, and the solubility (ie, poor solubility, solubility) in a solvent does not matter. In the oxime initiator which is an essential component of the photoinitiator mentioned later, what has the absorption maximum mentioned above is generally poorly soluble in a solvent. For example, the compound group which has some alkyloxyl group or long-chain alkyloxyl group, such as (X-20) and (X-22) illustrated later, may show solubility.

On the other hand, the maximum absorption of the photopolymerization initiator can be easily obtained 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 ^{to 5} mol by using an ordinary ultraviolet or visible light absorption spectrum meter. .

[1-2-1-3] (B) Structure of essential components of photopolymerization initiator

Moreover, the said photoinitiator which concerns on the photosensitive composition of this invention is characterized by the following general formula (I).

[Formula 5]

(In formula, R <^2> may respectively be a C2-C20 alkanoyl group, a C3-C25 alkenoyl group, a C3-C8 cycloalkanoyl group, a C7-C20 benzoyl group, and C2-C20. 10 alkoxycarbonyl group, a C7-20 phenoxycarbonyl group, a C1-C20 heteroaryl group, a C1-C20 heteroaryloyl group, or a C1-C20 aminocarbonyl group is shown.

X and Y each independently represent an arbitrary substituent)

Here, the alkanoyl group is substituted with the substituent described in [1-3-1-6], and an alkoxycarbonyl alkanoyl group, a phenoxycarbonyl alkanoyl group, and a heteroaryloxycarbonyl alkanoyl group are also mentioned. Included.

Preferred compounds among the compounds having the structure of general formula (I) are compounds represented by general formula (II).

[Formula 6]

(In formula, R <^1> represents a hydrogen atom, a C1-C20 alkyl group which may be substituted, respectively, a C2-C20 alkenyl group, or the following general formula (IIa).

[Formula 7]

(In formula, R <^2>' , R <^3' , R <^4>' , R <^5>' , R <^6>' and R <^7>' are R <^2> , R in general formula (II) each independently of general formula (II). Same as ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ )

R <^2> may respectively be a C2-C12 alkanoyl group, a C4-C6 alkenyl group, a C7-C20 benzoyl group, a C2-C6 alkoxycarbonyl group, and a C7-C20 phenoxycarbonyl group Indicates.

R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, an alkenoyl group having 3 to 12 carbon atoms, and 1 to 12 carbon atoms. Alkoxy group, C3-C15 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C12 alkoxycarbonyl group, C7-C20 phenoxycarbonyl group, or -OR ⁸ , -SR ⁹ , -SOR ⁹ , -SO ₂ R ⁹ or -NR ¹⁰ R ¹¹ , wherein 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 .

Provided that R ⁸ is a hydrogen atom, an 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, an alkenyl group having 3 to 6 carbon atoms and a 3 to 15 carbon atoms A cycloalkyl group, a phenyl group,-(CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20) or an alkylsilyl group having 3 to 20 carbon atoms.

R <^9> represents a hydrogen atom, a C1-C12 alkyl group which may be substituted, a C3-C12 alkenyl group, a C3-C15 cycloalkyl group, or a phenyl group, respectively.

R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, and a hydroxy having 2 to 4 carbon atoms. An alkyl group, a C2-C10 alkoxyalkyl group, a C3-C5 alkenyl group, a C3-C15 cycloalkyl group, a phenyl group, a benzoyl group, a C7-C20 phenylalkyl group, a biphenyl group may be shown, or may mutually substitute. You may couple | bond with the C2-C6 alkylene group.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure.)

More preferable compounds are compounds represented by the following general formula (III).

[Formula 8]

(Wherein, R ¹ and R ^2, each R ¹ and R ² in the formula (Ⅱ) Same meaning as

R ^{3 '} , R ^6' And R ^{7 '} Are each independently a hydrogen atom, a halogen atom, an 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, A benzyl group, a benzoyl group, a C2-C12 alkanoyl group, a C2-C12 alkoxycarbonyl group, or a C7-C20 phenoxycarbonyl group is shown.

R ¹² , R ¹³ , R ^14, and R ¹⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, an alkenoyl group having 2 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. , A cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a phenoxycarbonyl group, an amide group or a nitro group having 7 to 20 carbon atoms. .)

[1-2-1-3-1] substituent R ¹

R ¹ preferably represents a hydrogen atom, an alkyl group or aminoalkyl group having 1 to 12 carbon atoms which may be substituted, or an alkenyl group having 2 to 12 carbon atoms.

More preferably, they represent a hydrogen atom, the C1-C8 alkyl group or aminoalkyl group which may be substituted, respectively, or a C2-C8 alkenyl group.

[1-2-1-3-2] substituent R ²

R ² is preferably an alkanoyl group having 2 to 8 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group having 7 to 15 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and having 7 to 15 carbon atoms A phenoxycarbonyl group is shown.

More preferably, a C2-C5 alkanoyl group, a C4-C6 alkenyl group, a C7-C12 benzoyl group, a C2-C4 alkoxycarbonyl group, and a C7-C10 phenoxycarbonyl group may respectively be substituted. Indicates.

Meanwhile, R ² The "benzoyl group" defined in the above is one or more -OR ⁸ , -SR ⁹ , -SOR ⁹ , -SO ₂ R ⁹ , and / or in addition to the substituents described in [1-2-1-3-9]. Also included are those substituted by -NR ¹⁰ R ¹¹ .

[1-2-1-3-3] substituents R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, an alkenoyl group having 3 to 8 carbon atoms, and carbon atoms An alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a phenoxycarbonyl group having 7 to 8 carbon atoms, or -OR ⁸ , -SR ⁹ , -SOR ⁹ , -SO ₂ R ⁹ or -NR ¹⁰ R ¹¹ , wherein at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is selected from -OR ⁸ , -SR ⁹ or -NR ¹⁰ R ¹¹ may be represented and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure.

More preferably, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenoyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, Phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C5 alkoxycarbonyl group, C7-C10 phenoxycarbonyl group or -OR ⁸ , -SR ⁹ , -SOR ⁹ , -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 represents -OR ⁸ , -SR ⁹ or -NR ¹⁰ R ¹¹ , and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure.

In addition, the "phenyl group" defined by R <^3> , R <^4> , R <^5> , R <^6> and R < ⁷ > is respectively one or more -OR <^8> , -SR other than the substituent as described in [1-2-1-3-9]. ^And those substituted by ⁹ , -SOR ⁹ , -SO ₂ R ⁹ , and / or -NR ¹⁰ R ¹¹ .

Also, -OR ⁸ , -SR ⁹ Or —NR ¹⁰ R ¹¹ is R ⁸ , R ⁹ , R ¹⁰ and / or R ¹¹ May be bonded to each other to form a ring structure, and the ring structure is preferably a 5-membered ring or a 6-membered ring.

[1-2-1-3-4] substituent R ⁸

R ⁸ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenylalkyl group which may be substituted, alkanoyl group having 2 to 6 carbon atoms, alkenyl group having 3 to 8 carbon atoms, alkenoyl group having 3 to 6 carbon atoms, A cycloalkyl group having 5 to 8 carbon atoms, a phenyl group,-(CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20) or an alkylsilyl group having 3 to 15 carbon atoms.

More preferably, a hydrogen atom, a C1-C10 alkyl group or phenylalkyl group which may be substituted, a C2-C4 alkanoyl group, a C3-C6 alkenyl group, a C3-C4 alkenoyl group, C5-C5 6 represents a cycloalkyl group, a phenyl group,-(CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20) or an alkylsilyl group of 3 to 12 carbon atoms.

Meanwhile, R ⁸ "Alkyl group", which is defined in, in addition to the substituents described in [1-2-1-3-9], and include those that are substituted by one or more ^{-OR 16 CN, -OR 17 (CO} ) OR 18.

On the other hand, R ^16, R ¹⁷ are, each independently, an alkylene group having 1 to 4 carbon atoms which may have a substituent, preferably represents an ethylene group, R is ¹⁸ carbon atoms which may have a substituent 1 to 8, preferably C1-C4 alkyl group is shown.

R ⁸ In addition to being substituted by the substituent as described in [1-2-1-3-9], the "phenyl group" defined in these includes what is represented by following formula (IV).

[Formula 9]

(In formula, R <^1> , R <^2> , R <^3> , R <^4> , R <^6> and R <^7> are synonymous with the said Formula (II), respectively.

M ¹ is a direct bond, an ether group, a sulfide group, a C1-C12 alkylene group, a C1-C12 cycloalkenylene group, a C1-C12 alkenylene group, a phenylene group, a biphenylene group, or a ter Phenylene, naphthylene, -NR ¹⁰ -,-(CO) OR ^16a -O (CO)-,-(CO) O- (CH ₂ CH ₂ O) m- (CO)-(m is an integer of 1 or more) ),-(CO) -R ^16b- (CO)-, or an alkyleneoxy group having 1 to 12 carbon atoms, -R ^17a -S-, a piperazino group, or -R ^17b -NH-. In addition, these may be a plurality of combinations, and each may have a substituent.

On the other hand, R ^16a and R ^16b are each independently an alkylene group having 2 to 12 carbon atoms which may be substituted, and R ^17a and R ^17b are each independently an alkylene group having 1 to 12 carbon atoms which may be substituted)

[1-2-1-3-5] substituent R ⁹

R ⁹ preferably represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenylalkyl group, an alkenyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a phenyl group, each of which may be substituted.

More preferably, they represent a hydrogen atom, a C1-C10 alkyl group or phenylalkyl group which may be substituted, a C3-C4 alkenyl group, a C5-C6 cycloalkyl group, or a phenyl group, respectively.

Meanwhile, R ⁹ "Alkyl group", which is defined in, in addition to the substituents described in [1-2-1-3-9], and include those that are substituted by one or more ^{-OR 16 CN, -OR 17 (CO} ) OR 18.

On the other hand, R ^16, R ¹⁷ are, independently of one another, an alkylene group having 1 to 4 carbon atoms that may be substituted, and preferably represents an ethylene group, R ¹⁸ is the group having 1 to 8 carbon atoms, preferably optionally substituted C 1 is The alkyl group of -4 is shown.

In addition, R ⁹ The "phenyl group" defined in these is substituted with the substituent as described in [1-2-1-3-9], and the thing represented by said formula (IV) is also included.

[1-2-1-3-6] Substituents R ¹⁰ and R ¹¹

R ¹⁰ and R ¹¹ are preferably independently of each other a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, alkanoyl group having 2 to 8 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms and 3 to 5 carbon atoms The alkenyl group, a C5-C8 cycloalkyl group, a phenyl group, a benzoyl group, or a biphenyl group may be shown, or may be couple | bonded through the C2-C6 alkylene group which may be mutually substituted. Moreover, it is more preferable that the said C1-C8 alkyl group is unsubstituted or substituted by the hydroxyl group, the alkoxy group, and the phenyl group.

More preferably R ¹⁰ and R ¹¹ Are independently of each other a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, an alkenoyl group having 3 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms and a 5 to 6 carbon atoms The cycloalkyl group, the phenyl group, the benzoyl group, or the biphenyl group may be represented or may be bonded via an alkylene group having 2 to 6 carbon atoms which may be substituted with each other. Moreover, it is more preferable that the said C1-C8 alkyl group is unsubstituted or substituted by the hydroxyl group, the alkoxy group, and the phenyl group.

Meanwhile, R ¹⁰ The "phenyl group" defined in these is substituted with the substituent as described in [1-2-1-3-9], and the thing represented by said formula (IV) is also included.

[1-2-1-3-7] Substituents R ^{3 '} , R ^6' and R ^{7 '}

R ^{3 '} , R ^6' and R ^{7 '} are preferably, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, an alkenoyl group having 3 to 8 carbon atoms, and 1 to 8 carbon atoms. An alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a phenoxycarbonyl group having 7 to 10 carbon atoms.

More preferably, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, A phenyl group, a benzyl group, a benzoyl group, a C2-C6 alkanoyl group, a C2-C6 alkoxycarbonyl group, or a C7-C8 phenoxycarbonyl group is shown.

[1-2-1-3-8] substituents R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ As to

R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ Preferably, independently of each other, a hydrogen atom, a halogen atom, a C1-C8 alkyl group which may be substituted, a C3-C8 alkenoyl group, a C1-C8 alkoxy group, a C5-C8 cycloalkyl group , A phenyl group, benzyl group, benzoyl group, a C2-C8 alkanoyl group, a C2-C12 alkoxycarbonyl group, or a C7-C10 phenoxycarbonyl group.

More preferably, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted, an alkenoyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, A phenyl group, a benzyl group, a benzoyl group, a C2-C6 alkanoyl group, a C2-C6 alkoxycarbonyl group, or a C7-C8 phenoxycarbonyl group is shown.

[1-2-1-3-9] Substituents which may be substituted respectively

In the general formulas (I) to (III) related to the present invention, each of R ¹ to R ¹⁵ and R ^{3 'to} R ^7' may be independently substituted with a fluorine atom, a chlorine atom, Halogen atoms such as bromine and iodine; Hydroxyl group; Thiol group; Nitro group; Cyano group; Arbitrary organic groups etc. are mentioned. As an arbitrary organic group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group, n-heptyl group C1-C18 linear or branched alkyl groups, such as a n-octyl group and t-octyl group; Cycloalkyl groups having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyloxy group, t-amyloxy group, n-hexyloxy group, n- Linear or branched alkoxy groups having 1 to 18 carbon atoms such as heptyloxy group, n-octyloxy group and t-octyloxy group; Methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hex C1-C18 linear or branched alkylthio groups, such as a silthio group, n-heptylthio group, n-octylthio group, and t-octylthio group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; Aralkyl groups having 7 to 18 carbon atoms such as a benzyl group and a phenethyl group; Linear or branched alkenyloxy groups having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group and hexenyloxy group; Linear or branched alkenylthio groups having 2 to 18 carbon atoms such as vinylthio group, propenylthio group and hexenylthio group; -COR ¹⁹ Acyl group represented by; Carboxyl groups; An acyloxy group represented by -OCOR ²⁰ ; Amino group represented by -NR ²¹ R ²² ; Acylamino group represented by -NHCOR ²³ ; Carbamate groups represented by -NHCOOR ²⁴ ; Carbamoyl group represented by -CONR ²⁵ R ²⁶ ; Carboxylic acid ester group represented by -COOR ²⁷ ; Sulfamoyl groups represented by -SO ₃ NR ²⁸ R ²⁹ ; Sulfonic acid ester group represented by -SO ₃ R ³⁰ ; Saturation such as 2-thienyl group, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophenedioxide group or the like Trialkyl silyl groups, such as an unsaturated heterocyclic group and a trimethylsilyl group, etc. are mentioned.

On the other hand, R ¹⁹ to R ³⁰ Represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, or an aralkyl group which may be substituted, respectively. These positional relationship is not specifically limited, When it has a some substituent, they may be the same or different.

Further, the substituent of the present invention, In addition, there may be mentioned a substituent such as = N-OC (= O) R 2. As such a compound, R <^1> is a C1-C20 alkyl group substituted with = N-OC (= O) R <^2> , a C5-C8 cycloalkyl group, a C2-C20 alkanoyl group, and C7-C20 May be a benzoyl group, a C2-C12 alkoxycarbonyl group or a phenoxycarbonyl group, or a C1-C20 amide group.

In the above, the substituent may have not only the singular but also the same kind and / or a plurality of substituents, and 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 heterocycle. , You may further have a substituent on a ring and a substituent may also form a ring further.

The specific example of the preferable compound of this invention is shown below.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

As mentioned above, the said photoinitiator which concerns on this invention contains the compound well-known in itself, For example, it can use suitably in the compound of patent documents 1-6 mentioned above.

On the other hand, the essential component of (B) photoinitiator which comprises the photosensitive composition of this invention contains 10-100 weight% with respect to the whole photoinitiator, Preferably it is 50-100 weight%, More preferably, it contains 80-100 weight% do. When there are too few essential components of a photoinitiator, it will be easy to produce a sensitivity fall.

[1-2-2] (B) Arbitrary component of photoinitiator

Although the photoinitiator which is (B) component which comprises the photosensitive composition of this invention can be used independently of said photoinitiator, it is also possible to use together other photoinitiator as needed.

