JP2008031414A - Laser-decomposable resin composition and pattern-forming material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a laser-decomposable resin composition that forms a pattern by a simple treatment, is usable in a thick film and easily removes waste generated in carving and a pattern-forming material using the same. <P>SOLUTION: The laser-decomposable resin composition comprises (A) a complex of a laminar inorganic compound and an organic compound and (B) a binder polymer. The pattern-forming material uses the same. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laser-decomposable resin composition, and more particularly to a composition having both high degradability and storage stability that can be engraved by a laser, and a pattern forming material using the composition.

  Degradable resin, degradable resin composition is, for example, a resin that decomposes in response to external factors such as thermal factors, mechanical factors, photochemical factors, radiochemical factors, chemical factors, Widely known. Properties and characteristics such as changes in shape (liquefaction, vaporization) before and after the decomposition of the resin or composition, molecular weight, hardness, viscoelasticity, glass transition point (Tg), solubility, and adhesiveness caused by the decomposition of the resin It is used in various fields.

  Examples of such degradable resins and degradable resin compositions include, for example, biodegradable plastics (polylactic acid, etc.) for reducing the environmental impact of plastic materials, drugs, perfumes, etc. in the fields of medicine, cosmetics, life science, etc. And a sustained release material for gradually releasing the components. However, they are gradually decomposed in oxygen, light, enzymes, living organisms, soil, etc. in a natural environment, and the initial state is kept stable and does not cause a great change in properties at a stretch by external stimulation.

  In addition, in order to simplify recyclability and disposal, a resin that decomposes by light and heat, an adhesive that reduces adhesiveness, and the like have been developed. Furthermore, it is also known to form a porous material by mixing ceramics, carbon fiber, and the like with a decomposable resin and removing the decomposable resin by firing or the like. However, these process and process the entire material, and do not form a necessary pattern only in a necessary portion. In addition, a large amount of energy is required for the decomposition treatment.

  For example, a toner containing a thermally decomposable resin is used for image formation, and a change in properties due to heat at the time of heat fixing is used to achieve both storage stability and image fixability as a toner. ing. However, the resin itself does not have sufficient responsiveness to patterned stimuli.

  On the other hand, as a pattern forming material, for example, as a photoresist, a composition containing a photoacid generator and an acid-decomposable resin is exposed to a pattern, and if necessary, the resin is decomposed into a pattern by heat treatment, What forms a pattern by development processing is widely known as a so-called chemically amplified resist. Although this composition has both storage stability and pattern formability at a practical level, a development process in which processing conditions are sufficiently controlled is essential for pattern formation, and is applicable to thin films. For example, it is difficult to form a pattern with a thick film of several tens of μm or more.

  There is also known a method of forming an image by using a process of irradiating a laser beam imagewise to remove a part of a thin film (ablation) (Patent Document 1). However, the compounds taken up as the thermally decomposable resin are merely exemplified as ordinary general-purpose resins such as polyester, polycarbonate and polyurethane, and the film thickness is only about 1 to 2 μm. In addition, an example using a compound that defines thermal decomposability is also known (Patent Document 2). However, even in this case, the film thickness remains at about 1 to 2 μm.

  Moreover, as a mask material for paste printing on a printed wiring board, a mask that forms a pattern of about 100 to 200 μm using a photodegradable resin sheet and a manufacturing method thereof are disclosed (Patent Document 3). . However, this publication does not disclose specific compounds, and a controlled development process is essential to adjust the degree of exposure and development to form a pattern.

On the other hand, as a method for forming a pattern with a simple process on a thick film, for example, pattern formation by laser processing is known, and the substrate itself is removed or deformed by irradiating laser light like an image. It will change color. For example, as a laser marker, information such as a lot number is written on a product made of various base materials (for example, a video tape or a household electrical appliance). However, in this case, the base material itself uses ordinary resin as it is.
In pattern formation by laser processing, it is desirable that a laser engraving portion (concave portion) be formed promptly. For this purpose, a highly sensitive laser-decomposable pattern forming material is required.
In particular, in the flexographic printing plate precursor that directly draws with a laser (so-called flexographic printing plate for laser engraving), the ease of engraving with laser light (engraving sensitivity) affects the plate making speed, so a highly sensitive laser-decomposable resin A flexographic printing plate for laser engraving using the composition is desired.

