JP2006293024A - Blue-violet laser sensitive composition, image forming material for blue-violet laser and imaging material for blue-violet laser - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blue-violet laser sensitive composition which excels in sensitivity to blue-violet laser light and in developability and ensures easy stripping and removal of a resist image after resist processing when used for resist image formation, and which is free from edge fusion even if stored in a roll shape as a dry film material. <P>SOLUTION: The blue-violet laser sensitive composition contains (A) an alkali-soluble resin containing (meth)acrylates represented by formula (I) as copolymerized components, wherein R<SP>1</SP>represents H or methyl and R<SP>2</SP>represents a saturated or unsaturated hydrocarbon group containing a tertiary carbon atom and/or a quaternary carbon atom, (B) an ethylenically unsaturated compound, (C) a photopolymerization initiator and (D) a sensitizing dye having an absorption maximum in a wavelength region of 355-430 nm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an etching resist by direct drawing with a blue-violet laser beam in the formation of printed circuit boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, semiconductor packages and other fine electronic circuits. The present invention relates to a blue-violet laser photosensitive composition useful for forming a resist image for a plating resist, a solder resist, and the like, and particularly to a blue-violet laser photosensitive composition suitable for use in the production of a printed wiring board.

Conventionally, an image forming material (a) or the like has been used for forming printed circuit boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, fine electronic circuits such as semiconductor packages, and the like. Lithographic methods are widely used.
The image forming material (a) is a dry composition in which a photosensitive composition layer is formed by applying a coating liquid of a photosensitive composition on a temporary support film and drying it, and covering the surface of the photosensitive composition layer with a coating film. A film resist material or the like.

  The lithography method is performed according to the following procedure. First, the photosensitive image forming material (b) is produced by peeling off the coating film of the image forming material (a) and laminating it on the substrate to be processed. For the image forming material (b), the photosensitive composition coating liquid is directly applied onto the substrate to be processed and dried to form a photosensitive composition layer, and the surface of the photosensitive composition layer is protected as necessary. It is also produced by covering with a layer.

  Next, the photosensitive composition layer of the image forming material (b) on the substrate to be processed is subjected to image exposure through a mask film on which a circuit and an electrode pattern are drawn. Then, the temporary support film or the protective layer is peeled off, and a resist image corresponding to the circuit pattern is formed by developing using the difference in solubility between the exposed portion and the unexposed portion in the developer. Then, the substrate to be processed is etched, plated, or soldered using the resist image as a resist, and then the resist image is removed to form a circuit or electrode pattern drawn on the mask film on the substrate.

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

  On the other hand, the practical application of an ultraviolet solid laser having a wavelength of about 350 to 365 nm, which can be operated in a bright room environment such as yellow light illumination, has been studied. Conventional ultraviolet solid-state lasers have drawbacks such that the life of the light source is as short as about 1,000 hours, the beam diameter cannot be narrowed down so that thin lines can be drawn, and high-resolution patterns cannot be handled. However, due to the remarkable progress of laser technology in recent years, the life of the light source has been extended to 10,000 to 20,000 hours, the beam diameter can be narrowed down to 10 μm or less, and work under a yellow light is possible. Utilization of a semiconductor laser that can stably oscillate in a blue-violet region with a wavelength of 390 to 430 nm has come into practical use.

  Correspondingly, various studies have been made as a blue-violet laser-sensitive composition, for example, an ethylenically unsaturated compound, a hexaarylbiimidazole compound as a polymerization initiator, and a dialkylaminobenzene compound as a sensitizing dye. Specific polymer binders in which a part of the carboxyl group of the compound and carboxyl group-containing polymer is reacted with the epoxy group of the epoxy group-containing ethylenically unsaturated compound to have an ethylenically unsaturated bond in the side chain, etc. There has been proposed a lithographic printing plate using a photopolymerizable composition in combination with a photosensitive layer (Patent Document 1). However, since the photosensitive composition layer disclosed therein is for a lithographic printing plate, it is thin and has a thickness of 5 μm or more. There was a problem that the exposure sensitivity was not sufficient and the developability was poor. In addition, there is a problem that it is difficult to remove and remove the resist image after the resist processing which seems to be caused by the epoxy group-containing ethylenically unsaturated compound remaining in the polymer binder.

  Further, as a thick blue-violet laser image forming material, for example, the film thickness of the resist material layer is 10 μm or more, and the absorbance at the exposure wavelength of the photosensitive resist material layer is 0.3 or less per 1 μm film thickness. An image forming material characterized by this has been proposed (Patent Document 2). However, a dry film resist material (corresponding to the image forming material (a) in the present application) having a photosensitive resist material layer constituting the image forming material disclosed therein has a film thickness when stored in a roll shape. When the thickness is increased, there is a problem of so-called edge fusion, in which the photosensitive layer oozes out from the end face of the roll and causes a film to stick or dust is generated.

On the other hand, as the high-resolution image forming material (a), for example, a binder polymer containing a (meth) acrylic acid ester having a branched or cyclic saturated hydrocarbon group having 9 or more carbon atoms as a copolymerization component; A photosensitive element using a photosensitive resin composition containing an ethylenically unsaturated compound and a photopolymerization initiator has been proposed (Patent Document 3). However, the photosensitive element disclosed therein can obtain high resolution when exposed at an exposure amount of 100 mJ / cm ² or more using a high-pressure mercury lamp or the like, and is 50 mJ / cm ² or less from the viewpoint of throughput. For laser direct drawing with blue-violet laser light, which requires image formation with a large amount of exposure, the sensitivity is insufficient, and furthermore, a high energy amount can be given to the photosensitive layer in a short time. However, since the photopolymerization reaction occurs non-uniformly, there is a problem that resolution is lowered due to swelling during development.
JP 2002-296664 A Japanese Patent Laid-Open No. 2004-199031 JP 2004-317874 A

  The present invention has been made in view of the above-described prior art, and when used for resist image formation, it has excellent sensitivity to blue-violet laser light and developability, and peeling of a resist image after resist processing. A blue-violet laser photosensitivity that is easy to remove and does not cause edge fusion even when stored in the form of a roll as a dry film material, and is particularly suitable for direct drawing with blue-violet laser light An object is to provide a composition. Another object of the present invention is to provide a blue-violet laser image forming material and a blue-violet laser image forming material suitable for direct drawing with a blue-violet laser beam by using the blue-violet laser photosensitive composition. .