As other photoinitiators, for example, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, hexaarylbiimidazoles, titanocenes, halogenated hydrocarbon derivatives, for example And organic boron salts, organic peroxides, onium salts, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanol, and oxime ester compounds soluble in a coating solvent.

Examples of the acetophenones include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and 1-hydroxy-1- (p -Dodecylphenyl) ketone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-2-methylphenylpropanone And α-aminoacetophenone described later.

Moreover, as said benzophenones, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromo Benzophenone, Michler's ketone and the like, and as the hydroxybenzenes, for example, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-benzylbenzophenone, 2 -(2-hydroxy-5-methylphenyl) benzotriazole, 4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like; As the furnace, for example, thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-di Isopropyl thioxanthone, 2-chloro thioxanthone, and the like, and as the anthraquinones, for example, 2-methylanthraquinone and the like, and as the ketals, for example, benzyldimethyl Ketal etc. are mentioned, respectively.

As the hexaarylbiimidazoles, for example, 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 ', 5,5'-tetra (o, p-dichloro Phenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- tetra (p-chloronaphthyl) biimidazole, etc. are mentioned. Especially, a hexaphenyl biimidazole compound is preferable, It is more preferable that the o-position of the benzene ring couple | bonded with the 2,2'- position on the imidazole ring substituted by the halogen atom, The 4,4 on the imidazole ring It is particularly preferable that the benzene ring bonded to the ', 5,5'- position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

As the titanocene, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopenta Dienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-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) titaniumbis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitaniumbis [2,6-difluoro-3- (1- Pyrrolyl) phenyl]. Especially, the titanium compound which has a dicyclopentadienyl structure and a biphenyl structure is preferable, and it is especially preferable that the o-position of a biphenyl ring was substituted by the halogen atom.

Examples of the halogenated hydrocarbon derivatives include halomethylated s-triazine derivatives, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (Dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 , 4-epoxyphenyl) -4,6-bis (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 (trichloromethyl)- 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-ethoxycar Bonylnaphthyl) -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 Halomethylated s-tri such as 2-methyl-4,6-bis (tribromomethyl) -s-triazine and 2-methoxy-4,6-bis (tribromomethyl) -s-triazine Azine derivatives are mentioned, and bis (trihalomethyl) -s-triazine is especially preferable.

Moreover, as said organoborate, an organic ammonium complex, an organoboron phosphonium complex, an organoboron sulfonium complex, an organoboron sulfonium complex, an organoboron iodonium complex, an organoboron transition metal coordination complex, etc. are mentioned, for example. Examples of the organoboron anion include n-butyl-triphenylboron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion and 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 anion, n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl )- Alkyl-triphenylboron anions such as small anions are preferred, and onium compounds such as ammonium cation, phosphonium cation, sulfonium cation and iodonium cation are preferred as counter cations, and organic ammonium such as tetraalkylammonium Cation is particularly preferred.

Moreover, as said organic peroxide, t-butyl benzoic acid peroxide ester, 3, 3 ', 4, 4'- tetra (t-butylperoxycarbonyl) benzophenone etc. are mentioned, for example.

Moreover, as said onium salt, ammonium salts, such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyl iodonium hexafluoro alsenate, diphenyl iodonium tetrafluoro borate, diphenyl iodonium p-toluene Sulfonate, diphenyl iodonium camphor sulfonate, dicyclohexyl iodonium hexafluoroalsenate, dicyclohexyl iodonium tetrafluoroborate, dicyclohexyl iodonium p-toluenesulfonate, dicyclohexyl iodonium camphor sulfo Iodonium salts such as nate, triphenylsulfonium hexafluoroalsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium camphorsulfonate, tricyclohexylsulfonium hexafluoro Roalsenate, tricyclohexylsulfonium tetrafluoroborate, tricyclohexylsulfonium p-toluene Sulfonium salts, such as a sulfonate and a tricyclohexyl sulfonium camphor sulfonate, etc. are mentioned.

Examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane and bis (α-naphthylsulphate). Bis (sulfonyl), such as a fonyl) methane, bis ((beta) -naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, and phenylsulfonyl (cyclohexylsulfonyl) methane Methane compounds, phenylcarbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl Carbonyl (sulfonyl) methane compounds, such as (phenylsulfonyl) methane, phenylcarbonyl (cyclohexylsulfonyl) methane, and phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) diazomethane, Bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthyl Sulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazo Methane compounds, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) Carbonyl (sulfonyl), such as crude methane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, and phenylcarbonyl (t-butylcarbonyl) diazomethane ) Diazomethane compound, etc. are mentioned.

Moreover, as said carbamic acid derivatives, for example, benzoylcyclohexylcarbamate, 2-nitrobenzylcyclohexylcarbamate, 3,5-dimethoxybenzylcyclohexylcarbamate, 3-nitrophenylcyclohexyl Carbamate etc. Moreover, as said sulfonamides, N-cyclohexyl-4-methylphenyl sulfonamide, N-cyclohexyl-2-naphthyl sulfonamide, etc. are mentioned, for example, The said triarylmethanol As examples, triphenylmethanol, tri (4-chlorophenyl) methanol, etc. are mentioned, respectively.

In addition, as said oxime ester compound, For example, it is described in Unexamined-Japanese-Patent No. 2000-80068, Specifically, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), etc. are mentioned. Can be.

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

[Formula 15]

[In 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, and 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 Each independently 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, and R ³⁴ And R ³⁵ are connected to each other, or R ³⁴ Or R ³⁵ With R ³² Or R ³³ These may be connected to each other to form a cyclic structure, and the benzene ring may have a substituent.]

Here, as an alkyl group of R <^32> , R <^33> , R <^34> and R <^{35> in} the said General formula (VI), it is preferable that it is C1-C15, especially 1-10. Moreover, as a substituent in an alkyl group, an allyl group, and a phenyl group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acetoxy alkoxy group, an alkoxyalkoxy group, an alkylcarbonylalkyl group, an alkylthio group, a haloalkyl group , A phenyl group, a halogen atom and the like. In addition, R ³⁴ And R ³⁵ are connected to each other, or R ³⁴ Or R ³⁵ With R ³² Alternatively, examples of the cyclic structure in which R ³³ is linked to each other include pyrrolidine, piperidine, piperazine, morpholine, oxazolidine, pyridine and the like.

Moreover, as a substituent in a benzene ring, an alkyl group, a hydroxyl group, an alkoxy group, an allyloxy group, a phenoxy group, a benzoyl group, a silyloxy group, a mercapto group, an alkylthio group, an allylthio group, a cycloalkylthio group, benzyl Thiothio, phenylthio group, alkylsulfonyl group, phenylsulfonyl group, alkylsulfinyl group, alkylamino group, allylamino group, pyrrolidinyl group, piperazinyl group, piperazinyl group, morpholinyl group, halogen atom and the like In addition, the benzene ring may form a condensed ring, and as the condensed ring, fluorenone, dibenzosuberon, indolin, quinoxaline, carbazole, phenazine, acridanone, benzodioxol, benzo Furan, xanthene, xanthone, phenoxazine, benzothiazole, phenothiazine and the like.

Specific examples of the α-aminoacetophenone derivative represented by the above general formula (VI) include the following compounds, which are classified by the basic skeleton of the compound and exemplified for each carbon number thereof. Among these, particularly preferred are R ³² and R ^33. Each independently represents a methyl group, an ethyl group, or a benzyl group, and R ³⁴ With R ³⁵ Is a methyl group or a morpholino group each connected to each other to form a cyclic structure, and the benzene ring is an unsubstituted or substituted compound having a methylthio group, a dimethylamino group, or a morpholino group, particularly preferably p It is a compound which has a morpholino group only in a position.

As propane-1-one classified into carbon number 3 of the basic skeleton of 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-dimethoxyphenyl ) -Propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylthiophenyl) -propane-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-2- 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) -propane-1-one, 1-phenyl-2-dimethylamino-2-benzyl-propane-1-one, 1, 3-diphenyl-2-dimethylamino-2-benzyl-propane-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-propane-1-one, 1- (4- Fluorophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-benzoylphenyl) -2-dimethylamino-2-benzyl-propan-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 , 1,3-bis (4-methylthiope ) -2-dimethylamino-2-methyl-propan-1-one, 1- (4-butylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4 -Cyclohexylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane-1-one, 1- (4-benzylthiophenyl) -2-dimethylamino-2-benzyl-propane-1-one , 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-propane-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane -1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (2-chloropentenyl) -propane-1-one, 1- (4-morpholinophenyl) -2- Dimethylamino-2-benzyl-propane-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane-1-one, 1- (N-methylyn Dolin-5-yl) -2-dimethylamino-2-benzyl-propan-1-one, 1- (N-butylphenoxazin-2-yl) -2-morpholino-2-benzyl-propane-1- On etc. can be mentioned.

As butan-1-one classified into carbon number 4 of the basic skeleton of general formula (VI), 1-phenyl-2-dimethylamino-2-benzyl-butan-1-one and 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-meth 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-dimethylamino-2-benzyl -Butan-1-one, 1- (4-ethoxycarbonylmethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (1,1,2-trimethylpropyl Dimethylsilyloxy) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- ( 4-claw Rophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,4-dichlorophenyl) -2-dimethylamino-2-benzyl-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-butan-1-one, 1- (4-methylthiophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butan-1-one, 1- [4- (2-methoxyethylthio) phenyl] -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-dimethylami 2-benzyl-butan-1-one, 1- (4-benzenesulfonylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylsulfinylphenyl) -2- Dimethylamino-2-benzyl-butan-1-one, 1- (4-aminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-methylaminophenyl) -2-dimethyl Amino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethyl Amino-2- (4-methylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (1-chloro Hexenylmethyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (2-pinene-10-yl) -butan-1-one, 1- (4-dimethyl Amino-2-methylphenyl) -2-dimethylamino-2-benzyl-butan-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- On, 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-butan-1-one, 1- [4- (N-acetyl-3-methoxypropylamino) phenyl] -2-dimethylamino-2-benzyl-butane- 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) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -part -1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-butylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethyl Amino-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) -butan-1-one, 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, 1- (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] -butan-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-morpholinophenyl) -2-dimethylamino-2- Benzyl-butan-1-one-dodecylbenzenesulfonate, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-p-toluenesulfonate, 1- (4 -Morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-camphorsulfonate, 1- (4-morpholinophenyl) -2-diethylamino-2-benzyl-butane-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) -butan-1-one , 1- (4-morpholinophenyl) -2-dibutylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2-benzyl-butane -1-one, 1- (3-chloro-4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2,6-dimethylmorpholine-4 -Yl) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,4-dimethyl-1,2,3,4-tetrahydroquinoxalin-6-yl) -2- Dimethylamino-2-benzyl-butan-1-one, 1- (N-butylcarbazol-3-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (1,3-benzo Dioxol-5-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,3-dihydrobenzofuran-5-yl) -2-dimethylamino-2-benzyl-butane -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-bene Jyl-butanoyl) -fluorenone, 2- (2-dimethylamino-2-benzyl-butanoyl) -dibenzosuberon, 3,6-di (2-dimethylamino-2-benzyl-butanoyl) -9 -Butyl-carbazole, etc. are mentioned.

As pentan-1-one classified into carbon number 5 of the basic skeleton of 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) -pentane -1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-isobutylbenzyl) -pentan-1-one, 1- (4-morpholinophenyl) -2 -Butylmethylamino-2- (4-butoxybenzyl) -pentan-l-one, etc. are mentioned.

In addition, as penten-1-one, 1-phenyl-2-dimethylamino-2-methyl-4-penten-1-one and 1-phenyl-2-dimethylamino-2-ethyl-4-penten-1-one , 1-phenyl-2-dimethylamino-2-benzyl-4-penten-l-one, 1-phenyl-2-morpholino-2-methyl-4-penten-l-one, 1-phenyl-2- Morpholino-2-benzyl-4-penten-l-one, 1,2-diphenyl-2-morpholino-4-penten-l-one, 1- (4-methylphenyl) -2-morpholino 2-methyl-4-penten-l-one, 1- (4-dodecylphenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-methoxyphenyl) -2-dibutylamino-2-methyl-4-penten-l-one, 1- (4 -Methoxyphenyl) -2-piperidino-2-ethyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-oxazolidino-2-methyl-4-pentene-1- On, 1- (4-methoxyphenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-methoxyphenyl) -2-morpholino-2-phenyl- 4-penten-l-one, 1- (3,4-dimethoxyphenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- [4- (2-methoxyethoxy ) Phenyl] -2-morpholino -2-methyl-4-penten-l-one, 1- [4- (2-methoxyethoxy) phenyl] -2-morpholino-2-ethyl-4-penten-l-one, 1- [ 4- (2-hydroxyethoxy) phenyl] -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-isopropyloxyphenyl) -2-dimethylamino-2-benzyl -4-penten-l-one, 1- (4-butyloxyphenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- [4- (2-allyloxyethoxy) Phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (2-allyloxyethoxy) phenyl] -2-morpholino-2-ethyl-4-pentene -1-one, 1- (4-trimethylsilyloxyphenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-fluorophenyl) -2-dimethylamino-2 -Methyl-4-penten-l-one, 1- (4-fluorophenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-fluorophenyl) -2- Dimethylamino-2-benzyl-4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-fluoro Phenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-4-methyl 4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-5-methyl-4-penten-l-one, 1- (4-fluorophenyl) -2-morpholino-2-benzyl-4-penten-l-one, 1- (3,4-dichlorophenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- ( 3,5-dichloro-4-methoxyphenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-bromophenyl) -2-morpholino-2-methyl 4-penten-l-one, 1- (4-bromophenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-bromophenyl) -2-mor Polyno-2-t-butyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-4-penten-l-one, 1- (4-methyl Thiophenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-phenyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-piperidino-2-ethyl-4-pentene-1 -One, 1- (4-methylthiophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl -4-penten-l-one , 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-morpholino-2 -Phenyl-4-penten-l-one, 1- (4-methylthiophenyl) -2-morpholino-2-benzyl-4-penten-l-one, 1- (4-ethylthiophenyl) -2 -Morpholino-2-ethyl-4-penten-l-one, 1- (4-isopropylthiophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4 -Allylthiophenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-methyl- 4-penten-l-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-ethyl-4-penten-l-one, 1- [4- (2- Hydroxyethylthio) phenyl] -2-morpholino-2-propyl-4-penten-l-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2- t-butyl-4-penten-l-one, 1- [4- (2-methoxycarbonylethylthio) phenyl] -2-morpholino-2-methyl-4-penten-l-one, 1- (4-methylsulfonylphenyl) -2-dimethylamino-2-ethyl-4-penten-l-one, 1- (4-butylsulfinylphenyl) -2-dimethyla No-2-ethyl-4-penten-l-one, 1- [4- (4-methylphenylthio) phenyl] -2-morpholino-2-ethyl-4-penten-l-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-l-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-methyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2- Dimethylamino-2-ethyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-4-penten-l-one, 1- (4-dimethylaminophenyl ) -2-methylphenylamino-2-ethyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2- (pyrrolidin-1-yl) -2-methyl-4-pentene-1 -One, 1- (4-dimethylaminophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-ethyl -4-methyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-benzyl-4-penten-l-one, 1- (4-dimethylaminophenyl) -2- (2,6-dimethylmorpholin-4yl) -2-ethyl-4-penten-l-one, 1- (4-diethylaminophenyl) -2-dimethylamino-2-benzyl-4-penten-l-one, 1- [4-bis (2-methoxyethyl) aminophenyl] -2-morpholino-2 -Methyl-4-penten-l-one, 1- (4-butylaminophenyl) -2-dibutylamino-2-methyl-4-penten-l-one, 1- (4-butylaminophenyl) -2 -Morpholino-2-methyl-4-penten-l-one, 1- (4-dibutylaminophenyl) -2-morpholino-2-methyl-4-penten-l-one, 1- (4 -Diallylaminophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (pyrrolidin-1-yl) phenyl] -2-morpholino-2- Methyl-4-penten-l-one, 1- (4-piperidinophenyl) -2-piperidino-2-methyl-4-penten-l-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-l-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-penten-l-one, 1- (4-morpholinophenyl) -2-dimethyl Mino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-isopropyl-4-penten-l-one, 1- (4-morpholi Nophenyl) -2-dimethylamino-2-benzyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-diethylamino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-butylmethyl Amino-2-methyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-allylmethylamino-2-ethyl-4-penten-l-one, 1- (4-morpholi Nophenyl) -2-diallylamino-2-ethyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2-ethyl-4-penten-l-one , 1- (4-morpholinophenyl) -2- (piperazin-1-yl) -2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholi No-2-methyl-4-penten-l-one, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (4-morpholi Nophenyl) -2-morpholino-2-ethyl-4-penten-l-one-dodecylbenzenesulfonate, 1- (4-morpholinofe ) -2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-benzyl-4-pentene-1 -One, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2-morpholine-2-methyl-4-penten-l-one, 1- [4- (2,6 -Dimethylmorpholin-4-yl) phenyl] -2- (2,6-dimethylmorpholin-4-yl) -2-ethyl-4-penten-l-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-l-one, 1- (N-butylcarbazol-3-yl) -2-morpholino-2-ethyl-4-penten-l-one, 1- (5,10-dibutyl-5,10-dihydrophenazin-6-yl) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (1,3-benzodi Oxol-5-yl) -2-morpholino-2-methyl-4-penten-l-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-l-one, 1- (N-methylphenothiazin-2-yl) -2- Dimethylamino-2-allyl-4-penten-l-one, 3,6-di (2-morpholino-2-methyl-4-pentenoyl) -carbazole, 2- (2-dimethylamino-2- Allyl-4-pentenoyl) -acridanone, 2- (2-morpholino-2-methyl-4-pentenoyl) -xanthone, 2- (4-morpholinobenzoyl) -2-ethyl-N -Methyl-1,2,3,6-tetrahydropyridine and the like.