In pattern formation by laser processing, enormous amounts of engraving debris are generated after laser engraving, and it is desired to remove these debris simply by, for example, washing with water.
Japanese Patent Laid-Open No. 10-119436 Japanese Patent Laid-Open No. 10-244751 JP-A-8-258442

  An object of the present invention is to provide a laser-decomposable resin composition that can form a pattern by a simple process, can be used for a thick film, and can easily remove residue generated by engraving.

As a result of extensive studies, the present inventors have improved the water dispersibility of the resin composition by coexisting a composite of a layered inorganic compound such as a binder polymer and a clay-polymer hybrid and an organic compound, The inventors have found that the ability to remove debris generated when a concavo-convex pattern is formed by laser pattern formation or laser engraving is greatly improved, and the present invention has been completed.
That is, the said subject is achieved by the following structure.

(1) A laser-decomposable resin composition comprising (A) a composite of a layered inorganic compound and an organic compound, and (B) a binder polymer.
(2) The laser decomposition according to (1) above, wherein the layered inorganic compound in the composite of (A) the layered inorganic compound and the organic compound is swellable with respect to water and / or an organic solvent. Resin composition.
(3) The laser-decomposable resin composition as described in (1) or (2) above, wherein the organic compound in the complex of the (A) layered inorganic compound and the organic compound is cationic.
(4) The complex of (A) the layered inorganic compound and the organic compound is a complex formed by mixing the layered inorganic compound and the organic compound in a medium. The laser-decomposable resin composition according to any one of (1) to (3).
(5) The laser-decomposable resin composition according to any one of (1) to (4), wherein the laser-decomposable resin composition further contains (C) a polymerizable compound.
(6) A laser decomposable resin composition obtained by curing the laser decomposable resin composition as described in (5) above.
(7) A pattern forming material comprising a layer made of the laser-decomposable resin composition according to any one of (1) to (6) above.
(8) The pattern forming material as described in (7) above, wherein the pattern forming material is a flexographic printing plate precursor for laser engraving.

  The laser-decomposable resin composition of the present invention has good water dispersibility, and a pattern forming material using this composition can easily remove residue generated when a concavo-convex pattern is formed by laser engraving.

  The laser-decomposable resin composition of the present invention contains (A) a complex of a layered inorganic compound and an organic compound and (B) a binder polymer. Below, each component contained in a laser-decomposable resin composition will be described in detail.

(A) Composite of layered inorganic compound and organic compound The layered inorganic compound in the composite of layered inorganic compound and organic compound may be anything as long as it is generally classified as a layered silicate, but the kaolinite group, Those belonging to the pyrophyllite group, talc group, smectite group, vermiculite group, and mica group are preferable from the viewpoint of easy formation of a complex with an organic compound.
Among these, (i) kaolinite belonging to the kaolinite group, dickite, halloysite, chrysotile, lizardite, amesite, (ii) pyrophyllite belonging to the pyrophyllite group, (iii) talc belonging to the talc group, (iv) smectite. More preferred are montmorillonite, hectorite, saponite belonging to the family, (v) muscovite, biotite belonging to the mica family. More preferably (iii) talc belonging to the talc group, (iv) montmorillonite, hectorite, saponite belonging to the smectite group, (v) muscovite, biotite belonging to the mica group, and most preferably (iv) the smectite group. It belongs to montmorillonite and hectorite.
As the layered inorganic compound, either a natural product or a synthetic product may be used, or a natural product and a synthetic product may be used in combination.
Further, from the viewpoint of improving the interaction with the organic compound, these layered inorganic compounds are preferably swellable rather than non-swellable.

Here, being swellable means that the layered inorganic compound is 0.1 to 20% by mass in water or an organic solvent.
It is defined that the turbidity measured with a turbidimeter (manufactured by Mitsubishi Chemical, integrating sphere turbidimeter) is 1000 ppm or less.
The swellable layered compound is preferably selected from talc, montmorillonite, hectorite, saponite, muscovite and biotite.