As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by using a specific polymer as a polymer binder in the photosensitive composition, and have reached the present invention. Therefore, the gist of the present invention is a blue-violet laser-sensitive composition containing the following component (A), component (B), component (C), and component (D).
(A) Alkali-soluble resin containing (meth) acrylates represented by the following general formula (I) as a copolymerization component (B) Ethylenically unsaturated compound (C) Photopolymerization initiator (D) 355-430 nm Sensitizing dye having absorption maximum in wavelength range

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated or unsaturated hydrocarbon group containing a tertiary carbon atom and / or a quaternary carbon atom.)
Another gist of the present invention is an image forming material for a blue-violet laser, wherein the blue-violet laser-sensitive composition layer is formed on a temporary support film.
Another gist of the present invention is a blue-violet laser image-forming material, wherein the blue-violet laser image-forming material is laminated on the substrate to be processed on the blue-violet laser-sensitive composition layer side.

  The present invention, when used for resist image formation, is excellent in sensitivity to blue-violet laser light and developability, and it is easy to peel and remove the resist image after resist processing. A photosensitive composition that does not cause edge fusion even when stored in a form and that is particularly suitable for direct drawing with a blue-violet laser beam can be provided. In addition, the present invention can provide a blue-violet laser image forming material and a blue-violet laser image forming material suitable for direct drawing with a blue-violet laser beam by using the blue-violet laser photosensitive composition.

The constituent features of the present invention described below are representative examples of embodiments of the present invention and are not specified in these contents. In the present invention, “(meth) acryl” means “acryl” and / or “methacryl”.
[1] Blue-violet laser-sensitive composition The blue-violet laser-sensitive composition of the present invention comprises the following components (A), (B), (C), and (D). And Further, if necessary, it may further contain components other than those described above.

(A) Alkali-soluble resin containing specific (meth) acrylates as copolymerization component (B) Ethylenically unsaturated compound (C) Photopolymerization initiator (D) Increase having an absorption maximum in the wavelength range of 355 to 430 nm Hereinafter, each component will be described in detail.

[1-1] (A) Alkali-soluble resin containing specific (meth) acrylates as copolymerization component The alkali-soluble resin of component (A) constituting the blue-violet laser-sensitive composition of the present invention is on the substrate. In the present invention, (meth) acrylates represented by the following general formula (I) are intended to improve the formability, resolution, and developability of the photosensitive composition as a layer. As a copolymerization component (containing a structural repeating unit derived from (meth) acrylates represented by the following general formula (I)) is essential.

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated or unsaturated hydrocarbon group containing a tertiary carbon atom and / or a quaternary carbon atom.)
Specific examples of R ² include tert-butyl group, isobutyl group, tert-amyl group,
A branched saturated hydrocarbon group having 4 to 20 carbon atoms, such as an isoamyl group and a pinacolyl group;
Norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, 2-ethyladamantyl group, menthyl group, isomenthyl group, 2-tert-butylcyclohexyl group,
4-tert-butylcyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3, Cyclic saturated hydrocarbons having 6 to 20 carbon atoms such as 5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, decahydro-1-naphthyl group, decahydro-2-naphthyl group, 3,3,5-trimethylcyclohexyl group Group;
A branched unsaturated hydrocarbon group having 5 to 20 carbon atoms, such as a group represented by the following structural formula;

A cyclic unsaturated hydrocarbon group having 7 or more carbon atoms, such as a group represented by the following structural formula;

Etc.
Among them, a saturated or unsaturated hydrocarbon group in which the carbon atom directly bonded to the carboxyl group is a tertiary carbon atom, and a saturated or unsaturated hydrocarbon group containing a quaternary carbon atom are preferable, and among them, the number of carbon atoms A saturated hydrocarbon group of 10 or less is particularly preferred.
Specific examples of the (meth) acrylates represented by the general formula (I) include the following compounds.

tert-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-amyl (meth) acrylate, isoamyl (meth) acrylate, pinacolyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl ( (Meth) acrylate, 2-adamantyl (meth) acrylate, menthyl (meth) acrylate, isomenthyl (meth) acrylate, 2-tert-butylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, 1-
Methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 3-methylcyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 2,3-dimethylcyclohexyl (meth) acrylate, 3,5-dimethyl Cyclohexyl (meth) acrylate, 2,6-dimethylcyclohexyl (meth) acrylate.

  In the alkali-soluble resin (A) component, examples of the copolymer component having an alkali-soluble group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy. -Ethylenically unsaturated phenols containing phenolic hydroxyl groups such as α-methylstyrene and p-hydroxy-α-methylstyrene; (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid And ethylenically unsaturated carboxylic acids containing a carboxyl group such as citraconic acid. Among them, ethylenically unsaturated carboxylic acids containing a carboxyl group are preferable, and (meth) acrylic acid is particularly preferable.

  In addition, the alkali-soluble resin in the present invention is obtained in addition to (meth) acrylates represented by the general formula (I) and each constituent repeating unit derived from the copolymer component having the alkali-soluble group. From the standpoint of resolution of the resist image, for example, hydroxyalkyl such as hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. It is preferable that the structural repeating unit derived from (meth) acrylates is included.

  In the present invention, the content of the structural repeating unit derived from the (meth) acrylate represented by the general formula (I) in the alkali-soluble resin is 5% by weight or more with respect to all the structural repeating units of the copolymer. It is preferably 10% by weight or more, more preferably 50% by weight or less, and particularly preferably 35% by weight or less. If the content of the structural repeating unit derived from the (meth) acrylates represented by the general formula (I) is too small, the exposed portion swells during development, and the resolution tends to decrease, and the amount is too large. In addition, the hydrophobicity of the non-exposed portion is increased, so that developability is deteriorated and a residue tends to be easily generated.

  Further, the content of the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acids in the alkali-soluble resin is preferably 10% by weight or more, more preferably 15% by weight or more based on the total constitutional repeating unit of the copolymer. Is preferably 50% by weight or less, and particularly preferably 35% by weight or less. If the content of the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acid is too small, the non-exposed part of the photosensitive composition tends to be inferior to the developer after exposure as a photosensitive composition. There is a tendency that the film thickness of the exposed portion with respect to the liquid is reduced, or the resolution is poor.