As hexane-1-one classified by carbon number 6 of the basic skeleton of general formula (VI), 1- (4-methylthiophenyl) -2-morpholino-2-allyl- hexane-1-one, 1- ( 4-morpholinophenyl) -2-dimethylamino-2-benzyl-hexan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-4,5,5-trimethyl -Hexane-1-one, 1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-butylbenzyl) -hexan-1-one, 1- (4-morpholinophenyl)- 2-dioctylamino-2- (4-methylbenzyl) -hexan-1-one etc. are mentioned.

In addition, as hexen-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-hexen-1-one and 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-hexen-1-one, etc. are mentioned.

As heptane-1-one classified into carbon number 7 of the basic skeleton of general formula (VI), 1- (4-dimethylaminophenyl) -2-dimethylamino-2- [4- (2-methoxy) benzyl]- Heptane-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-heptan-1-one, and the like.

Furthermore, 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-methylthio Benzoyl) -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. are mentioned.

Octane-1-one classified by carbon number 8 of the basic skeleton of general formula (VI) as 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-octan-1-one, 1- ( 4-morpholinophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -octan-1-one, etc. are mentioned.

And the arbitrary component of the (B) photoinitiator which comprises the photosensitive composition of this invention contains 0 to 90 weight% with respect to the whole photoinitiator, Preferably it is 0 to 50 weight%, More preferably, it contains 0 to 20 weight% do.

[1-3] (C) alkali-soluble resin

As alkali-soluble resin which is (C) component which comprises the photosensitive composition of this invention, phenolic hydroxyl group containing resin, carboxyl group containing resin, etc. are mentioned. For example, polyvinyl phenol resins, phenol resins such as novolak resins and resol resins, carboxyl group-containing vinyl resins, and carboxyl group-containing epoxy resins are preferable. Among these, carboxyl group-containing vinyl resin and carboxyl group-containing epoxy resin are more preferable. When using the image forming material which apply | coated the photosensitive composition of this invention as a single-layer image forming material which does not use the overcoat especially, a carboxyl group-containing epoxy resin for the purpose of suppressing the sensitivity fall by oxygen in air, and also improving heat resistance and chemical-resistance. Is particularly preferred. Below, carboxyl group-containing vinyl resin and carboxyl group-containing epoxy resin as a preferable (C) component are explained in full detail.

[1-3-1] Carboxyl group-containing vinyl resin

Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 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) acryloyl morpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylamino (Meth) acrylamide, a copolymer of other vinyl compounds such as vinyl acetate and the like. It is preferable that these carboxyl group-containing vinyl resins are 50-300 KOH.mg/g, and it is especially preferable that they are 100-250KOH.mg/g. Moreover, it is preferable that the weight average molecular weights of polystyrene conversion are 10,000-200,000, and it is especially preferable that it is 20,000-100,000.

Among these, as a carboxyl group-containing vinyl resin contained in the photosensitive composition in this invention, it is a copolymer containing the structural repeating unit derived from ethylenic unsaturated carboxylic acids, alkyl (meth) acrylates, and styrene. desirable. As this copolymer, 10-50 weight%, 15-80 weight%, and 1-40 weight of the structural repeating unit derived from ethylenic unsaturated carboxylic acid, alkyl (meth) acrylates, and styrene, respectively. It is preferable to contain in the ratio of%, It is more preferable to contain in the ratio of 15-50 weight%, 15-80 weight%, and 1-15 weight%, respectively, It is 15-35 weight%, 30-30, respectively It is especially preferable to contain 80 weight% and 5-15 weight%.

Here, specifically, as the styrene monomer in the copolymer, for example, α-substituted alkyl styrene such as styrene, α-methyl styrene, α-ethyl styrene, o-methyl styrene, m-methyl styrene, Nuclear substituted hydroxy styrene, such as p-methylstyrene, 2, 5- dimethyl styrene, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, dihydroxy styrene, p- Nuclear substituted styrene halides, such as chloro styrene, p-bromo styrene, and dibromo styrene, etc. are mentioned. Moreover, as an acrylate ester type monomer, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl ( Meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, etc. are mentioned. Here, carbon number of (meth) acrylic acid becomes like this. Preferably it is 1-12, More preferably, it is 1-8 alkyl ester, and hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycy Substituted alkyl esters, such as dill (meth) acrylate, benzyl (meth) acrylate, aminoethyl (meth) acrylate, and N, N- dimethylaminoethyl (meth) acrylate, etc. are mentioned.

Moreover, as said copolymer, in addition to the structural repeating unit derived from each of the said styrene monomer, the (meth) acrylic acid ester monomer, and the (meth) acrylic acid monomer, for example, crotonic acid, isocrotonic acid, maleic acid, anhydride Unsaturated carboxylic acids such as maleic acid, itaconic acid, citraconic acid, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide And (meth) acrylic acid derivatives such as N, N-dimethylaminoethyl (meth) acrylamide, and structural repeating units derived from copolymerizable other monomers such as vinyl compounds such as vinyl acetate and vinyl chloride. It is preferable that content of the structural repeating unit derived from these other monomers is 10 mol% or less of the whole copolymer.

Moreover, as other carboxyl group-containing vinyl resin, carboxyl group-containing vinyl resin which has ethylenically unsaturated bond in a side chain is mentioned. As this carboxyl group-containing vinyl resin, the following are mentioned, for example.

(i) It is a reaction product obtained by making an aliphatic epoxy group containing unsaturated compound or alicyclic epoxy group containing unsaturated compound react with a carboxyl group containing polymer.

As an aliphatic epoxy group containing unsaturated compound, for example, allyl glycidyl ether, glycidyl (meth) acrylate, (alpha)-ethyl glycidyl (meth) acrylate, glycidyl crotonate, and glycidyl isochloro Tonate, crotonylglycidyl ether, monoalkyl monoalkyl monoglycidyl ester of fuconate, monoalkyl monoglycidyl ester of fumaric acid, monoalkyl monoglycidyl ester of maleic acid, and the like.

As an alicyclic epoxy group containing unsaturated compound, it is 3, 4- epoxycyclohexyl methyl (meth) acrylate, 2, 3- epoxy cyclopentyl methyl (meth) acrylate, 7,8- epoxy [tricyclo [5.2, for example] .1.0] dec-2-yl] oxymethyl (meth) acrylate, etc. are mentioned.

The proportion of the aliphatic epoxy group-containing unsaturated compound or alicyclic epoxy group-containing unsaturated compound to react is usually 5 to 90 mol%, preferably 30 to 70 mol% with respect to the carboxyl group of the carboxyl group-containing polymer.

(ii) It is a reaction product obtained by copolymerizing the compound which has 2 or more types of unsaturated groups, unsaturated carboxylic acid, such as (meth) acrylic acid, or unsaturated carboxylic acid ester further.

As a compound which has 2 or more types of unsaturated groups, for example, allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamil (meth) acrylate, and crotonyl (meth) acryl Rate, metharyl (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, etc. are mentioned.

The proportion at which the unsaturated carboxylic acid is reacted is usually 10 to 90 mol%, preferably 30 to 80 mol%, based on the entirety of the compound having an unsaturated group.

Moreover, the acrylic resin which has an ethylenic double bond in the side chain of the said carboxyl group-containing vinyl resin is also preferable. By using such acrylic resin, since the photocurability improves when using the photosensitive composition of this invention as a coloring resin composition for color filters, the resolution of a color filter and the adhesiveness of a pixel and a board | substrate can be improved further. .

As a method of introducing an ethylenic double bond into the side chain of acrylic resin, the method described in Unexamined-Japanese-Patent No. 50-34443, Unexamined-Japanese-Patent No. 50-34444, etc.,

(1) A method of reacting a carboxyl group of the acrylic resin with a compound having a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group

(2) The method of making acrylic acid chloride etc. react with the hydroxyl group which acrylic resin has is mentioned.

Specifically, (meth) acrylic acid glycidyl, allyl glycidyl ether, (alpha)-ethyl acrylate glycidyl, crotonyl glycidyl ether, (iso) crotonic acid glycidyl to acrylic resin which has a carboxyl group and a hydroxyl group By reacting compounds such as ether, (3,4-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. . Especially, what made the alicyclic epoxy compound like (3, 4- epoxycyclohexyl) methyl (meth) acrylate react with acrylic resin which has a carboxyl group or a hydroxyl group is preferable.

[1-3-2] Carboxyl group-containing epoxy resin

Specific examples of the unsaturated group and carboxyl group-containing epoxy resin include, for example, ester bonds (-CO0-) formed 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. The ethylenically unsaturated bond is added through this, and the carboxyl group which remain | survived through the ester bond formed by the carboxyl group of polyhydric carboxylic acid or its anhydride reacted with the hydroxyl group produced at that time is mentioned.

As said epoxy resin, the thing which reacted and added epichlorohydrin, epibromohydrin, hydroxymethyl epoxy, etc. with the phenol group of the said phenolic hydroxyl group containing resin with alkali or an acidic catalyst etc. is mentioned, for example. Specifically, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, a trisphenol epoxy resin, etc. are mentioned. Especially, the epoxy resin which has a phenol novolak epoxy resin, a cresol novolak epoxy resin, a biphenol fluorene diglycidyl ether, and its repeating unit is especially preferable.

Moreover, as said (alpha), (beta)-unsaturated monocarboxylic acid, it is (meth) acrylic acid, crotonic acid, a maleic acid, fumaric acid, itaconic acid, a citraconic acid, a pentaerythritol tri (meth) acrylate succinic anhydride, for example. Additives, pentaerythritol tri (meth) acrylate tetrahydro phthalic anhydride, dipentaerythritol penta (meth) acrylate succinic anhydride, dipentaerythritol penta (meth) acrylate phthalic anhydride, di Pentaerythritol penta (meth) acrylate tetrahydro phthalic anhydride, and the reaction product of (meth) acrylic acid and (epsilon) -caprolactone, etc. are mentioned. Among them, (meth) acrylic acid is particularly preferable.

Moreover, as said polyhydric carboxylic acid or its anhydride, Specifically, succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyl tetrahydrophthalic acid, 4-methyl tetrahydrophthalic acid, 3-ethyl tetrahydrophthalic acid, 4-ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, anhydrides thereof, and the like. Can be mentioned. Especially, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferable, and tetrahydrophthalic anhydride is especially preferable.

In view of sensitivity, resolution, and adhesion to a substrate as a photosensitive composition, in the present invention, the epoxy resin is a phenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, trisphenol A novolak resin, a bisphenol A novolak resin, a polycondensation resin of triphenol and epichlorohydrin, a biphenol fluorene diglycidyl ether and an epoxy resin having a repeating unit thereof, and α, β-unsaturated monocarboxylic acid It is especially preferable that it is (meth) acrylic acid, and polyhydric carboxylic acid or its anhydride is tetrahydrophthalic anhydride or succinic anhydride. Specifically, after adding a pentaerythritol tri (meth) acrylate tetrahydro phthalic anhydride adduct to biphenol fluorene diglycidyl ether, the thing which ring-opened addition of tetrahydrophthalic anhydride is mentioned, for example. Can be. In addition, the pentaerythritol tri (meth) acrylate tetrahydro phthalic anhydride has a structure in which a (meth) acrylate group is partially added and reacted.

And it is preferable that it is 20-200 mg.KOH / g, and it is still more preferable that it is 30-180 mg.KOH / g. Moreover, it is preferable that the weight average molecular weights by gel permeation chromatography are 2,000-200,000, and it is more preferable that it is 3,000-150,000.

The said unsaturated group and carboxyl group-containing epoxy resin in this invention can be manufactured by a conventionally well-known method. Specifically, the epoxy resin is dissolved in organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Subsequently, tertiary amines such as triethylamine, benzyldimethylamine, tribenzylamine, quaternary such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and trimethylbenzylammonium chloride Reaction is carried out in the presence of a catalyst such as phosphorus compounds such as ammonium salts and triphenylphosphine, or styrenes such as triphenylstyrene, and coexistence of thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether and methylhydroquinone. Let's do it. Reaction adds the said (alpha), (beta)-unsaturated monocarboxylic acid normally in the amount which becomes 0.7-1.3 chemical equivalent, Preferably it is 0.9-1.1 chemical equivalent with respect to 1 chemical equivalent of the epoxy group of an epoxy resin, Usually 60- The addition reaction is carried out at a temperature of 150 ° C, preferably 80 to 120 ° C. Subsequently, polyhydric carboxylic acid or its anhydride is added in an amount of usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to one chemical equivalent of the hydroxyl group formed in the reaction, and the reaction is continued under the above conditions. do.

The specific example of the structural repeating unit of the unsaturated group and carboxyl group-containing epoxy resin as (C) component is shown below.

[Formula 16]

And the unsaturated group and carboxyl group-containing epoxy resin as (C) component are urethane bonds, a siloxane bond, or the like, in order to provide flexibility to the resist obtained in the use which requires cut resistance, such as a flexible wiring board. You may introduce a polyacrylonitrile butadiene structure.

As a method of introducing the urethane bond, for example, as described in JP-A-2003-155320, an epoxy resin and an α, β-unsaturated monocarboxylic acid are reacted, such as isophorone diisocyanate. The method of introducing the urethane bond obtained by making polyfunctional isocyanate react is mentioned. Furthermore, the compound obtained by the said method is further reacted with the carboxylic acid which has two hydroxyl groups in a molecule | numerator, unsaturated group containing carboxylic acid, or monovalent or polyhydric acid anhydride, such as 2-dimethylol propionic acid, as needed. You can also do it.

As an example of resin in which the said urethane bond was introduce | transduced, the urethane modified resin of bisphenol A or bisphenol F is mentioned. Specifically, "UEX3002" (acid value 100), "UEX3009" (acid value 60) by Nippon Kayaku Co., Ltd., etc. are mentioned.

As a method of introducing the siloxane bond, a method of reacting mono or diaminosiloxane, mono or dimercaptodimethylsiloxane with the epoxy group of the epoxy resin is mentioned. Moreover, you may make the compound obtained by the said method react with unsaturated group containing carboxylic acid or monovalent or polyvalent acid anhydride further as needed.

As a method of introducing the polyacrylonitrile-butadiene structure, there may be mentioned a method of reacting an acrylonitrile-butadiene copolymer in which both ends are carboxylic acid-modified to an epoxy group of an epoxy resin. Thereby, a rubber characteristic can be provided. Moreover, you may make the compound obtained by the said method react with unsaturated group containing carboxylic acid or monovalent or polyvalent acid anhydride further as needed.

[1-3-3] other preferred resins

As alkali-soluble resin which is another preferable (C) component, polyvinyl phenol resin, novolak resin, and other phenolic hydroxyl group containing resin are mentioned.