  The amount of the layered inorganic compound in the complex (A) is 0.05 to 80% by mass, more preferably 0.1, with respect to the total mass of the complex (A) from the viewpoint of maintaining good water dispersibility. -50 mass%, most preferably 0.5-20 mass%.

The organic compound in the composite of the layered inorganic compound and the organic compound may be a low molecular compound or a high molecular compound, or a combination of a plurality of these compounds. From the viewpoint of improving the film strength of the resin composition, a polymer compound is preferable.
In the case of low molecular weight compounds, amphoteric compounds such as ε-caprolactam derivatives and amino acid derivatives and cationic compounds are preferable, more preferably cationic compounds, particularly preferably cationic radically polymerizable monomers, most preferably cationic functional groups. Is a radically polymerizable monomer having an ammonium group.
Specific examples of the low molecular weight cationic organic compound are shown below, but are not limited thereto.

  In the case of a polymer compound, as long as it has a cationic group-containing unit, the main chain structure is not particularly limited, and various skeletons can be applied. From the viewpoint of ease of synthesis, (meth) acrylic resin, urethane resin, styryl resin, and acetal resin are preferable. The weight average molecular weight (as polystyrene standard by GPC) is generally 1000 to 1000000, preferably 5000 to 500000.

A (meth) acrylic resin, a urethane resin, and a styryl resin, which also have a viewpoint that various functional functional groups are easily introduced into the side chain, are more preferable. More preferred are (meth) acrylic resins and urethane resins, and most preferred are (meth) acrylic resins.
The side chain preferably has an alkylene oxide group, an acidic group, a salt structure in which the acidic group is neutralized, and a cationic functional group. More preferably, it has a cationic functional group. More preferred is when the cationic functional group is an ammonium group. Most preferred is a cationic polymer having a structure in which the cationic functional group is an ammonium group and a small amount of ammonium groups are introduced into the polymer described in the below-mentioned (B) binder polymer.
The content of the cationic group-containing unit in the polymer compound (calculated assuming that the total of all monomers of the polymer compound raw material is 100 mol%) is from 0.01 to 50 mol from the viewpoint of not reducing the film strength of the resin composition. %, More preferably 0.1 to 30 mol%, most preferably 1 to 15 mol%.

  Specific examples of the polymeric cationic organic compound are listed below, but are not limited thereto.

The content of the composite (A) in the laser-decomposable resin composition is from 0.01 to 99.9% by mass, more preferably from 0.1 to 95% by mass, from the viewpoint of maintaining good water dispersibility. Most preferably, it is 1-80 mass%.

  In the present invention, it is preferable that the layered inorganic compound is swellable or the organic compound is cationic in terms of improving the water dispersibility of the resin composition and improving the removal of debris generated during laser engraving. It is particularly preferable that the layered inorganic compound is swellable and the organic compound is cationic.

  When the layered inorganic compound is swellable, the laminated inorganic compound is swollen and peeled off by the medium, and the charge on the surface of the inorganic compound is exposed and solvated, resulting in efficient mutual interaction with the organic compound to be combined. Acts to form a complex. Since this composite is a form that combines an inorganic compound (water dispersion promoting site) and an organic compound (site that promotes mixing with other coexisting polymer), the other polymer (in this case, binder polymer) In the resin composition of the resulting composite and binder polymer, the inorganic compound is finely dispersed in the binder polymer. For this reason, it is considered that the good water dispersibility of the inorganic compound promotes the water dispersion of the binder polymer.

On the other hand, when the organic compound is cationic, the interaction with the negative charge of the layered inorganic compound is improved, and the formation of a complex occurs effectively. As a result, fine dispersion of the inorganic compound is promoted, and it is considered that the good water dispersibility of the inorganic compound promotes the water dispersion of the binder polymer as in the above case.
When the layered inorganic compound is swellable and the organic compound is cationic, it is considered that the above-described effects are synergistically exhibited.