The content of the structural repeating unit derived from the hydroxyalkyl (meth) acrylates in the alkali-soluble resin is preferably 1% by weight or more with respect to all the structural repeating units of the copolymer, and is preferably 5% by weight. The above is particularly preferable, and it is preferably 30% by weight or less, and particularly preferably 20% by weight or less.
As the repeating unit constituting the alkali-soluble resin of the component (A) in the present invention, (meth) acrylates represented by the general formula (I), ethylenically unsaturated carboxylic acids, and hydroxyalkyl (meth) acrylates In addition to the structural repeating unit derived from the above, methyl (meth) acrylate, ethyl (meth) acrylate, n- or i-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n- Tertiary and quaternary carbon-free alkyl (meth) acrylates such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; and / or styrene , Α-methylstyrene, α-ethylstyrene, o-me Styrenes such as til styrene, m-methyl styrene, p-methyl styrene, 2,5-dimethyl styrene, p-chloro styrene, p-bromo styrene and dibromo styrene may be contained.

  As the alkyl (meth) acrylates not containing tertiary and quaternary carbon, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like are particularly preferable. . In addition, the content of the structural repeating unit derived from the alkyl (meth) acrylates not containing the tertiary and quaternary carbon in the alkali-soluble resin is 15% by weight or more based on the total structural repeating unit of the copolymer. It is preferably 30% by weight or more, more preferably 80% by weight or less, and particularly preferably 65% by weight or less. When the content of the constitutional repeating unit derived from alkyl (meth) acrylates is too small, tackiness is insufficient in the case of using the photosensitive composition as a dry film resist material, and the production and handling as a dry film resist material On the other hand, if it is too much, introduction of other constitutional repeating units is quantitatively restricted, and it becomes difficult to balance various performances as a carboxyl group-containing copolymer. .

  As the styrenes, styrene and α-methylstyrene are particularly preferable, and the content of the constitutional repeating unit derived from the styrenes in the alkali-soluble resin is 1% by weight or more with respect to all the constitutional repeating units of the copolymer. It is preferably 5% by weight or more, more preferably 40% by weight or less, and particularly preferably 15% by weight or less. If the content of the constitutional repeating unit derived from styrene is too small, the photosensitive layer after exposure or the resist image after development tends to be inferior in scratch resistance as a photosensitive composition, whereas if it is too much, the photosensitivity is insensitive. When the composition is used as a dry film resist material, the photosensitive composition layer tends to crack easily when the composition is used as a dry film resist material.

  In the present invention, the alkali-soluble resin preferably has an acid value of 100 to 300 mg · KOH / g, and the weight average molecular weight in terms of polystyrene is preferably 20,000 or more, and preferably 30,000 or more. More preferably, it is more preferably 40,000 or more. Further, it is preferably 150,000 or less, more preferably 100,000 or less, and particularly preferably 90,000 or less. If the weight average molecular weight is too small, the film strength as the photosensitive composition layer is lowered, and developability becomes unstable and chipping properties tend to be deteriorated. The viscosity of the coating composition coating solution is too high, resulting in poor applicability and a tendency to deteriorate developability.

[1-2] (B) Ethylenically unsaturated compound In addition, the ethylenically unsaturated compound (B) constituting the blue-violet laser-sensitive composition of the present invention is irradiated with actinic rays. In such a case, a radically polymerizable ethylenically unsaturated bond that undergoes addition polymerization by the action of a photopolymerization initiating system containing a photopolymerization initiator of the component (C), which will be described later, and is optionally crosslinked or cured, is present in the molecule. A compound having one.
As the ethylenically unsaturated compound, a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid Unsaturated carboxylic acids such as, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, etc. may be used. From the point that the difference in sex can be enlarged, it is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, and the acrylate compound in which the unsaturated bond is derived from a (meth) acryloyloxy group Particularly preferred.

  As a compound having two or more ethylenically unsaturated bonds in the molecule, typically, esters of unsaturated carboxylic acid and polyhydroxy compound, urethane of hydroxy (meth) acrylate compound and polyisocyanate compound (meta ) Acrylates, and (meth) acrylic acid or epoxy (meth) acrylates of hydroxy (meth) acrylate compounds and polyepoxy compounds.

  Specific examples of the esters include unsaturated carboxylic acid as described above, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), trimethylene. Glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylol ethane, tetramethylol ethane, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene Reaction products with aliphatic polyhydroxy compounds such as oxide adducts, diethanolamine, triethanolamine, and more specifically, for example, ethylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylol Ethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Limethylolpropane 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 di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, so Examples thereof include rubitol penta (meth) acrylate, sorbitol hexa (meth) acrylate and the like, and similar crotonate, isocrotonate, maleate, itaconate, citraconate and the like.

  Furthermore, as the esters, unsaturated carboxylic acids as described above, aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts or glycidyl group-containing compound adducts In particular, for example, hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate] Bisphenol A bis [trioxyethylene (meth) acrylate], bisphenol A bis [pentaoxyethylene (meth) acrylate], bisphenol A bis [hexaoxyethylene (meth) acrylate] Bisphenol A bis [glycidyl ether (meth) acrylate] and the like, and a reaction product of an unsaturated carboxylic acid as described above and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, For example, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tri (meth) acrylate, etc., and a reaction product of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound, specifically For example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, a condensate of (meth) acrylic acid, maleic acid and diethylene glycol, a condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, Condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin. It is.

  Specific examples of urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and tetramethylol. Hydroxy (meth) acrylate compounds such as ethane tri (meth) acrylate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,6 Aliphatic polymers such as 11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Cycloaliphatic polyisocyanates such as isocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanates such as aromatic polyisocyanates and isocyanurates Aneto, a reaction product of a polyisocyanate compounds and the like.

  Moreover, as the epoxy (meth) acrylates, specifically, for example, (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene Glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylol Aliphatic polyepoxy compounds such as propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy Compounds, brominated phenol novolac polyepoxy compounds, aromatic polyepoxy compounds such as (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ethers, Examples thereof include reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

In addition to the above, as other ethylenically unsaturated compounds, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, etc. Is mentioned. These ethylenically unsaturated compounds may be used alone or in combination of two or more.
As the ethylenically unsaturated compound of the above component (B), in the present invention, ester (meth) acrylates or urethane (meth) acrylates are preferable, ester (meth) acrylates are particularly preferable, and the ester ( Among the (meth) acrylates, ester (meth) acrylates having a polyoxyalkylene group such as polyethylene glycol, polypropylene glycol, or a polyethylene oxide adduct of bisphenol A, and having two or more (meth) acryloyloxy groups are particularly preferred. preferable.