As polyvinyl phenol resin, p-hydroxy ((alpha) -methyl) styrene, for example, "((alpha) -methyl) styrene" shall mean "styrene" and / or "(alpha) -methylstyrene" here. .] And copolymers of (α-methyl) styrene.

As a novolak resin and other phenolic hydroxyl group containing resin, For example, 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, resor At least one kind of phenols such as lecinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, florogulusinol, and triphenolmethane is subjected to alkali or acid catalyst, for example, formaldehyde, paraform Aldehydes such as aldehydes, acetaldehydes, paraaldehydes, propionaldehydes, benzaldehydes, and furfural, or ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, epichlorohydrin, epibromohydrin, and hydroxymethyl epoxyoxy Of unsaturated polycyclic hydrocarbons such as an epoxy compound having a leaving group such as dicyclopentadiene Even can be given to each, by 1 species and condensation.

It is preferable that the weight average molecular weights of these phenolic hydroxyl group containing resins are 1,500-50,000.

In addition, in this invention, even if alkali-soluble resin which is (C) component contains alkali-soluble resin other than alkali-soluble resin as described in said [1-3-1]-[1-3-3] further, do. As alkali-soluble resin, For example, sole, such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Or a copolymer and polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinylpyrrolidone, acetyl cellulose and the like. Especially, carboxyl group-containing vinyl resin is preferable at the point of alkali developability.

Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 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) acryloyl morpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylami Ethyl (meth) acrylamide, a copolymer of vinyl compounds such as vinyl acetate and the like.

Among these, styrene- (meth) acrylate- (meth) acrylic acid copolymers are preferable, and each comprises 3 to 30 mol% of styrene, 10 to 70 mol% of (meth) acrylate, and 10 to 60 mol% of (meth) acrylic acid. Copolymers are more preferred. In particular, the copolymer which consists of 5-25 mol% of styrene, 20-60 mol% of (meth) acrylates, and 15-55 mol% of (meth) acrylic acid is preferable. Moreover, it is preferable that these carboxyl group-containing vinyl resins have an acid value of 30-250 mg.KOH / g, and the weight average molecular weights of polystyrene conversion are 1,000-300,000.

And as said carboxyl group-containing vinyl resin, it is preferable to have ethylenically unsaturated bond in a side chain. Specifically, for example, allylglycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, and glycidyl isoalkyl are used in the carboxyl group-containing polymer. Aliphatic epoxy group-containing unsaturated compounds such as crotonate, crotonylglycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, or 3 , 4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] decyl-2-yl] oxymethyl (meth 5 to 90 mol%, preferably 30 to 70 mol%, of an cyclic group-containing unsaturated compound such as acrylate, of the carboxyl group-containing polymer, and an allyl (meth) acrylate. , 3- Allyloxy-2-hydroxypropyl (meth) acrylate, cinnamil (meth) acrylate, crotonyl (meth) acrylate, metharyl (meth) acrylate, N, N-diallyl (meth) acrylamide, etc. Compound having 2 or more types of unsaturated groups, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl The ratio which occupies the compound which has 2 or more types of unsaturated groups, such as a tonate and vinyl (meth) acrylamide, and unsaturated carboxylic acid, such as (meth) acrylic acid, or unsaturated carboxylic acid ester in the whole compound which has an unsaturated group of the former. The reaction product obtained by copolymerizing to 10-90 mol%, Preferably it is about 30-80 mol%, etc. are mentioned.

And as alkali-soluble resins other than the said unsaturated group and carboxyl group-containing epoxy resin, it is an application which requires a corrosion resistance, such as a flexible wiring board, and epoxy-acrylonitrile butadiene copolymer resin which modified | denatured both the terminal and the both terminal is epoxy Modified dimethylsiloxane resin can be mentioned. And the hydroxyl group of phenol resins, such as the hydroxyl group of hydroxyl-containing (meth) acrylates, such as pentaerythritol triacrylate, as described in Unexamined-Japanese-Patent No. 10-142791, etc., or a phenol novolak resin, for example. And a phenol resin incorporating a urethane bond obtained by reacting polyfunctional isocyanate such as isophorone diisocyanate.

In the photosensitive composition of this invention, each content rate of the ethylenically unsaturated group containing compound which is the said (A) component, the photoinitiator which is the said (B) component, and alkali-soluble resin which is the said (C) component is based on the total amount of the photosensitive composition. It is preferable that (A) component is 1-70 weight%, (B) component is 0.001-50 weight%, (C) component is 5-70 weight%, (A) component is 5-50 weight%, It is further more preferable that (B) component is 0.01-20 weight%, and (C) component is 10-50 weight%.

When there is too little each said component, there exists a tendency for the sensitivity, photocurability, etc. as a composition to fall. On the other hand, when there are too many said each components, there exists a tendency for the problem that the tackiness as a composition becomes inadequate or substrate contamination arises at the time of image development.

[1-4] Other Ingredients

In addition to the component of that excepting the above, the photosensitive composition of this invention may contain the following component further.

[1-4-1] (D) Epoxy Compound

It is preferable that the photosensitive composition of this invention contains the epoxy compound which is (D) component for the purpose of the strength improvement of a photocured film, the heat resistance improvement, etc. other than the said (A)-(C) component. As an epoxy compound which is (D) component, the polyglycidyl ether compound, the polycarboxylic acid compound, and epichloro which are obtained by making a polyhydroxy compound and epichlorohydrin which comprise the repeating unit of what is called an epoxy resin react, It is a polyglycidyl ester compound obtained by making a hydrin react, and a polyglycidyl amine compound obtained by making an epichlorohydrin react with a polyamine compound.

As said epoxy compound, the diglycidyl ether type epoxy of polyethyleneglycol, the diglycidyl ether type epoxy of bis (4-hydroxyphenyl), bis (3, 5- dimethyl- 4-hydroxy, for example) Phenyl) diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl ether type epoxy, tetramethyl bisphenol A diglycidyl ether type epoxy, ethylene oxide addition bisphenol Polyglycidyl ether compounds, such as the diglycidyl ether type epoxy of A and the epoxy resin which comprises these repeating units, the diglycidyl ester type epoxy of hexahydrophthalic acid, the diglycidyl ester type epoxy of phthalic acid, etc. Polyglycidyl amine compounds such as polyglycidyl ester compound, bis (4-aminophenyl) methane diglycidylamine type epoxy, and carboxyl group-containing epoxy according to [1-3-2]. There may be mentioned on page precursor is an epoxy resin or the like.

Further, for example, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-bis {[(3-ethyl-3-oxeta Oxetane derivatives such as nil) methoxy] methyl} benzene, 1,4-benzenecarboxylic acid bis [(3-ethyl-3-oxetanyl) methyl] ester, phenol novolak oxetane, cresol novolak oxetane Can be mentioned.

Moreover, as a vinyl polymer which has an epoxy group in a side chain, allyl glycidyl ether, glycidyl (meth) acrylate, (alpha)-ethyl glycidyl (meth) acrylate, glycidyl crotonate, Aliphatic epoxy group-containing unsaturated compounds, such as glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl ester of fuconate, monoalkyl monoglycidyl ester of fumarate, and monoalkyl monoglycidyl ester of maleic acid Or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] decyl-2-yl] The copolymer etc. of epoxy group containing unsaturated compounds, such as alicyclic epoxy group containing unsaturated compounds, such as oxymethyl (meth) acrylate, and another vinyl type compound which can be copolymerized are mentioned.

Furthermore, in the photocured film, for the purpose of further improving the strength and the heat resistance, the crystalline epoxy compound having a melting point of 50 ° C. or more may be contained as necessary.

It is preferable that it is 60-160 degreeC, and, as for the melting point of the said crystalline epoxy compound, it is especially preferable that it is 70-150 degreeC. In addition, the compound preferably has 9 to 30 carbon atoms, and particularly preferably 10 to 25 carbon atoms. And it is preferable that it is 1-5 functional, and it is especially preferable that it is 2-3 functional.

Specifically as said crystalline epoxy compound, the triglycidyl isocyanurate which is a triglycidyl amine type epoxy compound obtained by reaction of isocyanuric acid and epichlorohydrin, a biphenol derivative, and epi, for example Bixylenol diglycidyl ether, bixylenol fluorene diglycidyl ether, biphenol fluorene diglycidyl ether, etc. which are diglycidyl ether type epoxy obtained by the reaction of chlorohydrin are mentioned.

In addition, a high melting point crystalline epoxy compound can be used in place of or in combination with the above crystalline epoxy compound. The crystalline epoxy compound generally has advantages such as improvement of film strength, improvement of humidity resistance, improvement of sensitivity, and the like as compared with the amorphous epoxy compound, but is easily melted due to heat generation by dispersion during dispersion. Since melting and dissolution at the time of dispersion can be prevented, the crystalline epoxy compound whose melting | fusing point is 150 degreeC or more normally, Preferably it is 180 degreeC or more, More preferably, it is 195 degreeC or more is preferable.

As the high melting point crystalline epoxy compound, for example, tetraglycidyl xylyl ethane, tetraglycidyl phenylol ethane, etc., which is a tetraglycidyl ether type epoxy obtained by reaction of a tetraphenol derivative and epichlorohydrin. Can be mentioned.

In the photosensitive composition of this invention, it is preferable that it is 0.5 to 70 weight% with respect to the total amount of the photosensitive composition, and, as for the content rate of the epoxy compound which is (D) component, it is more preferable that it is 2 to 50 weight%. When there is too little content of (D) component, there exists a tendency for the intensity | strength of the hardened | cured material obtained also to become inadequate. When there is too much content of (D) component, there exists a tendency for image formability to fall.

[1-4-2] (E) amino compound

The photosensitive composition of the present invention, in addition to the components (A) to (C), is a methylol group as a functional group for the purpose of improving the heat resistance of the cured product obtained, chemical resistance, and the like, and an alkoxymethyl group having a C 1 to C 8 alcohol condensation-modified property. It is preferable to contain the amino compound (E) component which has at least two. As these amino compounds, for example, melamine resin polycondensed melamine and formaldehyde, benzoguanamine resin polycondensed benzoguanamine and formaldehyde, glycoluril resin polycondensed glycoluril and formaldehyde, urea and form 2 or more types, such as urea resin which polycondensed aldehyde, melamine, benzoguanamine, glycoluril, or urea, and the resin which co-condensed formaldehyde, and the modified resin which carried out alcohol condensation modification of the methylol group of these resins, etc. are mentioned. have.

Specifically, as melamine resin and its modified resin, Mitsui Cytec Co., Ltd. "Cymel" (registered trademark) 300, 301, 303, 340, 736, 738, 370, 771, 325, 327, 703, 701, 266 , 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikarak" (registered trademark) MW-100LM (former trade name is E-2151), MX manufactured by Sanwa Chemical Co., Ltd. -750LM, MX-302, as the benzoguanamine resin and its modified resin, Mitsui Cytec Co., Ltd. "Cymel" (registered trademark) 1123, 1125, 1128, as glycoluril resin and its modified resin, Mitsui Cytec (registered trademark) 1170, 1171, 1174, 1172, manufactured by Mitsui Cytec Co., Ltd., and "Nicarac" (registered trademark) MX-270, manufactured by Sanwa Chemical Co., Ltd., as urea resin and modified resin thereof. "UFR" (registered trademark) 65, 300 by Cytec Co., Ltd., and "Nikarak" (registered trademark) MX-290 by Sanwa Chemical Co., Ltd. are mentioned.

As said amino compound (E) component, a melamine resin and its modified resin are preferable, The modified resin whose modification ratio of a methylol group is 70% or more is more preferable, The modified resin which is 80% or more is especially preferable.

In the photosensitive composition of this invention, it is preferable that it is 0.1-20 weight% with respect to the total amount of the photosensitive composition, and, as for the content rate of the amino compound which is the said (E) component, it is more preferable that it is 0.5-10 weight%.

[1-4-3] (F) sensitizing dyes

It is preferable that the photosensitive composition of this invention contains a sensitizing dye (F) component for the purpose of the sensitivity improvement of a composition other than the said (A)-(C) component. As a sensitizing dye, it is a light absorption pigment | dye which has absorption maximum in the ultraviolet-blue purple region of wavelength 340-430 nm, A dialkylaminobenzene type compound, a pyrromethene type compound, a trihydroxy pyrimidine derivative etc. are mentioned. Especially, a dialkyl amino benzene type compound is preferable.

Examples of the dialkylaminobenzene compound include dialkylaminobenzophenone compounds and dialkylaminobenzene compounds having a heterocyclic group as a substituent on a carbon atom at the p-position to an amino group on the benzene ring, and an amino group on the benzene ring. Preference is given to dialkylaminobenzene-based compounds having a substituent containing a sulfonylimino group at a carbon atom in the p-position, and to a dialkylaminobenzene-based compound having a carbostyryl skeleton.

As said dialkylamino benzophenone type compound, what is represented by the following general formula (i) is preferable.

[Formula 17]

[In formula, R ⁶² , R ⁶³ , R ⁶⁶ , and R ^67. Each independently represents an alkyl group which may have a substituent, and R ⁶⁴ , R ⁶⁵ , R ⁶⁸ , and R ⁶⁹ Each independently represents an alkyl group which may have a substituent or a hydrogen atom, and R ⁶² R ⁶³ and R ⁶² With R ⁶⁴ , R ⁶³ with R ⁶⁵ , R ⁶⁶ with R ⁶⁷ , R ⁶⁶ And R ⁶⁸ , and R ⁶⁷ and R ⁶⁹ May independently form a nitrogen-containing heterocycle.]

Here, carbon number of the alkyl group of R <^62> , R <^63> , R <^66> and R <^67> in Formula (i), and R <^64> , R <^65> , R <^68> and R <^69> It is preferable that carbon number when it is an alkyl group is 1-6.

In addition, when forming a nitrogen-containing heterocycle, it is preferable that it is a 5 or 6 membered ring, R ⁶² With R ⁶⁴ , R ⁶³ And R ⁶⁵ , R ⁶⁶ And R ⁶⁸ , or R ⁶⁷ And R ⁶⁹ It is preferable to form a tetrahydroquinoline ring of 6-membered ring, and R ⁶² With R ⁶³ And R ⁶⁴ And R ⁶⁵ , or / and R ⁶⁶ and R ⁶⁷ And R ⁶⁸ And R ⁶⁹ It is particularly preferable that the saccharide form a Julolidine ring. Moreover, the tetrahydroquinoline ring which has an alkyl group as a substituent at 2-position, or the julolidine ring containing the tetrahydroquinoline ring is especially preferable.

As a specific example of a compound represented by the said general formula (i), For example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and the following structure The compound of the is mentioned.

[Formula 18]

The heterocyclic group of the carbon atom in the p-position relative to the amino group on the benzene ring is preferably a 5- or 6-membered ring containing a nitrogen atom, an oxygen atom, or a sulfur atom, and particularly preferably a 5-membered ring having a condensed benzene ring. It is preferable and represented by the following general formula (i).

[Formula 19]

[In formula, R ⁷⁰ And R ⁷¹ Each independently represents an alkyl group which may have a substituent, and R ⁷² And R ⁷³ Each independently represents an alkyl group which may have a substituent or a hydrogen atom, and R ⁷⁰ And R ⁷¹ , R ⁷⁰ And R ⁷² , and R ⁷¹ And R ⁷³ Each independently may form a nitrogen-containing heterocycle. X represents an oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and the benzene ring condensed on a heterocycle may have a substituent.]

Here, carbon number of the alkyl group of R <^70> and R <^71> in Formula (i), and ^R72 And R ⁷³ It is preferable that carbon number in this alkyl group is 1-6. In addition, when forming a nitrogen-containing heterocycle, it is preferable that it is a 5 or 6 membered ring, R ⁷⁰ And R ⁷² , R ⁷¹ And R ⁷³ preferably form a tetrahydroquinoline ring of 6 membered ring, and R ⁷⁰ And R ⁷¹ And R ⁷² With R ⁷³ It is especially preferable to form this julolidine ring. Furthermore, the tetrahydroquinoline ring which has an alkyl group as a substituent at 2-position, or the julolidine ring containing the tetrahydroquinoline ring is especially preferable. Moreover, it is preferable that carbon number of the alkyl group when X is a dialkylmethylene group is 1-6, and it is preferable that carbon number of the alkyl group when an alkylimino group is 1-6.