The composite (A) is preferably formed through a step of mixing a layered inorganic compound and an organic compound in a medium.
The medium may be water or an organic solvent. The organic solvent is not particularly limited. However, 1-methoxy-2-propanol, 1-butanone, N, N-dimethylacetamide, N, N-dimethylformamide is easy to disperse the layered inorganic compound when forming the complex. Dimethyl sulfoxide, 1-methyl-2-pyrrolidone, acetone, alcohol solvents (methanol, ethanol, 2-propanol, etc.), tetrahydrofuran, γ-butyrolactone, and the like.

  It is also preferable to use a mixed medium of water and an organic solvent, and the ratio of water and the organic solvent can be adjusted at any time according to the properties of the layered inorganic compound and the organic compound used such as hydrophilicity and hydrophobicity. In particular, in the case of a cationic organic compound, the range of water: organic solvent = 95: 5 to 5:95 (mass ratio) is preferable in that the precipitate of the complex precipitates during formation of the complex and does not deteriorate the workability. More preferably, it is the range of water: organic solvent = 80: 20-20: 80 (mass ratio), Most preferably, it is the range of water: organic solvent = 70: 30-30: 70 (mass ratio).

  The step of mixing the layered inorganic compound and the organic compound in the medium is not particularly limited, and can be performed by any method. For example, in a container such as a sample bottle, a medium having a mass of about 1 to 100 times the mass of the organic compound is added, the layered inorganic compound and the organic compound are added at a desired ratio, and the temperature is room temperature to 50 ° C. for 1 to 5 hours. Stir to a certain extent. Thereby, a composite_body | complex (A) can be prepared as a dispersion liquid.

[B] Binder polymer The binder polymer contained in the laser-decomposable resin composition of the present invention is preferably a binder polymer having a carbon-carbon unsaturated bond in at least one of the main chain and the side chain. A polymer containing at least one of an olefin (carbon-carbon double bond) and a carbon-carbon triple bond in the main chain is more preferable in terms of high mechanical strength of the formed film, and a polymer containing an olefin in the main chain is more preferable. Particularly preferred.

  Examples of the polymer containing at least one of an olefin and a carbon-carbon triple bond in the main chain include SB (polystyrene-polybutadiene), SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene). -Polyethylene / polybutylene-polystyrene) and the like.

The number average molecular weight of the binder polymer is preferably in the range of 10,000 to 1,000,000. A more preferable range is from 50,000 to 500,000. When the number average molecular weight is in the range of 0.1 million to 1,000,000, the mechanical strength of the formed film can be ensured. The number average molecular weight is measured using gel permeation chromatography (GPC), and evaluated with respect to a polystyrene sample having a known molecular weight.

  The addition amount of the binder polymer in the laser-decomposable resin composition of the present invention is generally 1 to 99% by mass, preferably 5 to 80% by mass in the total solid content of the composition.

  In the present invention, the above binder polymer and the following general resin may be used in combination. The addition amount of the combined resin is generally 1 to 90% by mass, preferably 5 to 80% by mass with respect to the binder polymer.

The type of resin may be an elastomer or a non-elastomer.
The number average molecular weight of the combination resin is preferably in the range of 10,000 to 1,000,000. A more preferable range is from 50,000 to 500,000. When the number average molecular weight is in the range of 0.1 million to 1,000,000, the mechanical strength of the formed film can be ensured. The number average molecular weight is measured using gel permeation chromatography (GPC), and evaluated with respect to a polystyrene sample having a known molecular weight.