[1-3] (C) Photopolymerization Initiator The photopolymerization initiator of component (C) constituting the blue-violet laser-sensitive composition of the present invention coexists with a sensitizing dye of component (D) described later. A radical generator that receives photoexcitation energy of a sensitizing dye to generate active radicals when irradiated with light under the above, and leads to polymerization of the ethylenically unsaturated compound of component (B), for example, Examples include hexaarylbiimidazole compounds, titanocene compounds, halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, diaryliodonium salts, organic borates, and organic peroxides. Among these, hexaarylbiimidazole compounds and titanocene compounds are preferable, and hexaarylbiimidazole compounds are particularly preferable from the viewpoints of sensitivity as a photosensitive composition, adhesion to a substrate, and storage stability.

  As the hexaarylbiimidazole compound, specifically, for example, 2,2′-bis (o-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (p-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (p-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (fluorophenyl) -4,4 ′, 5,5′- Tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5 , 5'-tetra ( -Methylphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dimethoxyphenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (p -Methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) ) -4,4 ′, 5,5′-tetra (p-chlorophenyl) biimidazole, 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-dichlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o-chloro- p-methoxyphenyl) biimidazole 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Particularly preferred are those in which the benzene ring bonded to the 4 ′, 5,5′-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

  Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadienyl titanium bisphenyl. Cyclopentadienyl 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 (methyl Cyclopentadienyl) titanium bis (2,3,4,5,6) Pentafluorophenyl), dicyclopentadienyl-titanium-bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like. Of these, titanium compounds having a dicyclopentadienyl structure and a biphenyl structure are preferred, and those in which the o-position of the biphenyl ring is substituted with a halogen atom are particularly preferred.

[1-4] (D) Sensitizing dye having absorption maximum in wavelength range of 355 to 430 nm The sensitizing dye of component (D) constituting the blue-violet laser-sensitive composition of the present invention has a wavelength range of 355 to 430 nm. And absorbs light in the blue-violet region of the wavelength range efficiently, transmits the photoexcitation energy to the photopolymerization initiator of the component (C), and decomposes the photopolymerization initiator. And a light-absorbing dye having a sensitizing function for generating an active radical that induces polymerization of the ethylenically unsaturated compound as the component (B). Here, the absorption maximum wavelength is a wavelength showing a maximum value when the sensitizing dye is dissolved in tetrahydrofuran and the absorption wavelength is measured, and the absorption maximum wavelength in the wavelength region of 355 to 430 nm is the maximum wavelength. The longest wavelength is preferred.

  Examples of the sensitizing dye include (i) a diaminobenzophenone compound having a basic skeleton represented by the following formula described in JP-A No. 2000-10277 and JP-A No. 2004-198446, and (ii) JP-A No. 2004. -Aminophenyl-benzimidazole / benzoxazole / benzothiazole compounds having the following formula as described in the specification of JP-A-198446, etc., and (iii) the following formula as described in JP-A-2004-252421, etc. as the basic skeleton (Iv) an aminocarbostyryl compound having a basic skeleton represented by the following formula described in JP-A No. 2004-221958 and the like, (v) JP-A No. 2002-169282, JP-A No. 2004-2004 A merocyanine compound having a basic skeleton represented by the following formula described in the specification of 191938, etc .; (vi) JP 2002-268239 A (Vii) an imide-based compound having the following formula as a basic skeleton described in Japanese Patent Application No. 2003-291606, (viii) Benzimidazole / benzoxazole / benzothiazole compounds having a basic skeleton, (ix) triazole compounds having the following formula as a basic skeleton, (x) cyanostyryl compounds having the following formula as a basic skeleton, (xi) A stilbene compound having a basic skeleton, (xii) an oxadiazole / thiadiazole compound having the following formula as a basic skeleton, (xiii) a pyrazoline compound having the following formula as a basic skeleton, and (xiv) a formula having the following formula as a basic skeleton A coumarin compound, (xv) a triphenylamine compound having the following skeleton as described in Japanese Patent Application No. 2004-218915, etc., and (xvi) Japanese Patent Application No. 2003-340924 Acridone based compounds having a basic skeleton of the following formula according to Saisho like, include a carbazole-based compounds having a basic skeleton of the following formula described in (xvii) No. 2004-218915 Pat like.

  In the following formulae, X and Z each independently represent a nitrogen atom, an oxygen atom, a sulfur atom, or C—R, Y represents an arbitrary linking group, and n is an integer of 1 or more. The compounds of the following formulas showing the basic skeleton are, for example, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, aralkyl groups, alkenyloxy groups, alkenyls, respectively. Substituents such as thio group, acyl group, acyloxy group, amino group, acylamino group, carboxyl group, carboxylic acid ester group, carbamate group, carbamoyl group, sulfamoyl group, sulfonic acid ester group, saturated or unsaturated heterocyclic group These substituents may further have a substituent, and a plurality of substituents may be bonded to each other to form a cyclic structure.

Of these, dialkylaminobenzene compounds, triphenylamine compounds, acridone compounds, carbazole compounds, and the like are preferable. Among them, as the dialkylaminobenzene compound, in particular, a dialkylaminobenzophenone compound, a dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring, benzene A dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom with respect to an amino group on the ring, or a dialkylaminobenzene compound having a carbostyryl skeleton is preferred.
The dialkylaminobenzophenone compound is preferably a compound represented by the following general formula (II).

[In the formula (II), R ³ , R ⁴ , R ⁷ , and R ⁸ each independently represents an optionally substituted alkyl group, and R ⁵ , R ⁶ , R ⁹ , and R ¹⁰ each independently represents an alkyl group which may have a substituent or a hydrogen atom, R ³ and R ⁴ , R ⁷ and R ⁸ , R ³ and R ⁵ , R ⁴ and R ⁶ , R ⁷ and R ⁹ , and R ⁸ and R ¹⁰ may each independently form a nitrogen-containing heterocycle. ]
Here, the carbon number of the alkyl group of R ³ , R ⁴ , R ⁷ and R ⁸ in the formula (I), and the carbon when R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are alkyl groups, The number is preferably 1-6. Further, when forming a nitrogen-containing heterocycle, it is preferably a 5- or 6-membered ring, and R ³ and R ⁵ , R ⁴ and R ⁶ , R ⁷ and R ⁹ , or R ⁸ and R ¹⁰ are 6-membered rings. It is preferable that R ³ and R ⁴ and R ⁵ and R ⁶ , and / or R ⁷ , R ⁸ , R ⁹ and R ¹⁰ form a julolidine ring. Particularly preferred. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred.
Specific examples of the compound represented by the general formula (II) include compounds having the following structure.