As a specific example of a compound represented by said formula (i), 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p, for example -Dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- ( p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzoimidazole, 2- (p-diethylaminophenyl) benzoimidazole, 2- (p-dimethylaminophenyl) -3, 3-dimethyl-3H-indole, 2- (p-diethylaminophenyl) -3,3-dimethyl-3H-indole, and the compound of the following structure are mentioned.

[Formula 20]

Moreover, as a dialkylamino benzene type compound which has a heterocyclic group as a substituent at the carbon atom of p-position with respect to the amino group on a benzene ring other than the compound represented by said Formula (i), 2- (p-dimethylamino Phenyl) 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 etc. are mentioned.

Moreover, as a dialkylaminobenzene type compound which has a substituent which contains a sulfonyl imino group in the carbon atom of a p-position with respect to the amino group on a benzene ring, it is preferable to represent with a following formula (i).

[Formula 21]

[In formula, R ⁷⁴ And R ⁷⁵ Each independently represents an alkyl group which may have a substituent, and R ⁷⁶ and R ⁷⁷ Each independently represents an alkyl group which may have a substituent or a hydrogen atom, and R ⁷⁴ With R ⁷⁶ , R ⁷⁴ With R ⁷⁶ , and R ⁷⁵ And R ⁷⁷ Each independently may form a nitrogen-containing heterocycle, R ⁷⁸ represents a monovalent or hydrogen atom, and R ⁷⁹ Indicates 1 go.]

Here, carbon number of the alkyl group of R <^74> and R <^75> in formula (i), and ^R76 and ^R77 It is preferable that carbon number in this alkyl group is 1-6. In addition, when forming a nitrogen-containing heterocycle, it is preferable that it is a 5 or 6 membered ring, R ⁷⁶ and R ⁷⁷ Is preferably a hydrogen atom.

Moreover, as 1 group of R ⁷⁸ and R ⁷⁹ , 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, an aralkyl group, for example. , Aryl alkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino group, acylamino group, carbamate group, sulfonamide group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio group, An imino group, a cyano group, a heterocyclic group, etc. are mentioned. Among these, R ⁷⁸ is preferably a hydrogen atom, and R ⁷⁹ is preferably an aryl group.

Moreover, it is preferable that it is represented by the following general formula (VII) as a dialkylaminobenzene type compound which formed the carbostyryl frame | skeleton.

[Formula 22]

In 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 an alkyl group which may have a substituent or a hydrogen atom, and R ⁸⁰ And R ⁸¹ , R ⁸⁰ And R ⁸² , and R ⁸¹ And R ⁸³ may each independently form a nitrogen-containing heterocycle, and 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 formula (X) in R ^80, R ^81, and the carbon number of the alkyl group of R ^84, and R ^82, carbon atoms when the R ^83, and R ⁸⁵ is an alkyl group preferably has 1 to 6. In addition, when forming a nitrogen-containing heterocycle, it is preferable that it is a 5 or 6 membered ring, R ⁸² and R ⁸³ Is preferably a hydrogen atom. Moreover, as R ⁸⁵ , it is preferable that it is a phenyl group.

As a sensitizing dye of the said (F) component, it is a carbon atom of a p-position with respect to the amino group on the benzene ring represented by said dialkylamino benzophenone type compound represented by said Formula (i), and said Formula (i). The dialkylaminobenzene type compound which has a substituent containing a sulfonyl imino group, or the dialkylaminobenzene type compound which provided the carbostyryl frame | skeleton represented by said Formula (VII) is especially preferable.

In the photosensitive composition of this invention, it is preferable that it is 0.1-20 weight% with respect to the total amount of the photocurable composition, and, as for the content rate of the sensitizing dye which is the said (F) component, it is more preferable that it is 0.5-10 weight%.

[1-4-4] (G) Epoxy Curing Agent

The photosensitive composition of this invention may contain the epoxy hardening | curing agent (G) component for the purpose of the photocurability, thermosetting improvement, etc. of a composition other than the said (A)-(C) component. Examples of the epoxy curing agent as the component (G) include succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and 3-ethyl. Tetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, Polyhydric carboxylic acid anhydrides such as trimellitic anhydride and biphenyltetracarboxylic anhydride, organic phosphines such as tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, imidazole, 2 -Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- (2-cyanoethyl) -2- Phenylimidazole, 1- (2-hour Imidazoles such as noethyl) -2-ethyl-4-methylimidazole, dicyandiamide, benzylmethylamine, 4-methylbenzyl-N, N-dimethylamine, 4-methoxybenzyl-N, N- Amine compounds such as 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-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2,4-dia Quaternary ammonium salts such as amino-s-triazines such as mino-6-methacryloyloxyethyl-s-triazine and isocyanuric acid adducts, benzyltrimethylammonium chloride and phenyltributylammonium chloride, tri- phosphonium salts such as n-butyl-2,5-dihydroxyphenyl-phosphonium bromide and hexadecyltributylphosphonium chloride; and the like, and among them, those having a -NH- group are preferable, and amine compounds And amino- s-triazines are preferred, and dicyandiamide and 2,4,6-triamino-s-triazine are particularly preferred.

It is preferable that the content rate of the epoxy hardening | curing agent which is the said (G) component is 0.1 weight% or less with respect to the total amount of the photosensitive composition from a viewpoint of the stability with time as a photosensitive composition.

[1-4-5] (H) Polymerization Accelerators

In addition to said (A)-(C) component, the photosensitive composition of this invention may contain the polymerization accelerator (H) component for the purpose of the improvement of the photoinitiation ability of a composition, etc. As a polymerization accelerator which is (H) component, it is preferable to contain the ester of an amino acid or a bipolar ion compound, and it is preferable that it is represented by a following formula (VIIa) or (XIb) as ester of this amino acid or a bipolar ion compound. .

[Formula 23]

Of the formula (Ⅹ1a) and (Ⅹ1b), R ²⁶ and R ²⁷ Each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and R ²⁸ and R ²⁹ Each independently represents an alkyl group which may have a substituent or a hydrogen atom, and R ³⁰ Represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, and R ³¹ has an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent A heterocyclic group which may be present, and s is an integer of 0-10.]

Here, as an alkyl group of R <^26> , R <^27> , R <^28> , R <^29> , R <^30> , and R <^31> in Formula (VII1) and (VII1b), it is preferable that carbon number is 1-8, and it is more preferable that it is 1-4. desirable. Moreover, as an alkenyl group of R <^30> , a vinyl group, an allyl group, an isopropenyl group, etc. are mentioned, for example, Furthermore, as an aryl group of R <^26> , R <^27> , R <^30> , and R <^31> , it is a phenyl group, nap, for example. As a heterocyclic group of R <^26> , R <^27> and R <^30> , a silyl group etc. are mentioned, for example, a furyl group, furanyl group, a pyrrolyl group, a pyridyl group, etc., respectively.

As the substituents in these alkyl groups and alkenyl groups, for example, alkoxy groups, alkoxycarbonyl groups, alkenyloxy groups, alkenyloxycarbonyl groups, phenyl groups, halogen atoms and the like may be used in these aryl groups and heterocyclic groups. As a substituent of, for example, the alkyl group which may further have substituents, such as an alkoxy group and a phenyl group, the alkoxy group, the same alkenyl group, the same alkenyloxy group, the same acyl group, the same acyloxy group, the same Alkoxycarbonyl groups, likewise phenoxy groups, likely alkylthio groups, likely alkylsulfonyl groups, and aldehyde groups, carboxyl groups, hydroxyl groups, sulfo groups, nitro groups, cyano groups, halogen atoms and the like.

In the present invention, one of R ²⁶ and R ^{27 in} the formula (VII1a) may be a hydrogen atom and the other may have a substituent in the ester of the amino acid represented by the formula (VII1a) or (VII1b) or a bipolar compound. Phenyl group, R ²⁸ and R ²⁹ Together is a hydrogen atom, R ³⁰ A phenyl group which may have an alkyl group, or a substituent which may have a substituent, R ²⁶ and R ²⁷ s of 0, 1, or 2, the amino acid ester, or the formula (Ⅹ1b) Together are a hydrogen atom, or one is an alkyl group which may have a substituent, R ²⁸ and R ^{2 9} together are a hydrogen atom, R ³¹ It is an alkyl group which may have this substituent, or a phenyl group which may have a substituent, and it is preferable that it is an amino acid bipolar ion compound whose s is 0, 1, or 2. In the formula (VIIa), s is O, one of R ²⁶ and R ²⁷ is a hydrogen atom, the other is a phenyl group, R ²⁸ and R ²⁹ Is an ester of N-phenylglycine which is a hydrogen atom, in particular, N-phenylglycinebenzyl ester wherein R ³⁰ is a benzyl group, or in the general formula (VIIb), s is O, R ²⁶ , R ²⁷ , R ²⁸ , And any of R ²⁹ is a hydrogen atom and R ³¹ Particularly preferred is a bipolar ion compound of N-phenylglycine which is this phenyl group.

Moreover, in this invention, as a polymerization accelerator which is (H) component, you may further contain polymerization accelerators other than the ester of the said amino acid, or a bipolar ion compound. For example 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) Mercapto group-containing compounds, such as quinazolin, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristyropropionate, and pentaerythritol tetrakistyropropionate, hexanedithiol and trimethyl Polyfunctional thiol compounds such as all propane tristhioglyconate and pentaerythritol tetrakistiopionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine or its ammonium salt, sodium salt, ester salt, and phenylalanine Or amino acids having aromatic rings, or derivatives thereof, such as ammonium salts, sodium salts, and esters thereof.

In the photosensitive composition of this invention, it is preferable that it is 20 weight% or less with respect to the total amount of the photosensitive composition, and, as for the content rate of the polymerization accelerator which is the said (H) component, it is more preferable that it is 1-10 weight%.

[1-4-6] (I) Inorganic fillers

Moreover, the photosensitive composition of this invention may contain the inorganic filler (I) component for the purpose of the improvement of the intensity | strength as hardened | cured material, etc. other than the said (A)-(C) component. As an inorganic filler which is (I) component, for example, talc, such as "ST-2000" by Nippon Talc, "BST", silica, such as "R972" and "R974" by Nippon Aerosil Co., Ltd. And barium sulfate such as "B-30", "BF-1" and "BF-40" manufactured by Sakai Chemical Co., Ltd., and magnesium oxide. These inorganic fillers can be surface-treated with a silane coupling agent etc. as needed. An average particle diameter is 0.005 micrometer or more normally, Usually 50 micrometers or less, Preferably it is 20 micrometers or less, More preferably, it is used disperse | distributing to 10 micrometers or less.

In the photosensitive composition of this invention, it is preferable that it is 70 weight% or less with respect to the total amount of the photosensitive composition, and, as for the content rate of the inorganic filler which is said (I) component, it is more preferable that it is 1-50 weight%.

[1-4-7] (J) Colorants

The photosensitive composition of this invention may contain the (J) color material other than the said (A)-(C) component. (J) A color material means what colors the composition especially when using the photosensitive composition of this invention as a color filter, soldering resist, or other coloring composition. Although a salt pigment can be used as a coloring material, a pigment is preferable from a viewpoint of heat resistance, light resistance, etc. As the pigment, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments and black pigments can be used. As the structure, various inorganic pigments and the like can be used in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindrinone, dioxazine, indanthrene and perylene. Below, the specific example of the pigment which can be used is shown by a pigment number. C.I. exemplified below. Means color index (C.I.).

As a red pigment, C.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, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254 , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, Preferably C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment red 177, 209, 224, 254 is mentioned.

As a blue pigment, C.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. Among these, Preferably C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. Pigment blue 15: 6.

As a green pigment, C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among these, Preferably C.I. Pigment green 7, 36 is mentioned.

As a yellow pigment, C.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, and 208. Among these, Preferably C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. Pigment yellow 83, 138, 139, 150, 180 is mentioned.

As an orange pigment, C.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. Among these, Preferably, C.I. Pigment oranges 38 and 71.

As a purple pigment, C.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. Among these, Preferably C.I. Pigment violet 19, 23, more preferably C.I. Pigment violet 23 is mentioned.

Moreover, a black color material can also be used as a color material. The black color material may be a black color material alone, or may be a mixture of red, green, blue and the like. In addition, these color materials can be suitably selected from pigments or dyes of inorganic or organic.

The colorants that can be mixed to prepare the black colorant include Victoria Pure Blue (42595), Oramine O (41000), Katyron Brilliant Pravin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170 ), Safranin OK70: 100 (50240), Eriograsin X (42080), No.120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T -564D (21095), Shimla First Red 4015 (12345), Lionol Red 7B4401 (15850), First Gem Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Leonogen red GD (Pigment Red 168), Leonol Green 2YS (Pigment Green 36), etc. (In addition, the number in said () means color index (CI)).

Moreover, regarding the pigment which can be mixed and used other, it is C.I. Yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Violet Pigments 19, 23, 29, 30, 37, 40, 50, C.I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. Green pigment 7, C.I. Brown pigment 23, 25, 26 etc. are mentioned.

As a black color material which can be used independently, carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, etc. are mentioned.

Among these, carbon black and titanium black are preferable from the viewpoint of light shielding rate and image characteristics. Examples of the carbon blacks include the following carbon blacks.

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, OIL1lB, OIL30B, OIL31B manufactured by Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40 , Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack340, SpecialBlack250, SpecialBlackl00, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Cabot Company: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL480, REGALR RREG660R , VULCAN XC72R, ELFTEX-8 colombian carbon company: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1040 , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3400, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Moreover, the following are mentioned for titanium black.

As a method for producing titanium black, a method of heating and reducing a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine titanium dioxide obtained by high temperature hydrolysis of titanium tetrachloride Is reduced in a reducing atmosphere containing hydrogen (Japanese Laid-Open Patent Publication No. 57-205322), a method of high temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Laid-open Patent Publication No. 60-65069, Japanese Laid-Open Patent Publication Japanese Patent Application Laid-Open No. 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and high temperature reduction in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), and the like, are not limited thereto.

As an example of the commercial item of titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C etc. by Mitsubishi Material Corporation are mentioned.

As an example of another black pigment, aniline black, iron oxide type black pigment, and red, green, blue tricolor organic pigment can be mixed and used as a black pigment.

As the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengalla, chromium oxide and the like can also be used.

The said pigment can also use multiple types together. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used together as a pigment, or a blue pigment and a purple pigment can be used together.

Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. .

As an azo dye, it is C.I. Exid Yellow 11, C.I. EXID ORANGE 7. C.I. Exid Red 37, C.I. Exid Red 180, C.I. EXID BLUE 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Moldant Red 7, C.I. Moldant Yellow 5, C.I. Moldant Black 7 etc. are mentioned.

As an anthraquinone type dye, it is C.I. Bat Blue 4, C.I. EXID BLUE 40, C.I. Exid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Disperse Blue 60 etc. are mentioned.

In addition, as a phthalocyanine dye, it is for example C.I. Bat blue 5 and the like, for example, as a quinoneimine dye, for example C.I. Basic Blue 3, C.I. Basic blue 9 and the like, for example, as a quinoline dye, for example C.I. Solvent Yellow 33, C.I. Exid Yellow 3, C.I. Disperse Yellow 64 etc. are mentioned as a nitro dye, for example, C.I. Exid Yellow 1, C.I. EXID Orange 3, C.I. Disperse yellow 42 etc. are mentioned.

As a color material used for the photosensitive composition of this invention, when using a soldering resist, it is preferable to use the color material which does not contain a halogen atom, for example.

In addition, when the color material which occupies for the total solid of the photosensitive composition of this invention is an inorganic or organic pigment, the average particle diameter of a pigment is normally 1 micrometer or less, Preferably it is 0.5 micrometer or less, More preferably, it disperse | distributes to 0.25 micrometer or less Used. Moreover, it is preferable to use a dispersion material and / or a dispersion aid together for pigment dispersion in order to improve dispersibility and dispersion stability.

Surfactants, polymer dispersants, and the like are usually used as the dispersant, but a polymer dispersant is particularly preferred because of its excellent dispersion stability over time. As the polymer dispersant, for example, the nitrogen atom-containing dispersant described in JP 2005-126674 A and the like is preferable. As the nitrogen atom-containing dispersant, for example, a urethane-based dispersant, a graft copolymer containing nitrogen atoms, and a side chain. The AB block copolymer and / or BAB block copolymer etc. which consist of an A block which has quaternary ammonium salt group, and B block which does not have quaternary ammonium salt group are mentioned. A dispersing agent may be used individually by 1 type, and may mix and use two or more types.