  As the resin, a resin that is easily liquefied or a resin that is easily decomposed is preferable. Examples of resins that are easily decomposed include styrene, α-methylstyrene, α-methoxystyrene, acrylic esters, methacrylic esters, ester compounds, ether compounds, nitro compounds, carbonates as monomer units that are easily decomposed in the molecular chain. Preferably, compounds, carbamoyl compounds, hemiacetal ester compounds, oxyethylene compounds, aliphatic cyclic compounds, and the like are included. Especially polyethers such as polyethylene glycol, polypropylene glycol, polytetraethylene glycol, aliphatic polycarbonates, aliphatic carbamates, polymethyl methacrylate, polystyrene, nitrocellulose, polyoxyethylene, polynorbornene, polycyclohexadiene hydrogenated product Alternatively, a polymer having a molecular structure such as a dendrimer having many branched structures is a representative example of those that are easily decomposed. A polymer containing a large number of oxygen atoms in the molecular chain is preferred from the viewpoint of degradability. Among these, a compound having a carbonate group, a carbamate group, and a methacryl group in the polymer main chain is preferable because of its high thermal decomposability. For example, polyesters and polyurethanes synthesized from (poly) carbonate diol and (poly) carbonate dicarboxylic acid as raw materials, polyamides synthesized from (poly) carbonate diamine as raw materials, and the like can be cited as examples of polymers having good thermal decomposability. . These polymers may contain a polymerizable unsaturated group in the main chain and side chain. In particular, when it has a reactive functional group such as a hydroxyl group, an amino group, or a carboxyl group, it is easy to introduce a polymerizable unsaturated group.

Although it does not specifically limit as a thermoplastic elastomer, Urethane type thermoplastic elastomer, ester type thermoplastic elastomer, amide type thermoplastic elastomer, silicone type thermoplastic elastomer, etc. can be mentioned. In order to further improve the thermal decomposability, it is also possible to use a polymer in which an easily decomposable functional group such as a carbamoyl group or a carbonate group having a high decomposability is introduced into the main chain. Further, it may be used by mixing with a polymer having higher thermal decomposability. Since the thermoplastic elastomer is fluidized by heating, it can be mixed well with the composite used in the present invention. The thermoplastic elastomer is a material that can be fluidized by heating and can be molded like a normal thermoplastic, and exhibits rubber elasticity at room temperature. The molecular structure consists of soft segments such as polyether or rubber molecules, and hard segments that prevent plastic deformation at around room temperature, as with vulcanized rubber. The hard segments include frozen phase, crystalline phase, hydrogen bonding, and ionic crosslinking. There are various types.

The kind of thermoplastic elastomer can be selected according to the use of the resin composition. For example, urethane, ester, amide, and fluorine thermoplastic elastomers are preferred in fields where solvent resistance is required, and urethane, olefin, ester, and fluorine heat are required in fields where heat resistance is required. A plastic elastomer is preferred. Moreover, hardness can be changed greatly with the kind of thermoplastic elastomer.
The thermoplastic resin is not particularly limited as non-elastomeric, but is not limited to polyester resin, unsaturated polyester resin, polyamide resin, polyamideimide resin, polyurethane resin, unsaturated polyurethane resin, polysulfone resin, polyethersulfone resin, Polyimide resin, polycarbonate resin, wholly aromatic polyester resin and the like can be mentioned.

  Moreover, you may use a hydrophilic polymer as combined use resin. Examples of the hydrophilic polymer include a hydrophilic polymer containing hydroxyethylene as a structural unit. Specific examples include polyvinyl alcohol and vinyl alcohol / vinyl acetate copolymer (partially saponified polyvinyl alcohol) and modified products thereof. As the hydrophilic polymer, a single polymer may be used, or a plurality of types may be mixed and used. Examples of modified products include polymers in which at least some of the hydroxyl groups have been modified to carboxyl groups, polymers in which some of the hydroxyl groups have been modified to (meth) acryloyl groups, polymers in which at least some of the hydroxyl groups have been modified to amino groups, and side chains. Examples thereof include ethylene glycol, propylene glycol, and polymers introduced with these dimers.

  A polymer in which at least a part of the hydroxyl group is modified to a carboxyl group can be obtained by esterification with polyvinyl alcohol or partially saponified polyvinyl alcohol and a polyfunctional carboxylic acid such as succinic acid, maleic acid or adipic acid. .

  A polymer in which at least a part of the hydroxyl group is modified to a (meth) acryloyl group can be obtained by adding a glycidyl group-containing ethylenically unsaturated monomer to the carboxyl group-modified polymer, or polyvinyl alcohol or partially saponified polyvinyl alcohol and (meth) acrylic. It can be obtained by esterification with an acid.