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

[In Formula (III), R ³ and R ⁴ each independently represents an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently have a substituent. R ³ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁶ may each independently form a nitrogen-containing heterocycle, and X represents , An oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and the benzene ring condensed to the heterocyclic ring may have a substituent. ]
Here, the carbon number of the alkyl group of R ³ and R ⁴ in formula (III), and the carbon number when R ⁵ and R ⁶ are an alkyl group are preferably 1 to 6, and When forming a nitrogen heterocycle, a 5- or 6-membered ring is preferable, and R ³ and R ⁵ , or R ⁴ and R ⁶ preferably form a 6-membered tetrahydroquinoline ring, and R ³ It is particularly preferable that R ⁴ , R ⁵ and R ⁶ form a julolidine ring. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred. In addition, when X is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when it is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.
Specific examples of the compound represented by the general formula (III) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl). ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole, and Compounds of the serial structure.

Further, other than the compound represented by the general formula (III), p-
Examples of the dialkylaminobenzene compound having a heterocyclic group as a substituent at the carbon atom at the position include 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, and 2- (p-dimethyl). Aminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl) -1, Examples include 3,4-oxadiazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole.
Moreover, as the dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom with respect to the amino group on the benzene ring, those represented by the following general formula (IV) are preferable.

[In the formula (IV), R ³ and R ⁴ each independently represents an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently represent a substituent. also alkyl group, or a hydrogen atom, R ³ and R ^4, R ³ and R ^5, and each, independently of R ⁴ and R ^6, may form a nitrogen-containing heterocycle, R ¹¹ Represents a monovalent group or a hydrogen atom, and R ¹² represents a monovalent group. ]
Here, the carbon number of the alkyl group of R ³ and R ⁴ in formula (IV), and the carbon number when R ⁵ and R ⁶ are an alkyl group are preferably 1 to 6, and When forming a nitrogen heterocycle, it is preferably a 5- or 6-membered ring, but R ⁵ and R ⁶ are preferably hydrogen atoms. Examples of the monovalent group of R ¹¹ and R ¹² include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkenyloxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, Aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino group, acylamino group, carbamate group, sulfonamido group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio Group, imino group, cyano group, and heterocyclic group. Among these, R ¹¹ is preferably a hydrogen atom, and R ¹² is preferably an aryl group.
Moreover, as a dialkylaminobenzene type compound which formed the carbostyryl skeleton, what is represented by the following general formula (V) is preferable.

[In the formula (V), R ³ , R ⁴ and R ¹³ each independently represents an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently represents a substituent. An alkyl group which may have, or a hydrogen atom, R ³ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁶ may each independently form a nitrogen-containing heterocycle; R ¹⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ]
Here, the carbon number of the alkyl group of R ³ , R ⁴ , and R ¹³ in formula (V), and the carbon number when R ⁵ , R ⁶ , and R ¹⁴ are alkyl groups are 1-6. It is preferable that when a nitrogen-containing heterocyclic ring is formed, a 5- or 6-membered ring is preferable, but R ⁵ and R ⁶ are preferably hydrogen atoms. R ¹⁴ is preferably a phenyl group.

  In addition, as a triphenylamine compound, triphenylamine is a basic skeleton, and the three benzene rings may have a condensed ring such as a hydrocarbon ring or a heterocyclic ring, or an alkyl group or a cycloalkyl group. Alkenyl group, cycloalkenyl group, alkoxy group, alkenyloxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylate group, carbamoyl Group, amino group, acylamino group, carbamate group, sulfonamide group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio group, alkenylthio group, imino group, cyano group, nitro group, halogen atom, and heterocyclic group And may have a substituent such as , May further have a substituent, preferably one represented by the following general formula (VI) or (VII).

(In the above general formulas (VI) and (VII), the rings A to E each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and the ring A and ring B, the ring D and ring E may be bonded to each other to form a bonded ring containing N. In the general formula (VII), the linking group L represents a linking group containing an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring. The linking groups L and N are bonded by the aromatic hydrocarbon ring or aromatic heterocyclic ring, and n represents an integer of 2 or more.)
In addition, the acridone-based compound has an acridone ring as a basic skeleton, and the two benzene rings may have a condensed ring such as a hydrocarbon ring or a heterocyclic ring, or an alkyl group, a cycloalkyl group, or an alkenyl group. , Cycloalkenyl group, alkoxy group, alkenyloxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, arylalkenyl 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, alkenylthio group, imino group, cyano group, nitro group, halogen atom, heterocyclic group, etc. Group may be substituted, and those substituents are further substituted It may have. The hydrogen atom in the imino group may be substituted with a substituent such as an alkyl group or an acyl group.

  In addition, as a carbazole compound, etc., the carbazole ring is a basic skeleton, and the two benzene rings may have a condensed ring by a hydrocarbon ring or a heterocyclic ring, or an alkyl group, a cycloalkyl group, an alkenyl group. Group, cycloalkenyl group, alkoxy group, alkenyloxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, arylalkenyl 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, alkenylthio group, imino group, cyano group, nitro group, halogen atom, heterocyclic group, etc. May have a substituent, and these substituents are Substituent may have. The hydrogen atom in the imino group may be substituted with a substituent such as an alkyl group or an acyl group.

As the sensitizing dye of the component (D), in the present invention, a dialkylaminobenzophenone compound represented by the general formula (II), an amino group on the benzene ring represented by the general formula (IV) A dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom, a dialkylaminobenzene compound having a carbostyril skeleton represented by the general formula (A), and tri Phenylamine compounds are particularly preferred.

  The (A) component carboxyl group-containing copolymer constituting the blue-violet laser-sensitive composition of the present invention, the (B) component ethylenically unsaturated compound, the (C) component photopolymerization initiator, and the above (D) Each content rate of the sensitizing dye of a component is 20-80 weight% of (A) component with respect to the whole quantity of a photosensitive composition, (B) 20-80 weight% of component, (C) component Is 0.1 to 20% by weight, and component (D) is preferably 0.01 to 10% by weight.