The proportion of the color material in the total solid of the photosensitive composition of the present invention is usually 1 to 70% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight. When the content ratio of the color material is too small, the coloring power becomes low, the film thickness becomes thick with respect to the color density, and adversely affects the gap control during liquid crystal cell formation and the like. On the contrary, if the content ratio of the colorant is too large, dispersion stability deteriorates and there is a risk of problems such as reagglomeration and thickening.

[1-4-8] (K) surfactant

The photosensitive composition of the present invention, in addition to the components (A) to (C), is nonionic, anionic, cationic, positive, and the like for the purpose of coating property as a composition coating liquid and improvement of developability of the photosensitive composition layer. You may contain surfactant (K) components, such as a fluorine system.

Specifically as a nonionic surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene fatty acid Esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrate fatty acid esters, polyoxyethylene pentaerythrate fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbet Fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. are mentioned. As these commercial items, polyoxyethylene surfactants, such as "Emalgen 104P" and "Emalgen A60" by Cao Corporation, etc. are mentioned.

Moreover, a fluorine type and a silicone type thing can be used preferably. As a fluorine-type surfactant, the compound which has a fluoroalkyl or a fluoroalkylene group in at least any one site | part of a terminal, a main chain, and a side chain is preferable. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycoldi (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycoldi (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-decaplododecane, 1,1,2,2,3,3-hexafluorodecane and the like. Moreover, as these commercial items, "BM-1000", "BM-1100" by BM Chemie company, "Megapak F142D", "B F172" by Dainippon Ink and Chemicals, Inc., "F173", "Bridge F183 "," the copper F470 "," FC430 "by Sumitomo 3M Corporation," DFX-18 "by Neos Corporation, etc. are mentioned.

As silicone type surfactant, "Toray Silicone DC3PA", "Copper SH7PA", "Copper DC11PA" "Copper SH21PA", "Copper SH21PA", "Copper SH29PA", "Copper SH29PA" manufactured by Toray Silicon, Inc. '', '' East SH8400 '', `` TSF-4440 '', `` TSF-4300 '', `` TSF-4445 '', `` TSF-444 (4) (5) (6) (7) 6 '', manufactured by Toshiba Silicon Corporation Commercial items, such as "TSF-4460", "TSF-4452", "KP341" by Silicone Corporation, "BYK323" and "BYK330" by Big Chemical Co., Ltd. are mentioned.

As silicone type surfactant, polyether modified silicone type surfactant is more preferable.

Examples of the anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts and aliphatic alcohols. Sulfuric acid ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymeric surfactants, and the like. Can be mentioned. Of these, special high molecular surfactants are preferable, and special polycarboxylic acid type high surfactants are more preferable.

As a commercially available thing, for example, as alkyl sulfate ester salts, such as "Emar 10" by Cao Co., Ltd., such as "Perex NB-L" by Cao Co., Ltd., such as alkyl naphthalene sulfonate, etc. Examples of the activator include "Homogenol L-18" and "Homogenol L-100" manufactured by Kao Corporation.

Moreover, quaternary ammonium salts, imidazoline derivatives, amine salts, etc. are mentioned as said cationic surfactant.

Moreover, betaine type compounds, imidazolium salts, imidazoline, amino acids, etc. are mentioned as an amphoteric surfactant. Among these, quaternary ammonium salts are preferable, and stearyl trimethylammonium salts are more preferable. Commercially available products include, for example, "acetamine 24" manufactured by Kao Corporation as alkylamine salts, and "cottamine 24P" and "cottamine 86W" manufactured by Kao Corporation as quaternary ammonium salts. Can be.

The surfactant may be a combination of two or more kinds, and a combination of a silicone-based surfactant / fluorine-based surfactant, a silicone-based surfactant / special polymer-based surfactant, a fluorine-based surfactant / special polymer-based surfactant, and the like can be given. Especially, silicone type surfactant / fluorine type surfactant is preferable. As combination of this silicone type surfactant / fluorine type surfactant, "TSF4460" made by GE Toshiba Silicone Co., Ltd. "DFX-18" made by Neos Corporation, "BYK-300" "BYK-330" made by BICKEM Corporation "S-393" of the / SEIMI Chemical company, "K-340" / Shin-Etsu Silicone company make "F-478" / Dainippon ink company make "SH7PA" / Toray Silicone make, "DS -401 "," L-77 "by Nippon Unicar Co., Ltd. /" FC4430 "by Sumitomo 3M company, etc. are mentioned.

In addition, the photosensitive composition of this invention mainly selects the said surfactant suitably, and the contact angle (theta) (degree) with respect to the clean glass surface of the photosensitive composition droplet, and surface tension (sigma) (mN / m) are represented by following formula (1), ( It is preferable to adjust so as to satisfy 2) and (3). By satisfy | filling any one of following formula (1), (2), and (3), generation | occurrence | production of a coating nonuniformity and a dry nonuniformity can be prevented.

θ≤5 × (σ ₀ -σ) (1)

σ≤σ ₀ -1 (2)

θ≤15 (3)

[Wherein, sigma ₀ is the surface tension (mN / m) of the solvent alone used in the photosensitive composition.]

Moreover, it is preferable that the photosensitive composition of this invention satisfy | fills following formula (1 '), (2'), and (3 '), and following formula (1' '), (2' '), and (3) '') Is more preferable, and it is particularly preferable to satisfy the following formulas (1 '' '), (2' ''), and (3 '' ').

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 '')

θ≤3 × (σ ₀ -σ) (1 ''')

σ≤σ ₀ -2 (2 ''')

θ≤5 (3 '' ')

Further, 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 property, and surface tension σ ( It is preferable that mN / m) satisfy | fills following formula (4), It is more preferable to satisfy following formula (4 '), It is especially preferable to satisfy following formula (4 ").

| Σ-σ '| ≤0.4 (4)

| Σ-σ '| ≤0.3 (4')

| Σ-σ '| ≤0.2 (4' ')

In addition, in this invention, the said contact angle and the said surface tension are respectively measured by the following method, and the said dilution is based on the following method.

<Contact angle>

The glass substrate for liquid crystal panels is cleaned with a cleaning agent, and then optically washed by UV ozone treatment, and the contact angle with pure water is 0 degrees, that is, a clean glass substrate wetted while fully spreading. And the static contact angle of the photosensitive composition with respect to this glass substrate is measured at 23 degreeC using the contact angle measuring apparatus by a droplet method.

<Surface tension>

The surface is sufficiently glowing with an alcohol lamp or the like to prepare a purified platinum plate, and the static surface tension of the photosensitive composition is measured at 23 ° C. using a surface tension meter by a flat plate method.

<Dilution method>

At room temperature, a small amount of the same solvent as that used for the photosensitive composition is added dropwise to the photosensitive composition in the beaker under stirring to dilute it.

In the photosensitive composition of this invention, it is preferable that it is 10 weight% or less with respect to the total amount of the photosensitive composition, and, as for the content rate of (K) surfactant component, it is more preferable that it is 0.001-5 weight%.

[1-4-9] Other additives

The photosensitive composition of the present invention comprises various additives, for example, a thermal polymerization inhibitor such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, based on the total amount of the photosensitive composition. 40% by weight or less, plasticizers such as dioctylphthalate, dododecyl phthalate, and tricredil phosphate, 10% by weight or less, and 30% by weight of a pigment precursor, similarly to a sensitivity improving agent such as tertiary amine or thiol Flame retardants such as non-halogen condensed phosphate esters (specifically, for example, aromatic condensed phosphate esters "CR-733S" "CR-741" "CR-747" "PX-200", etc., manufactured by Daihachi Chemical Co., Ltd .; May be similarly contained in the ratio of 40 weight% or less.

[1-5] Spectral Sensitivity Characteristics and Minimum Exposure Dose

The photosensitive composition of this invention has the maximum peak of spectral sensitivity normally in the wavelength range of 340-430 nm, Preferably 350-430 nm, More preferably, 355-430 nm, Especially preferably, 360-430 nm. When the maximum peak of the spectral sensitivity is biased toward the short wavelength side, the sensitivity to laser light having a wavelength of 340 to 430 nm tends to be inferior as the photosensitive composition, while when the maximum peak of the spectral sensitivity is biased to the long wavelength side, it is safe under yellow light. This tends to fall.

In the present invention, the maximum peak of the spectral sensitivity is described in detail in, for example, "Photopolymer Technology" (Tsuguo Yamaoka, 1988 Nikkan Kogyo Shimbun, page 262). That is, an exposure wavelength is linearly changed in the horizontal axis direction of light spectroscopy of a photocurable image forming material sample having a photocurable composition layer formed on a substrate surface from a light source such as a xenon lamp or a tungsten lamp using a spectrophotometer. The exposure intensity is set so that the exposure intensity changes logarithmically in the vertical axis direction, and the exposure is performed. Thereafter, the image processing is performed to obtain an image corresponding to the sensitivity of each exposure wavelength, and to calculate the exposure energy that can be formed from the image height, and to plot the spectral sensitivity curve obtained by plotting the wavelength on the horizontal axis and the inverse of the exposure energy on the vertical axis. It indicates the maximum peak in

As a specific measurement example, the following are mentioned, for example.

The xenon lamp ("UI-501C" by Ushio Electric Co., Ltd.) was light-sourced using the diffraction spectrophotometer ("RM-23" by Narumi) from the sample which cut out the image forming material into the size of 50x60 mm. The exposure wavelength was linearly changed in the horizontal axis direction, and light irradiated in the wavelength range of 350 to 650 nm was set so as to change the exposure intensity in the vertical axis direction.

Subsequently, 30 degreeC 1weight% sodium carbonate aqueous solution was sprayed so that it might become 0.15 Mpa as a developing solution, and spray-developing was carried out for 2 times the minimum developing time, and the image according to the sensitivity of each exposure wavelength was obtained. The peak energy in the spectral sensitivity curve obtained by calculating the exposure energy which can form an image from the image height, and plotting the inverse of the exposure energy on the horizontal axis and the vertical axis was read.

Moreover, it is preferable that the minimum exposure amount [S410] which can form an image in wavelength _410nm of the photosensitive composition of this invention is 50 mJ / cm <2> or less, It is more preferable that it is 30 mJ / cm <2> or less, It is especially preferable that it is 20 mJ / cm <2> or less. When this minimum exposure amount [ _S410 ] is too large, it also changes depending on the exposure intensity of a laser light source, but there exists a tendency for exposure time to become long and utility falls. On the other hand, although the minimum of this minimum exposure amount [ _S410 ] is so preferable that it is small, it is 1 mJ / cm <2> or more normally.

Further, the photosensitive composition of the present invention, the [S _410] to the image forming minimum exposure amount _{[S 450 (mJ / ㎠)} ] ratio [S ₄₁₀ / S _450] of 0.1 or less on the possible at a wavelength of preferably 450㎚ and It is more preferable that it is 0.05 or less. When this ratio [S ₄₁₀ / S ₄₅₀ ] is too large, it tends to be difficult to achieve both blue-violet laser photosensitivity and safety light under yellow light.

Moreover, the photosensitive composition of this invention is the minimum exposure amount [S image forming minimum wavelength [S _{450 -650} (mJ / cm <2>)] image-capable at wavelength 450nm [S _{450 -650} (mJ / cm <2>)] at each wavelength of wavelength more than 450 nm and 650 nm or less [S] It is preferable that the ratio [S _{450 -650} / S ₄₅₀ ] to ₄₅₀ (mJ / cm 2)] is more than one. If the ratio [S _{450 -650} / S _450] is less than the above range, it tends to have both a safe light of the blue-purple laser light from below, such as photosensitive and yellow difficult.

And the minimum exposure amount [S ₄₁₀ ] that can be imaged at the wavelength 410 nm, the minimum exposure amount [S ₄₅₀ (mJ / cm 2) that can be imaged at a wavelength of 450 nm, and at wavelengths greater than 450 nm and 650 nm or less. The minimum exposure amount [S _{450 -650} (mJ / cm 2)] that can be formed in the image is determined as the imageable exposure energy calculated from the image height obtained in the maximum peak measurement of the spectral sensitivity using the spectral sensitivity measuring device described above. . The value obtained at that time means the minimum exposure amount which can form an image in the optimal image development conditions determined by changing image development conditions, such as a kind of developing solution, image development temperature, image development time, and the like. As the optimal developing conditions, a condition of spraying an alkaline developer at a temperature of 25 to 40 ° C and a pH of 11 to 14 at a pressure of 0.1 to 0.5 MPa for 0.5 to 3 minutes is usually adopted.

[2] image forming materials, image forming materials and image forming methods

The photosensitive composition of this invention can be used for forming the image forming material of this invention. The image forming material is usually formed by applying and drying the above-mentioned components on a temporary support film as a coating liquid obtained by dissolving or dispersing each component in a suitable solvent, and covering the surface of the formed photosensitive composition layer with a coating film as necessary. As such an image forming material, a dry film resist material etc. are mentioned, for example.

Moreover, the said image forming material can be used for further forming the image forming material of this invention. The image forming material usually has two types of manufacturing methods. One is manufactured by peeling the coating film and laminating it on the substrate to be processed, when the photosensitive composition layer side of the image forming material is covered with the coating film. Another one is manufactured in the following order. (1) It is set as the coating liquid which melt | dissolved or disperse | distributed each component of the said negative blue-violet laser photosensitive composition in the suitable solvent; (2) directly applied onto the substrate to be dried and dried; (3) The layer of the negative blue-violet laser photosensitive composition of this invention is formed on a to-be-processed substrate.

Moreover, an image forming material is used suitably for the following image forming methods. That is, the photosensitive composition layer of an image forming material is scanned and exposed by the laser beam of wavelength 340-430 nm, for example, and it develops and makes an image appear.

[2-1] Image Forming Material and Image Forming Material

As a temporary support film used for the image forming material of this invention, especially a dry film resist material etc., for example, conventionally well-known, such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. Film is used. It is preferable that the temporary support film is 10-10 micrometers or less of metal containing particle | grains, such as antimony of 10-30 micrometers in thickness, haze value 1.5% or less, and 10 micrometers or more in diameter, or its aggregate. In that case, when these films have solvent resistance, heat resistance, etc. which are necessary at the time of preparation of an image forming material, the photosensitive composition coating liquid can be apply | coated and dried directly on these temporary support films, and the image forming material of this invention can be manufactured. have. Moreover, even if these films are low in solvent resistance, heat resistance, etc., after forming a photosensitive composition layer on the film which has a mold release property, such as a polytetrafluoroethylene film and a release film, for example, solvent resistance is carried out on the layer. The image forming material of the present invention may be produced by laminating a temporary supporting film having low heat resistance or the like and then peeling off the film having releasability.

In addition, for the purpose of improving the transferability of the photosensitive layer, it is also possible to form a thermosetting transfer layer such as an ethylene vinyl acetate copolymer having a thickness of usually 10 to 50 µm on a temporary supporting film such as a polyethylene terephthalate film. Do.

Moreover, as a solvent used for a coating liquid, if it has sufficient solubility with respect to a used component, and gives favorable coating film property, it will not specifically limit. For example, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, Propylene glycol solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxarate, Ester solvents such as ethyl pyruvate, ethyl-2-hydroxybutylate, ethyl acetate acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohols such as heptanol, hexanol, diacetone alcohol, and furfuryl alcohol Ketone solvents such as solvents, cyclohexanone and methyl amyl ketone, High polar solvents, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, these mixed solvents, what added aromatic hydrocarbon to these, etc. are mentioned. The use ratio of a solvent is the range of about 1 to 20 times by weight ratio with respect to the total amount of a photocurable composition normally.

As a coating method, a conventionally well-known method, for example, rotation coating, wire bar coating, spray coating, dip coating, air knife coating, roll coating, blade coating, screen coating, curtain coating, etc. can be used. In that case, it is preferable that it is 5 micrometers or more as dry film thickness in terms of processability, such as image formation mentioned later and the etching, plating, etc. which are mentioned later, and it is more preferable that it is 10 micrometers or more. Moreover, it is preferable that it is 200 micrometers or less from a viewpoint of a sensitivity etc., and it is more preferable that it is 100 micrometers or less. As a drying temperature, it is 30-150 degreeC, for example, Preferably it is 40-110 degreeC. The drying time is, for example, 5 seconds to 60 minutes, and preferably 10 seconds to 30 minutes.