[1-5] Hydrogen Donating Compound In addition to the components (A) to (D), the blue-violet laser-sensitive composition of the present invention is a hydrogen donating compound for the purpose of improving photopolymerization initiation ability and the like. Examples of the hydrogen-donating compound include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2- Mercapto group-containing compounds such as mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylol Propane tristhioglyconate, pentaerythritol Polyfunctional thiol compounds such as tetrakisthiopropionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or salts thereof such as ammonium and sodium salts, derivatives such as dipolar ionic compounds thereof, phenylalanine, or the like Examples thereof include amino acids having an aromatic ring such as esters, salts thereof such as ammonium and sodium salts, and derivatives such as dipolar compounds, or derivatives thereof. Among them, in the present invention, mercapto group-containing compounds and amino acids or derivatives thereof are preferable.
In the blue-violet laser photosensitive composition of the present invention, the content ratio of the hydrogen-donating compound contained in addition to the components (A) to (D) is 5% by weight or less based on the total amount of the photosensitive composition. It is preferable that it is 2% by weight or less.

[1-6] Other components Further, the blue-violet laser-sensitive composition of the present invention includes, in addition to the above-described components, a polymerization inhibitor and a photosensitivity for preventing thermal or temporal polymerization of the photosensitive composition. A plasticizer for controlling film physical properties as a composition layer, a dye (visual paint) for visualizing an image to be formed, a color changing agent, and an adhesion of the formed image to a substrate to be processed An adhesion promoter, an antioxidant, a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, a flame retardant, a solvent, a surfactant, and the like may be contained as necessary.

  Examples of the polymerization inhibitor include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 2,6-di-t-butyl-p-cresol, 4-methoxy-2-hydroxybenzophenone. , Β-naphthol, naphthylamine, nitrobenzene, picric acid, p-toluidine, chloranil, phenothiazine, cuprous chloride and the like, and as a plasticizer, for example, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, etc. Phthalate esters, glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, phosphate esters such as tricresyl phosphate, triphenyl phosphate, benzenesulfonamide, -Amides such as toluenesulfonamide, Nn-butylacetamide, diisobutyl adipate, dioctyl adipate, dioctyl azelate, dimethyl sebacate, dibutyl malate and other aliphatic dibasic esters, glycerin triacetyl, triethyl citrate And glycols such as tributyl citrate, butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate, polyethylene glycol, polypropylene glycol and the like.

  Examples of visible paints include tris (4-dimethylaminophenyl) methane [leuco crystal violet], tris (4-diethylamino-2-methylphenyl) methane, leucomacarite green, leucoaniline, leucomethyl violet, and brilliant. Green, eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, meta Nyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, parame Lured, Congo Red, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue A, Phenacetalin, Methyl Violet, Malachite Green, Parafuchsin, Oil Blue # 603 (manufactured by Orient Chemical Industries), Victoria Pure Blue BOH, Spiron Blue GN [ Hodogaya Chemical Co., Ltd.], rhodamine 6G and the like. Among them, leuco dyes such as leuco crystal violet are 0.01 to 1.5% by weight, particularly 0.05 to 0%, based on the total amount of the photosensitive composition. Further, it is preferable to contain 0.001 to 0.5% by weight, particularly 0.002 to 0.2% by weight of crystal violet, macalite green, brilliant green and the like.

  Examples of the color changing agent include, in addition to the visible colorant, for example, diphenylamine, dibenzylamine, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4′-biphenyldiamine, o Examples of the adhesion-imparting agent include benzimidazole, henzothiazole, benzoxazole, benzotriazole, 2-mercaptobenzothiazole, and 2-mercaptobenzimidazole.

[2] Image forming material for blue-violet laser and image forming material for blue-violet laser The blue-violet laser photosensitive composition of the present invention is an image forming material for blue-violet laser of the present invention (hereinafter referred to simply as image formation in section [2]). Can be used to form the material (sometimes referred to as material (a)). The image forming material (a) is usually formed on a temporary support film as a coating solution in which each of the above components is dissolved or dispersed in an appropriate solvent, dried, and if necessary, a photosensitive composition layer formed. It is formed by covering the surface with a coating film. Examples of such an image forming material (a) include a dry film resist material.

  The image forming material (a) further forms the image forming material for blue-violet laser of the present invention (hereinafter, simply referred to as an image forming material (b) in Chapter [2]). Can be used. There are usually two types of image forming materials (b). One is prepared by peeling off the coating film when the photosensitive composition layer side of the image forming material (a) is covered with a coating film and laminating it on a substrate to be processed. The other is created by the following procedure. (1) A coating solution in which each component of the blue-violet laser composition is dissolved or dispersed in an appropriate solvent is used; (2) directly coated on the substrate to be processed and dried; (3) the substrate to be processed. A layer of the blue-violet laser-sensitive composition of the present invention is formed thereon.

The image forming material (b) is suitably used in the following image forming method. That is, the photosensitive composition layer of the image forming material (b) is scanned and exposed with a laser beam and developed to reveal an image.
As the temporary support film when used as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. At that time, when those films have the solvent resistance, heat resistance, etc. necessary for the production of the dry film resist material, the photosensitive composition coating solution is directly applied on the temporary support film. It can be applied and dried to produce a dry film resist material, and even if those films have low solvent resistance, heat resistance, etc., for example, polytetrafluoroethylene film, release film, etc. First, a photosensitive composition layer is formed on a film having releasability, and then a temporary support film having low solvent resistance or heat resistance is laminated on the layer, and then the film having releasability is peeled off. By doing so, a dry film resist material can also be produced. In particular, when high resolution is pursued, the haze value of the temporary support film is preferably 0.01 to 1.8%, and the thickness of the temporary support film is preferably 10 to 30 μm.

  The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility with respect to the components used and gives good coating properties. For example, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve solvent, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether and other propylene glycol solvents, Butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate Ester solvents such as ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as methanol, isopropanol, heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketones such as cyclohexanone, methyl ethyl ketone Examples thereof include solvents, aromatic solvents such as toluene, highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons thereto. Among these, from the standpoints of solubility, surface tension, viscosity, ease of drying, and the like, single or mixed solvents such as methyl ethyl ketone, methanol, isopropanol, and toluene are preferable. The ratio of the solvent used is usually in the range of about 0.5 to 2 times by weight with respect to the total amount of the photosensitive composition.

  As the coating method, a conventionally known method such as a die coating method, a knife coating method, a roll coating method, a spray coating method, or a spin coating method can be used. The coating amount at that time is usually 5 μm or more in terms of dry film thickness and 10 μm or more as a dry film resist material in terms of image forming properties to be described later and workability such as subsequent etching and plating. The thickness is preferably 15 μm or more, more preferably 200 μm or less, and even more preferably 100 μm or less from the viewpoint of sensitivity and the like. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 30 to 130 ° C., and the drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes. It is done.

In addition, when used as a dry film resist material or the like, it is preferable to cover the surface of the formed photosensitive composition layer with a coating film until it is laminated on a substrate to be processed. Conventionally known films such as polyethylene film, polypropylene film and polytetrafluoroethylene film are used. In particular, when high resolution is pursued, the surface roughness of the coating film is preferably such that Ra of the surface in contact with the photopolymerizable composition is 0.15 μm or less, and Rmax is 1.5 μm or less. The number of fish eyes having a diameter of 80 μm or more contained in the coating film is preferably 5 / m ² or less.

  Further, when the photosensitive composition layer side of the dry film resist material is covered with a coating film, the coating film is peeled off and laminated by heating, pressurizing, or the like. The substrate to be processed in preparing the resist image forming material by directly applying and drying the photosensitive composition coating liquid is exposed to a laser beam and developed by exposing the photosensitive composition layer formed thereon. A pattern such as a circuit or an electrode is formed on the surface by etching or plating using the displayed image as a resist. Copper, aluminum, gold, silver, chromium, zinc, tin, lead The metal plate itself such as nickel may be used, but usually, for example, epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol Resin, thermoplastic resin such as melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, fluorine resin, Paper, glass, and inorganic materials such as alumina, silica, barium sulfate, calcium carbonate, or composite materials such as glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin Etc., and a metal foil such as metal oxide such as indium oxide, tin oxide or indium oxide doped tin oxide is heated on the surface of the insulating support having a thickness of about 0.02 to 10 mm, and pressure bonding laminate Or by a method such as sputtering, vapor deposition, plating, etc. Metal-clad laminate formed with 00μm approximately conductive layer is preferably used.

  In the case where a resist image forming material is produced by directly applying and drying the photosensitive composition coating solution, the polymerization inhibiting action by oxygen of the photosensitive composition layer formed on the substrate to be processed For example, a protective layer formed by applying and drying a solution of, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, or hydroxyethyl cellulose is provided on the photosensitive composition layer. May be.

  Then, the photosensitive composition layer of the resist image forming material having the blue-violet laser-sensitive composition layer of the present invention on the substrate to be processed is scanned and exposed with a laser beam and developed to form a resist image. In that case, when the photosensitive composition layer is formed with the dry film resist material, the photosensitive composition is usually applied on the temporary support film or by directly applying the photosensitive composition coating liquid and drying it. When a physical layer is formed and the protective layer is provided, the photosensitive composition layer is usually subjected to scanning exposure with a laser beam from above the protective layer.

  As the laser exposure light source, a blue-violet laser light source that generates laser light in a blue-violet region with a wavelength range of 390 to 430 nm is preferable, and a light source that generates laser light with a wavelength range of 400-420 nm is more preferable. Specific examples include an indium gallium nitride semiconductor laser. Further, the exposure method is not particularly limited, but the plane scanning exposure method is preferable in view of the properties of the substrate to be processed, and the DMD method is effective for pursuing the resolution. The effect is particularly effective in this DMD type exposure method. Further, the laser beam spot diameter is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less, in order to exhibit sufficient resolution. The lower limit is usually about 2 μm from the technical viewpoint.

  In the present invention, when the photosensitive composition layer is formed of the dry film resist material, the development treatment after the laser exposure is performed by peeling off the temporary support film, or by applying the photosensitive composition coating liquid. In the case where the photosensitive composition layer is formed by directly applying and drying, and having the protective layer, the protective layer is peeled off, and then the alkali salt of sodium carbonate, potassium carbonate or the like is added in an amount of 0. It is carried out using a dilute alkaline aqueous solution of about 3 to 2% by weight. A surfactant, an antifoaming agent, an organic solvent as a development accelerator and the like may be added to the alkaline aqueous solution.

  The development is usually performed by immersing the image forming material in the developer or spraying the developer onto the image forming material, and a known developing method such as a paddle method, preferably about 10 to 50 ° C. More preferably, it is performed at a temperature of about 15 to 45 ° C. for a time of about 5 seconds to 10 minutes, preferably about 10 seconds to 2 minutes.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[1] Preparation of Examples 1 to 3 and Comparative Examples 1 to 3 [1-1] Preparation of Dry Film Resist Material As a blue-violet laser photosensitive composition, the following alkali-soluble resins (A1 to A5) and ethylenic unsaturated Compound (B1 to B2), photopolymerization initiator (C1), sensitizing dye (D1 to D2), and other components (X1 to X2) are added to the following solvent (Y1) in the formulation shown in Table 2, The coating solution prepared by stirring at room temperature was applied onto a polyethylene terephthalate film (thickness 25 μm) as a temporary support film in an amount that would result in a dry film thickness of 20 μm using an applicator with a depth of 100 μm. Dry in an oven for 10 minutes, and laminate a polyethylene film (thickness 25 μm) as a coating film on the formed blue-violet laser-sensitive composition layer to produce a dry film resist material It was.

<Alkali-soluble resin>
Copolymers of (A1) to (A5) shown in Table 1 below

<Ethylenically unsaturated compound>

<Photopolymerization initiator>
(C1) 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole <sensitizing dye>
(D1) The following compound (when the sensitizing dye is diluted 60,000 times with tetrahydrofuran and the UV extinction coefficient is measured in the wavelength region of 300 to 500 nm, the absorption maximum existing at the longest wavelength is 388 nm)

(D2) The following compound (absorption maximum 351 nm present at the longest wavelength when the sensitizing dye is diluted 60,000 times with tetrahydrofuran and the UV absorption coefficient is measured in the wavelength region of 300 to 500 nm)

<Visible paint>
(X1) leuco crystal violet (X2) crystal violet <solvent>
(Y1) methyl ethyl ketone

[1-2] Production of image forming material Separately, a copper foil surface of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm thick copper foil was manufactured by Sumitomo 3M Limited. After polishing with buffalo using “Scotch Bright SF”, washing with water, drying with an air stream and leveling, this is preheated to 80 ° C. in an oven, and then on the copper foil of the copper clad laminate. Using the hand-type roll laminator, the dry film resist material obtained in the above is laminated at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min. As a result, an image forming material having a blue-violet laser-sensitive composition layer formed on a copper-clad laminate was produced.