In addition, when used as image forming materials, such as a dry film resist material, it is preferable to cover the formed photosensitive composition layer surface with a coating film until the image forming material is laminated | stacked on a to-be-processed substrate. As this coating film, conventionally well-known films, such as a polyethylene film, a polypropylene film, a polyester film, and a polytetrafluoroethylene film, are used. Specifically, Mitsubishi Polyester Co., Ltd. film thickness 40 micrometers polyester film "S120" etc. are used preferably, for example. Moreover, it is preferable that the fish film has a film thickness of 10-50 micrometers, and 80 micrometers or more of fisheye is 10 pieces / m <2> or less, and it is preferable that center line average roughness Ra is 0.1 micrometer.

When the photosensitive composition layer side of the image forming material is covered with a coating film, the coating film is peeled off, laminated by heating, pressurizing or the like, or by directly applying and drying the photosensitive composition coating liquid of the present invention. An image forming material is produced. In this case, the substrate to be processed is subjected to etching processing, plating processing, solder processing, or the like on the surface of the substrate by etching the negative image shown by exposing and developing the photosensitive composition layer formed thereon with a laser beam or the like. Patterns, such as an electrode, are formed and the metal plate itself, such as copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, may be sufficient. Usually, thermosetting resins, such as an epoxy resin, a polyimide resin, a bismaleimide resin, an unsaturated polyester resin, a phenol resin, melamine resin, a saturated polyester resin, a polycarbonate resin, a polysulfone resin, an acrylic resin, a polyamide, for example Resins such as thermoplastic resins such as resins, polystyrene resins, polyvinyl chloride resins, polyolefin resins, and fluorine resins, paper, glass, and inorganic materials such as alumina, silica, barium sulfate, and calcium carbonate, or glass cloth-based epoxy It consists of composite materials, such as resin, a glass nonwoven fabric base epoxy resin, a paper base epoxy resin, and a paper base phenol resin, etc., The said metal or indium oxide, tin oxide, oxidation is carried out on the insulating support surface whose thickness is about 0.02-10 mm. Metal foils, such as metal oxides, such as indium dope tin oxide, etc. are heated, crimped a laminate, or sputter | spatters metal The deposition, the one by a method such as plating, forming a conductive layer has a thickness of about 1~100㎛ metal-clad laminate is preferably used.

When the image forming material of the present invention is produced by directly applying and drying the photosensitive composition coating liquid, the polymerization inhibitory effect of oxygen of the photosensitive composition is prevented on the photosensitive composition layer formed on the substrate to be processed. For this purpose, a protective layer may be formed by applying a solution such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose and drying.

The photosensitive composition of this invention which comprises the photosensitive composition layer laminated | stacked on the to-be-processed substrate is an ethylenically unsaturated group containing compound which is said (A) component, the photoinitiator which is said (B) component, and the said (C) component Alkali-soluble resin, Furthermore, the said (D)-(I) component etc. which are used as needed are contained. As said component (D), it is preferable that the particle | grains of 5 micrometers or less of particle diameters are the particulate form which occupies 50% or more of all the particles, and are disperse | distributed in the other component containing said (A)-(C) component. It is more preferable that particles having a particle diameter of 5 μm or less are dispersed in a particulate shape occupying 80% or more of all the particles, and particles having a particle diameter of 3 μm or less being dispersed in a particulate shape occupying 80% or more of all particles. Particularly preferred.

If the dispersion state of the said (D) component is other than the above-mentioned microparticle shape, stability with time as a photosensitive composition will deteriorate, or adhesiveness with respect to a board | substrate will deteriorate, and the objective of this invention cannot be achieved.

In the present invention, in order to disperse the component (D) in the form of fine particles as described above, after the powder (D) is finely pulverized into the form of the fine particles under mechanical shear stress by a mill roll or the like, You may disperse | distribute with a component in a coating solvent. Furthermore, after (D) component is finely pulverized into the said microparticle shape under mechanical shear stress by a mill roll etc. with alkali-soluble resin which is the said (C) component, it employ | adopts the method which disperse | distributes with each other component in a coating solvent. It is desirable to.

[2-2] Image Forming Method

In the said image forming material of this invention which has the photosensitive composition layer of this invention on a to-be-processed substrate, when the photosensitive composition layer is formed with the said image forming material, after peeling a temporary support film, or photosensitive The photosensitive composition layer is formed by directly applying and drying the composition coating liquid. When the protective layer or the like is formed, the protective layer or the like is peeled off, and then the photosensitive composition layer is subjected to scanning exposure using laser light as an exposure light source. After that, a negative treatment is formed on the substrate to be processed by developing.

Examples of the exposure light source include lasers such as carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, halogen lamps, and HeNe lasers, argon ion lasers, YAG lasers, HeCd lasers, semiconductor lasers and ruby lasers. Light source. In particular, a light source for generating laser light in the blue violet region in the ultraviolet of the wavelength region of 340 to 430 nm is preferable, and more preferably, the center wavelength thereof is about 405 nm. Specifically, an indium gallium nitride semiconductor laser which oscillates at 405 nm is mentioned.

The scanning exposure method by a laser light source is not specifically limited. For example, a planar scanning exposure system, an outer drum scanning exposure system, an inner drum scanning exposure system, etc. are mentioned. As the scanning exposure conditions, the output light intensity of the laser is preferably 1 to 100 Hz, more preferably 3 to 70 Hz, and the oscillation wavelength is preferably 355 to 430 nm, more preferably 400 to 420 nm, and the beam. The spot diameter is preferably 2 to 30 m, more preferably 4 to 20 m, the scanning speed is preferably 50 to 500 m / s, more preferably 100 to 400 m / s, and the scanning density is preferably 2,000 dpi. As mentioned above, More preferably, it exposes to 4,000 dpi or more, and carries out scanning exposure.

The developing treatment after the laser scanning exposure is preferably performed using an aqueous developer containing an alkali component and a surfactant. As an alkali component, for example, sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate Inorganic alkali salts such as sodium triphosphate, ammonium diphosphate, ammonium triphosphate, sodium borate, potassium borate, ammonium borate, and monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, tri Organic amine compounds such as ethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and the like. It is used at a concentration of about% by weight.

As surfactant, it is surfactant similar to what was illustrated in the said photosensitive composition. Especially, a nonionic, anionic, or amphoteric surfactant is preferable, and especially an amphoteric surfactant and especially a betaine type compound are preferable. The surfactant is preferably used at a concentration of 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, particularly preferably 0.001 to 5% by weight.

Moreover, the developing solution can contain organic solvents, such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, as needed. In addition, the pH of the developer is preferably set to 9-14, more preferably 11-14.

The development is usually carried out by a known developing method such as immersing the image forming material in the developing solution or spraying the developing solution on the image forming material, preferably at a temperature of 10 to 50 ° C, more preferably at a temperature of 20 to 40 ° C. In 5 seconds to 10 minutes. Moreover, in order to improve heat resistance, chemical resistance, etc. as a resist of a negative image formed as hardened | cured material after image development processing, it is preferable to heat-process for 10 minutes-1 hour, for example at 140-160 degreeC. Moreover, as needed, it is also possible to perform 50-1000mJ / cm <2> full-surface exposure using said exposure light source before heat processing.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[1] Test Example 1

[1-1] Preparation of Photosensitive Image Forming Material for Solder Resist

[1-1-1] Example 1

Components other than the component (B2a) described in Table 1 below and 20 parts by weight of a methyl isobutyl ketone (MIBK) solution were dispersed by a paint shaker to obtain a photosensitive composition solution (PA1).

Next, the poorly soluble photoinitiator dispersion solution which is the following (B2a) component, and the photosensitive composition solution (PA1) were mixed, and it stirred for 10 minutes with the ultrasonic dispersion machine, and obtained the coating solution.

The crude coating solution was applied onto the polyethylene terephthalate film (thickness 19 μm) as a temporary supporting film in an amount such that the dry film thickness was 40 μm using a wire bar, dried in an oven at 80 ° C. for 5 minutes, and formed. The polyethylene film (thickness 25 micrometers) as a coating film was laminated | stacked on the photosensitive composition layer, and the photosensitive image forming material was produced.

[1-1-2] Example 2

In Example 1, the image forming material was similarly manufactured except having used (B2b) instead of the photoinitiator which is (B2a) (refer Table 1 below).

[1-1-3] Example 3

In Example 1, the image forming material was similarly manufactured except having added (B3) as a photoinitiator (refer Table 1 below).

[1-1-4] Example 4

In Example 1, the image forming material was similarly manufactured except having added (B4) which is an oxime ester type photoinitiator soluble to a solvent (MIBK) as a photoinitiator (refer Table 1 below).

[1-1-5] Example 5

In Example 1, the image forming material was similarly manufactured except having added (B5) as a photoinitiator and (F1) as a sensitizing dye (refer Table 1 below).

[1-1-6] Example 6

In Example 1, (C3) was used instead of the component (C2), and the image forming material was similarly manufactured except having added (G1) (refer Table 1 below).

[1-1-7] Example 7

In Example 1, (D2) was used instead of the component (D1), and the image forming material was similarly manufactured except having added (G1) (refer Table 1 below).

[1-1-8] Example 8

In Example 1, the image forming material was similarly manufactured except having used the oxime initiator (B2d) soluble in the solvent instead of the photoinitiator (B2a) component (refer Table 1 below).

[1-1-9] Reference Example 1

In Example 1, the image forming material was similarly manufactured except having used the photoinitiator (B2c) instead of the photoinitiator (B2a) (refer Table 1 below).

* Content of B2a, B2b, B2c shows the quantity (weight part) of oxime initiator alone.

(A1) dipentaerythritol hexaacrylate

(B1) 1- (4-methylthiophenyl) -2-morpholino-2-methyl-propan-1-one

(B2a) After mixing the photoinitiator (absorption maximum 383 nm), alkali-soluble resin (C1), and MIBK which are represented by a following formula so that it may become a weight ratio 40:30:30, sand grinder ("RMH-03 by Imex Corporation) Type ”), and the photoinitiator dispersion liquid disperse | distributed to 0.3 micrometer of average particle diameters.

[Formula 24]

The average particle diameter of the said photoinitiator was measured using the laser diffraction scattering type particle size distribution measuring apparatus ("MT3300EX" by Nikkiso Corporation).

Furthermore, the said photoinitiator dispersion liquid was apply | coated in the amount which a dry film thickness becomes 40 micrometers using a wire bar on the polyethylene terephthalate film (19 micrometers in thickness) as a temporary support film, and dried in 80 degreeC oven for 5 minutes. About the coating sample, when the particle diameter of the photoinitiator in a coating film was measured using the optical microscope ("L-200" by Nikon Corporation) which has a digital measuring device, the particle diameter of 70% or more of photoinitiators is 2 micrometers. Or less.

(B2b) The photoinitiator dispersion liquid which disperse | distributed the photoinitiator (absorption maximum 383 nm) represented by a following formula in the same procedure as (B2a), and was disperse | distributed to 0.4 micrometer of average particle diameters.

[Formula 25]

(B2c) After mixing the same photoinitiator, alkali-soluble resin (C1), and MIBK which were used for (B2a) so that it may become a weight ratio 40:30:30, homogenizer ("DX-8" by Nippon Seiki Co., Ltd.) The photoinitiator dispersion liquid disperse | distributed by the process for 15 minutes.

As a result of measuring the average particle diameter of the said photoinitiator using the laser diffraction scattering type particle size distribution analyzer ("MT3300EX" by Nikkiso Corporation), since many precipitated particle | grains of 200 micrometers or more of particle diameters existed, measurement was not possible.

Furthermore, the said photoinitiator dispersion liquid was apply | coated in the amount which a dry film thickness becomes 40 micrometers using a wire bar on the polyethylene terephthalate film (19 micrometers in thickness) as a temporary support film, and dried in 80 degreeC oven for 5 minutes. About the coating sample, when the particle diameter of the photoinitiator in a coating film was measured using the optical microscope ("L-200" by Nikon Corporation) which has a digital measuring device, the particle diameter of 70% or more of photoinitiators is 170 micrometers. It was above.

(B2d) Photoinitiator represented by the following formula (absorption maximum 383 nm)

[Formula 26]

(B3) photoinitiator ("irgacure 907" by the Chiba specialty chemicals company)

(B4) (`` CGI242 '' made in Chiba specialty chemicals company)

(B5) 2,2'-bis (o-methylphenyl) -4,4'5,5'-tetraphenylbiimidazole

(C1) Isopropylene glycol monomethyl ether acetate of unsaturated group and carboxyl group-containing epoxy resin (acid value 100KOH.mg/g, weight average molecular weight 5,000, "PR-300PG" by Showa Polymer Co., Ltd.) of the following structural repeating unit. (PGMA) solution (solid content 63% by weight)

(C2) MIBK solution (70 wt% of solid content concentration) of unsaturated group and carboxyl group-containing epoxy resin (acid value 100KOH.mg/g, weight average molecular weight 4,000, "Kayalad ZAR-1527" by Nippon Kayaku Co., Ltd.) of the following structural repeating unit. %)

[Formula 27]

(C3) Unsaturated group and carboxyl group-containing epoxy resin which have the following structure (acid value 100KOH.mg/g)

[Formula 28]

Ra represents a hydroxyl group or a substituent represented by the following formula.

(D1) cresol novolac-type epoxy resin (weight average molecular weight 4,000, "180S70" by the Japan epoxy resin company)

(D2) tetraglycidylphenylolethane dispersed at an average particle diameter of 1.2 μm

(E1) Methanol-modified melamine compound ("Nicarak" (registered trademark) MW100LM manufactured by Sanwa Chemical Co., Ltd.)

(F1) sensitizing dye represented by the following formula

[Formula 29]

(G1) dicyandiamine

(I1) talc

(I2) barium sulfate

(J1) phthalocyanine blue

(K1) Big Chemicals surfactant `` BYK330 ''

[1-2] Preparation of Image Forming Material

The copper foil surface of the laminated substrate with thickness (1.5 mm in thickness, size of 250 mm x 200 mm) with the copper of polyimide resin to which copper foil of 35 micrometers in thickness was made, using "Scotchbright SF" by Sumitomo 3M company After polishing and washing with water, the resultant was dried with an air stream to face it. Subsequently, after preheating this to 60 degreeC in oven, roll temperature is carried out using a hand roll laminator in the peeling surface, peeling the polyethylene film from the photosensitive image forming material obtained above on the copper foil of the said laminated board with copper. The image forming material in which the photosensitive composition layer was formed on the laminated substrate with copper was manufactured by laminating at 100 degreeC, a roll pressure of 0.3 Mpa, and a lamination rate of 1.5 m / min.

[1-3] Laser Exposure Sensitivity

About the photosensitive composition layer of the obtained image forming material, exposure sensitivity was measured by the method shown below. The results are shown in Table 1. That is, a laser light source with a center wavelength of 405 nm and a laser output of 5 mW (fixed by Nichia Chemical Co., Ltd.) while fixing the photosensitive composition layer of the obtained image forming material on an aluminum cylinder having a diameter of 7 cm and changing the rotation speed at 10 to 100 rotations per minute. Scanning exposure was carried out using "NLHV500C") at an image plane roughness of 2 mW and a beam spot diameter of 20 µm while changing the beam scanning interval and scanning speed. Subsequently, a 30-degree-C aqueous solution of 1 weight% sodium carbonate was sprayed so that it might become 0.15 Mpa as a developing solution, and the negative image was shown by spray-developing for 2 times the minimum developing time. With respect to the obtained image, the exposure amount required to reproduce the line width of 20 µm was obtained, and it was set as the sensitivity to the blue violet laser.