[2] Evaluation of Examples 1 to 3 and Comparative Examples 1 to 3 [2-1] Exposure / Development The blue-violet laser-sensitive composition layer of each obtained image forming material was subjected to the following exposure / development conditions. , Exposed and developed.

<Exposure and development conditions>
Using a blue LD slot module “NDAV520E2” manufactured by Nichia Corporation with an oscillation wavelength of 407 nm and a rated light output of 500 mW, a beam spot diameter of 8 μm and an image surface light quantity of ² mW / cm ² , 8.0 mJ / cm ² , 11.2 mJ / Cm ² 16.0 mJ / cm ² , 22.3 mJ / cm ² , 32.0 mJ / cm ² , and 44.6 mJ / cm ² , 64.0 mJ / c
As exposure doses in 7 stages of m ² , scanning exposure was performed on line-and-space (line width: space width = 1: 1) of 10 μm to 30 μm and independent lines of 10 μm to 30 μm. After 20 minutes from the exposure, the polyethylene terephthalate film is peeled off and removed, and then a 1% by weight sodium carbonate aqueous solution at 32 ° C. is double the break point (time until the non-exposed area is completely dissolved). Development was carried out by spraying at 0.3 MPa for the development time.

[2-2] Exposure Sensitivity, Resolution, Adhesiveness Pattern images obtained at each exposure dose were observed with an optical microscope for the resolution of line-and-space and independent lines, and exposure sensitivity and resolution were as follows. The adhesion was evaluated and the results are shown in Table 2.
The exposure amount obtained by resolving 20 μm line and space as 1: 1 was defined as exposure sensitivity.
In the above exposure sensitivity, the resolution was the minimum resolved line and space.
Among the independent lines obtained at each exposure amount, the narrowest remaining line width was defined as adhesion.

[2-3] Edge Fusion Separately, each obtained resist image forming material is wound up in a roll shape and stored at room temperature (20 to 30 ° C.) for 3 months, and then the photosensitive layer exudes from the end surface of the roll. Were observed and evaluated according to the following criteria, and the results are shown in Table 2.

○: No oozing △: Some oozing but no film sticking ×: There is oozing and the film sticks

  The blue-violet laser photosensitive composition, blue-violet laser image forming material, and blue-violet laser image forming material of the present invention are printed wiring board, plasma display wiring board, liquid crystal display wiring board, large-scale integrated circuit, thin transistor, and semiconductor. It is useful for forming resist images for etching resists, plating resists, solder resists, etc. by direct drawing with blue-violet laser light in the formation of fine electronic circuits such as packages, and is particularly used for the production of printed wiring boards. Therefore, industrial applicability is extremely high.

Claims (8)

A blue-violet laser-sensitive composition comprising the following component (A), component (B), component (C), and component (D):
(A) Alkali-soluble resin containing (meth) acrylates represented by the following general formula (I) as a copolymerization component (B) Ethylenically unsaturated compound (C) Photopolymerization initiator (D) 355-430 nm Sensitizing dye having absorption maximum in wavelength range

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a saturated or unsaturated hydrocarbon group containing a tertiary carbon atom and / or a quaternary carbon atom.) The alkali-soluble resin of component (A) contains (meth) acrylates represented by general formula (I), ethylenically unsaturated carboxylic acids, and hydroxyalkyl (meth) acrylates as copolymerization components. The blue-violet laser-sensitive composition described in 1. The blue-violet laser photosensitivity according to claim 1 or 2, comprising an ester (meth) acrylate having a polyoxyalkylene group and having two or more (meth) acryloyloxy groups as the ethylenically unsaturated compound of component (B). Sex composition. The blue-violet laser-sensitive composition according to any one of claims 1 to 3, comprising a hexaarylbiimidazole compound as a photopolymerization initiator of component (C). The sensitizing dye of component (D) includes any one or more compounds selected from the group consisting of dialkylaminobenzene compounds, triphenylamine compounds, acridone compounds, and carbazole compounds. The blue-violet laser-sensitive composition according to any one of the above. The dialkylaminobenzene compound is a dialkylaminobenzophenone compound represented by the following general formula (II), a dialkylaminobenzene compound having a sulfonylimino group represented by the following general formula (III), and the following general formula (IV The blue-violet laser-sensitive composition according to claim 5, comprising any one or more compounds selected from the group consisting of dialkylaminobenzene-based compounds having a carbostyril skeleton represented by

[In the formula (II), R ³ , R ⁴ , R ⁷ , and R ⁸ each independently represents an optionally substituted alkyl group, and R ⁵ , R ⁶ , R ⁹ , and R ¹⁰ each independently represents an alkyl group which may have a substituent, or a hydrogen atom, R ³ and R ⁴ , R ⁷ and R ⁸ , R ³ and R ⁵ , R ⁴
And R ⁶ , R ⁷ and R ⁹ , and R ⁸ and R ¹⁰ may each independently form a nitrogen-containing heterocycle. ]

[In the formula (IV), R ³ and R ⁴ each independently represents an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently represent a substituent. also alkyl group, or a hydrogen atom, R ³ and R ^4, R ³ and R ^5, and each, independently of R ⁴ and R ^6, may form a nitrogen-containing heterocycle, R ¹¹ Represents a monovalent group or a hydrogen atom, and R ¹² represents a monovalent group. ]

[In the formula (V), R ³ , R ⁴ and R ¹³ each independently represents an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently represents a substituent. An alkyl group which may have, or a hydrogen atom, R ³ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁶ may each independently form a nitrogen-containing heterocycle; R ¹⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ] A blue-violet laser image-forming material comprising a layer of the blue-violet laser-sensitive composition according to any one of claims 1 to 6 formed on a temporary support film. A blue-violet laser image-forming material comprising the blue-violet laser image-forming material layer according to claim 7 laminated on a workpiece substrate on the blue-violet laser-sensitive composition layer side.