[1-4] Maximal peak of spectral sensitivity

It was about 400 nm when the maximum peak of spectral sensitivity was measured by the method shown below. The sample which cut out the image forming material into the size of 50x60 mm was made into the light source using the xenon lamp ("UI-501C" by Ushio Electric Co., Ltd.) using the diffraction spectrophotometer ("RM-23" by Narumi). The light spectroscopically detected in the wavelength range of 340-650 nm was irradiated for 10 second, setting it so that an exposure wavelength might change linearly in a horizontal axis direction, and an exposure intensity would change algebraically in a vertical axis direction. Subsequently, 30 degreeC 1weight% sodium carbonate aqueous solution was sprayed so that it might become 0.15 Mpa as a developing solution, and spray-developing was carried out for 2 times the minimum developing time, and the image according to the sensitivity of each exposure wavelength was obtained. Then, the exposure energy which can be image-formed was computed from the image height, and the maximum peak in the spectral sensitivity curve obtained by plotting the wavelength on the horizontal axis and the inverse of the exposure energy on the vertical axis was read.

[1-5] Measurement of [S ₄₁₀ ], [S ₄₁₀ / S ₄₅₀ ] and [S _{450 -650} / S ₄₅₀ ]

By the method shown below, the minimum exposure amount [ _S410 (mJ / cm <2>)] which can form an image in wavelength _410nm was measured, and it was as Table 1 shown. In addition, the image forming minimum exposure dose at a wavelength 410㎚ [S _410] The minimum exposure dose capable of image formation at a wavelength of 450㎚ _{[S 450 (mJ / ㎠)} ] ratio of the [S ₄₁₀ / S _450], and a wavelength of 450 _Ratio of _imageable minimum exposure amount [S _{450 -650} (mJ / cm 2)] at each wavelength of more than 650 nm or less and 650 nm or less [S ₄₅₀ (mJ / cm 2)] with respect to imageable minimum exposure amount [S ₄₅₀ (mJ / cm 2)] [ S _{450 -650} / S ₄₅₀ ] were measured and evaluated according to the following criteria.

In the same manner as described above, when exposure is performed by changing the wavelength in the wavelength range of 340 to 650 nm, and developing, the minimum exposure amount [S ₄₁₀ (mJ / cm 2)] that can be formed at a wavelength of 410 nm and the wavelength of 450 nm to obtain the respective image forming minimum exposure amount _{[S 450 (mJ / ㎠)} ], and a wavelength greater than 450㎚ 650㎚ image forming minimum exposure amount in each wavelength of not more than _{[S 450 -650 (mJ / ㎠} )], the The ratios [S ₄₁₀ / S ₄₅₀ ] and [S _{450 -650} / S ₄₅₀ ] were calculated and evaluated by the following criteria.

[1-5-1] Evaluation Criteria for [S ₄₁₀ / S ₄₅₀ ]

A: S ₄₁₀ / S ₄₅₀ is 0.03 or less.

B: S ₄₁₀ / S ₄₅₀ is more than 0.03 and not more than 0.05.

C: _S410 / _S450 is greater than 0.05 and less than or equal to 0.1.

D: S ₄₁₀ / S ₄₅₀ is greater than 0.1.

[1-5-2] Evaluation Criteria for [S _{450 -650} / S ₄₅₀ ]

A: S _{450 -650} / S ₄₅₀ is _greater than 10.

B: S _{450 -650} / S ₄₅₀ is more than 5 and not more than 10.

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] Safelights under yellow light

About the obtained photosensitive image forming material, it was as Table 1 when the safety property under yellow light was evaluated by the method shown below.

After the image forming material was left for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, and 30 minutes under yellow light illumination (condition of blocking light having a wavelength of about 470 nm or less), the measurement of the exposure sensitivity was performed. Scanning exposure and development were carried out in the same manner as in the above, and the leaving time until a change occurred in the image was determined in comparison with the above, and the evaluation was made according to the following criteria.

A: 20 minutes or more.

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] Adhesiveness to Substrates

About the obtained photosensitive image forming material, it was as Table 1 when the adhesiveness with respect to the to-be-processed board | substrate of the hardened layer was evaluated by the method shown below.

The image forming material was subjected to laser scanning exposure at the minimum exposure amount required for image formation to form a whole hardened layer. Subsequently, after heat-processing the obtained hardened layer at 150 degreeC for 60 minutes, a cutting line was carved by the cutter so that it might become 100 checkered patterns at 1 mm intervals on the hardened layer, and the flux (made by Tamura Chemical Co., Ltd.) was apply | coated to the surface. . Then, after immersing in a 295 degreeC solder bath for 30 second, the operation which returns to room temperature was repeated 6 times. Then, the cellophane tape (made by Nichiban Co., Ltd.) was stuck on the hardened layer, the number of the peeled checkerboards of the hardened layer at the time of peeling the tape was measured, and the following references | standards evaluated.

A: The number of the peeled board eyes of a hardened layer among 100 boards is 1 or more and less than 5.

B: The number of the peeled checkerboard eyes of a hardened layer among 100 checkers is 5 or more and less than 10.

C: The number of the peeled checkerboard eyes of a hardened layer among 100 checkers is 10 or more.

[2] Test Example 2

[2-1] Preparation of Photosensitive Image Forming Material for Solder Resist

[2-1-1] Example 9

The component of Table 2 was mixed in 100 weight part of mixed solvents of methyl ethyl ketone / isopropanol (weight ratio 8/2), it was made to disperse | distribute and milled by the mill roll provided with three rolls at room temperature.

Next, the crude coating liquid was applied on an polyethylene terephthalate film (thickness 19 μm) as a temporary supporting film in an amount such that the dry film thickness was 25 μm using an applicator, and dried in an oven at 90 ° C. for 5 minutes. . The photosensitive image forming material was produced by laminating | stacking the polyethylene film (thickness 25micrometer) as a coating film on the photosensitive composition layer formed by this, and standing for 1 day. About the obtained photosensitive image forming material, image formation material was formed and various evaluation was performed similarly to [1-2]-[1-7]. Moreover, about [1-7], the image forming material was left to stand at 40 degreeC for 5 days before laser scanning exposure. The results are shown in Table 2.

In addition, the time-lapse stability of the photosensitive composition coating liquid and the photosensitive composition layer was evaluated as follows, respectively.

[2-1-1-1] Stability of Photocurable Composition Coating Liquid Over Time

It was "A" when the stability with time was evaluated by the method shown below about the photosensitive composition coating liquid obtained above.

After leaving the composition coating liquid at 35 ° C. for 2 days, scanning exposure and development were performed in the same manner as in the measurement of the exposure sensitivity, the amount of change in sensitivity compared to the sensitivity was measured, and evaluated by the following criteria. It was.

A: Less than 1% of the sensitivity decrease after leaving was left compared with before leaving.

B: 1% or more and 20% or less of the sensitivity deterioration after leaving, compared with before leaving.

C: More than 20% and less than 60% of the sensitivity fall after neglect compared with before leaving.

D: The sensitivity fall after leaving more than 60% compared with before leaving.

[2-1-1-2] Stability with Time of the Photosensitive Composition Layer

Moreover, it was "A" as a result of evaluating temporal stability by the method shown below about the photosensitive composition layer of the photosensitive image forming material obtained above.

After leaving the image forming material at 35 ° C. for 2 days, scanning exposure and development were performed in the same manner as in the measurement of the exposure sensitivity, and the amount of change in sensitivity compared to the sensitivity was measured and evaluated by the following criteria. It was.

A: Less than 1% of the sensitivity decrease after leaving was left compared with before leaving.

B: 1% or more and 20% or less of the sensitivity deterioration after leaving, compared with before leaving.

C: More than 20% and less than 60% of the sensitivity fall after neglect compared with before leaving.

D: The sensitivity fall after leaving more than 60% compared with before leaving.

The results are shown in Table 2.

[2-1-2] Comparative Example 1

In Example 9, the photosensitive sample was produced like it except having used the photoinitiator of (B7) instead of the photoinitiator (B2e) (refer Table 2 below). When laser exposure sensitivity was calculated | required by the method similar to Example 9, all the photosensitive layers of an exposure part were eluted at the time of image development, and the photocurable photosensitive image was not formed at all. The laser sensitivity is considered to be significantly lower than in Example 9.

[2-1-3] Comparative Example 2

In Example 9, the photosensitive sample was produced likewise except using (B8) instead of the photoinitiator (B2e) (refer Table 2 below). When laser exposure sensitivity was calculated | required by the method similar to Example 9, all the photosensitive layers of an exposure part were eluted at the time of image development, and the photocurable photosensitive image was not formed at all. The laser sensitivity is considered to be significantly lower than in Example 9.

[Formula 30]

(B6) 2,4-diethyl thioxanthone

(B2e) A photoinitiator (absorption maximum 383 nm) represented by the following formula was used without performing a dispersion process.

[Formula 31]

(B7) photoinitiator represented by the following formula (absorption maximum 336 nm)

[Formula 32]

(B8) 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] represented by the following chemical formula (absorption maximum 325 nm)

[Formula 33]

(C4) Diethylene glycol monoethyl ether acetate of the unsaturated group and carboxyl group-containing epoxy resin (acid value 100KOH.mg/g, weight average molecular weight 4,000, Nippon Kayaku Co., Ltd. "kaylard ZFR-1122") of the following structural repeating unit. 10.5% mixed solvent solution with solvent naphtha (65 wt% solids).

[Formula 34]

(C5) methacrylic acid / methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / styrene copolymer (% by weight = 20/35/10/10 / 15/10, weight average molecular weight 46,000)

[2-2] Preparation of Photosensitive Image Forming Material for Wiring Board Etch Resist (Example 10, Comparative Example 3)

[2-2-1] Example 10

The compound shown in Table 2 was added to the solvent (methyl ethyl ketone: 100 weight part), and it stirred at room temperature, and prepared the coating liquid. Next, on the polyethylene terephthalate film (16 micrometers in thickness) as a temporary support film, it apply | coated in the amount which a dry film thickness becomes 20 micrometers using an applicator of 75 micrometers, it was made to dry by wind for 1 minute, and then in an 85 degreeC oven Dry for 90 seconds. On this photosensitive composition layer, the polyethylene film (22 micrometers in thickness) as a coating film was laminated | stacked using a laminator, and left to stand for 1 day, and the photosensitive image forming material was produced. The obtained photosensitive image forming material was formed and various evaluations were performed in the same manner as in Example 9. The results are shown in Table 2.

[2-2-2] Comparative Example 3

In Example 10, a photosensitive sample was produced in the same manner as in Example 10 except for using the polymerization initiator (B7) instead of the photopolymerization initiator (B2d), and the laser exposure sensitivity was determined by the same method as in Example 10. At the time of image development, all the photosensitive layers of an exposure part eluted and the photocurable photosensitive image was not formed at all. In view of this, it is considered that the laser sensitivity is significantly lower than that in Example 10.

The present invention provides a photosensitive composition which is highly sensitive to laser light, particularly ultraviolet-violet-violet laser light, and is excellent in time-lapse stability and adhesion to a substrate, and is used in organic electroluminescence and the like by an image forming material using the same. Formation of a conductor circuit and an electrode processing substrate becomes effective.

Also, the entire contents of the descriptions, claims, and summaries of Japanese Patent Application No. 2004-305938, filed October 20, 2004, and Japanese Patent Application No. 2005-197677, filed July 6, 2005 are here. It is incorporated by reference as an indication of the specification of this invention.

Claims (12)

As a photosensitive composition containing (A) an ethylenically unsaturated group containing compound, (B) photoinitiator, and (C) alkali-soluble resin, (B) photoinitiator has a structure of following General formula (I), and is an average particle The photosensitive composition containing the photoinitiator whose diameter is 0.001 micrometer or more and 150 micrometers or less. [Formula 1]

(In formula, R <^2> may respectively be a C2-C20 alkanoyl group, a C3-C25 alkenoyl group, a C3-C8 cycloalkanoyl group, a C7-C20 benzoyl group, and C2-C20. An alkoxycarbonyl group of 10, a phenoxycarbonyl group of 7 to 20 carbon atoms, a heteroaryl group of 1 to 20 carbon atoms, a heteroaryloyl group of 1 to 20 carbon atoms, or an aminocarbonyl group of 1 to 20 carbon atoms, respectively. Arbitrary substituents) The method of claim 1, The photosensitive composition in which the photoinitiator represented by General formula (I) has absorption maximum in the wavelength range of 340-430 nm. The method according to claim 1 or 2, The photosensitive composition which has the maximum peak of spectral sensitivity in the wavelength range of 340-430 nm. The method according to any one of claims 1 to 3, The photosensitive composition whose photoinitiator represented by general formula (I) is a compound represented by general formula (II). [Formula 2]

(In formula, R <^1> represents a hydrogen atom, the C1-C20 alkyl group or C2-C20 alkenyl group which may be respectively substituted, or the following general formula (IIa). [Formula 3]

(In formula, R <^2>' , R <^3' , R <^4>' , R <^5>' , R <^6>' and R <^7>' are R <^2> , R in general formula (II) each independently of general formula (II). Same as ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ ) R <^2> may respectively be a C2-C12 alkanoyl group, a C4-C6 alkenyl group, a C7-C20 benzoyl group, a C2-C6 alkoxycarbonyl group, and a C7-C20 phenoxycarbonyl group Indicates. R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, an alkenoyl group having 3 to 12 carbon atoms, and 1 to 12 carbon atoms. Alkoxy group, cycloalkyl group having 5 to 8 carbon atoms, phenyl group, benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, phenoxycarbonyl group having 7 to 20 carbon atoms, or -OR ⁸ , -SR ⁹ , -SOR ⁹ , -SO ₂ R ⁹ or -NR ¹⁰ R ¹¹ , wherein 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 . Provided that R ⁸ is a hydrogen atom, an 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, an alkenyl group having 3 to 6 carbon atoms and a 3 to 15 carbon atoms A cycloalkyl group, a phenyl group,-(CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20) or an alkylsilyl group having 3 to 20 carbon atoms. R <^9> represents a hydrogen atom, a C1-C12 alkyl group which may be substituted, a C3-C12 alkenyl group, a C3-C15 cycloalkyl group, or a phenyl group, respectively. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms and an alkenyl group having 3 to 5 carbon atoms , A cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a benzoyl group, or a biphenyl group. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure) The method according to any one of claims 1 to 4, The photosensitive composition whose alkali-soluble resin of (C) is a carboxyl group-containing epoxy resin and / or a carboxyl group-containing vinyl resin. The method according to any one of claims 1 to 4, Alkali-soluble resin of (C) is carboxyl group-containing vinyl-type resin, and content of each structural repeating unit derived from ethylenic unsaturated carboxylic acids, alkyl (meth) acrylates, and styrene is the whole structure of a copolymer. 10-50 weight%, 15-80 weight%, and 1-40 weight% of each with respect to a repeating unit. The method according to any one of claims 1 to 6, Furthermore, (I) photosensitive composition containing inorganic filler. The method according to any one of claims 1 to 7, Furthermore, the (J) photosensitive composition containing a color material. A photosensitive composition for blue violet lasers, comprising (A) an ethylenically unsaturated group-containing compound, (B) photopolymerization initiator, and (C) an alkali-soluble resin, wherein the photosensitive composition for blue violet lasers has a spectral sensitivity in a wavelength region of 345 to 430 nm. The photosensitive composition for a blue-violet laser which has the maximum peak of and (B) The photoinitiator has the absorption maximum in the wavelength range of 340-430 nm, and contains the photoinitiator which has a structure of following General formula (I). . [Formula 4]

(In formula, R <^2> may respectively be a C2-C20 alkanoyl group, a C3-C25 alkenoyl group, a C3-C8 cycloalkanoyl group, a C7-C20 benzoyl group, and C2-C20. 10 alkoxycarbonyl group, a C7-20 phenoxycarbonyl group, a C1-C20 heteroaryl group, a C1-C20 heteroaryloyl group, or a C1-C20 aminocarbonyl group is shown. X and Y each independently represent an arbitrary substituent) A layer of the photosensitive composition as described in any one of Claims 1-8, and / or the photosensitive composition for blue-violet laser as described in Claim 9 is formed on a temporary support film, The image forming material characterized by the above-mentioned. The image forming material of Claim 10 is laminated | stacked on the photosensitive composition layer side on the to-be-processed substrate, The image forming material characterized by the above-mentioned. The image forming method of Claim 11 which scan-exposes the photosensitive composition layer of the image forming material of Claim 11 with the laser beam of wavelength 340-430nm, develops, and makes an image appear.