  A polymer in which at least a part of the hydroxyl group is modified with an amino group can be obtained by esterification with polyvinyl alcohol or partially saponified polyvinyl alcohol and a carboxylic acid containing an amino group such as carbamic acid.

  Polymers with ethylene glycol, propylene glycol, and their multimers introduced in the side chain are heated with polyvinyl alcohol or partially saponified polyvinyl alcohol and glycols under sulfuric acid catalyst, and by-product water is removed from the reaction system. It can be obtained by removing.

Among these polymers, a polymer in which at least a part of the hydroxyl group is modified to a (meth) acryloyl group is particularly preferably used. This is because, by directly introducing an unreacted crosslinkable functional group into the polymer component, the strength of the formed film can be increased, and both the flexibility and strength of the formed film can be achieved.

  The weight average molecular weight (in terms of polystyrene by GPC measurement) of the hydrophilic polymer is preferably 10,000 to 500,000. If the weight average molecular weight is 10,000 or more, the form retainability as a single resin is excellent, and if it is 500,000 or less, it is easy to dissolve in a solvent such as water, which is convenient for preparing a crosslinkable resin composition.

  Further, the combination resin may be a solvent-soluble resin. Specific examples include polysulfone resins, polyether sulfone resins, epoxy resins, alkyd resins, polyolefin resins, polyester resins, and the like.

  The combined resin usually does not have a highly reactive polymerizable unsaturated group, but may have a highly reactive polymerizable unsaturated group at the end or side chain of the molecular chain. When a polymer having a highly reactive polymerizable unsaturated group such as a methacryloyl group is used, a film having extremely high mechanical strength can be produced. In particular, in polyurethane-based and polyester-based thermoplastic elastomers, it is possible to introduce a highly reactive polymerizable unsaturated group into the molecule relatively easily. The term “intramolecular” as used herein includes the case where a polymerizable unsaturated group is directly attached to both ends or one end of the polymer main chain, the end of the polymer side chain, the polymer main chain, or the side chain. It is. For example, it is possible to directly use a polymerizable unsaturated group introduced at the molecular end. Alternatively, a hydroxyl group, amino group, epoxy group, carboxyl group, acid anhydride group, ketone group, hydrazine residue can be used. , An isocyanate group, an isothiocyanate group, a cyclic carbonate group, a compound having a molecular weight of about several thousand having a plurality of reactive groups such as an ester group and a binder having a plurality of groups capable of binding to the reactive group (for example, a hydroxyl group or an amino group) Polyisocyanate, etc.) in the case of (2), reacting with an organic compound having a polymerizable unsaturated group and a group that reacts with the terminal binding group after the molecular weight is adjusted and converted to the terminal binding group. And a method such as a method of introducing a polymerizable unsaturated group at the terminal.

  The laser-decomposable resin composition of the present invention may contain a polymerizable compound (monomer), an initiator, and various other components as necessary, in addition to the composite of a layered inorganic compound and an organic compound and a binder polymer. Good. Hereinafter, the polymerizable compound (monomer), the initiator, and other components will be described.

Polymerizable compound (monomer)
Hereinafter, the case where an addition polymerizable compound is used as the polymerizable compound (monomer) will be described in more detail as an example.
<Addition polymerizable compound>
The addition polymerizable compound having at least one ethylenically unsaturated double bond, which is a preferred polymerizable compound used in the present invention, is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in this industrial field, and in the present invention, these can be used without particular limitation. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or copolymers thereof, and mixtures thereof. Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. An ester of an acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. In addition, unsaturated carboxylic acid ester having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, amide and monofunctional or polyfunctional isocyanate, addition reaction product of epoxy, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanato group or an epoxy group, an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, an amine or a thiol, a halogen group Also suitable are substitution reaction products of unsaturated carboxylic acid esters, amides with monofunctional or polyfunctional alcohols, amines, and thiols having a leaving substituent such as a tosyloxy group. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

  Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, Those having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.

  The ester monomers can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

_{CH 2 = C (R) COOCH} 2 CH (R ') OH (V)
(However, R and R ′ represent H or CH _3. )
Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable.

  Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a cured composition in a short time.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both photosensitivity and intensity by using a compound) is also effective. The addition-polymerizable compound is preferably used in the range of 5 to 80% by mass, more preferably 25 to 75% by mass with respect to the non-volatile components in the composition. These may be used alone or in combination of two or more.
Before and / or after laser decomposition, the laser-decomposable resin composition containing a polymerizable compound can be polymerized and cured by energy such as light and heat.

Initiators As initiators, those known to those skilled in the art can be used without limitation. Specifically, for example, Bruce M. Monroe et al., Chemical Revue, 93, 435 (1993) and RSD Davidson, Journal of Photochemistry and biology A: Chemistry, 73.81 (1993); JPFaussier, "Photoinitiated Polymerization-Theory and Applications ": Rapra Review vol. 9, Report, Rapra Technology (1998); M. Tsunooka et al., Prog. Polym. Sci., 21, 1 (1996). FDSaeva, Topics in Current Chemistry, 156, 59 (1990); GGMaslak, Topics in Current Chemistry, 168, 1 (1993); HBShuster et al, JACS, 112, 6329 (1990); IDFEaton et al, JACS, 102 , 3298 (1980) and the like, a group of compounds that cause oxidative or reductive bond cleavage is also known.

Hereinafter, a specific example of a preferable initiator will be described in detail with respect to a radical initiator which is a compound that generates radicals by light and / or heat energy and initiates and accelerates the above-described polymerizable compound and polymerization reaction. Are not limited by these statements.

  In the present invention, preferred radical initiators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, f) ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, (l) azo compounds, etc. Can be mentioned. Specific examples of the above (a) to (l) are given below, but the present invention is not limited to these.

(A) Aromatic ketones (a) Aromatic ketones preferred as the radical initiator used in the present invention include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. Fouassier, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example, the following compounds are mentioned.

  Among these, examples of particularly preferable (a) aromatic ketones include the following compounds.

(B) Onium salt compound As the radical initiator (b) preferable as the radical initiator used in the present invention, compounds represented by the following general formulas (1) to (3) are exemplified.

In formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of onium salts that can be suitably used in the present invention include those described in paragraphs [0030] to [0033] of JP-A-2001-133969 previously proposed by the present applicant, Those described in paragraph numbers [0015] to [0046] of JP-A No. 2001-343742, JP-A No. 2002-148790, JP-A No. 2001-343742, JP-A No. 2002-6482, JP-A No. 2002-116539, Specific aromatic sulfonium salt compounds described in JP-A No. 2004-102031 can be exemplified.

(C) Organic peroxide Preferred as the radical initiator used in the present invention (c) The organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiarybutylperoxy) -3,3,5. -Trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene Idroperoxide, paraffin hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl Cumyl peroxide, dicumyl peroxide, bis (tertiarybutylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-xanoyl peroxide, peroxy Succinic oxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydi -Bonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxyacetate, tertiary butyl peroxypivalate, tertiary butyl peroxyneodecanoate, tarsha Tributyl peroxyoctanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t -Butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3, 3'4 4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumi Ruperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate), and the like.

Among them, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4 4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylper) Peroxyesters such as (oxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred.

(D) Thio compound (d) Thio compound preferable as the radical initiator used in the present invention includes a compound having a structure represented by the following general formula (4).

(Wherein R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, R ²⁷ represents a hydrogen atom or an alkyl group, and R ²⁶ and R ²⁷ are bonded to each other to form an oxygen, sulfur and nitrogen atom. (A group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may contain a selected heteroatom.)
Specific examples of the thio compound represented by the general formula (4) include the following compounds.

(E) Hexaarylbiimidazole compounds (e) Hexaarylbiimidazole compounds preferred as the radical initiator used in the present invention include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2 , 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra Phenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraf Phenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', Examples include 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

(F) Ketoxime ester compound (f) Ketoxime ester compounds preferable as the radical initiator used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3 -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, Examples include 3-p-toluenesulfonyloxyiminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

(G) Borate compound As an example of the (g) borate compound preferable as a radical initiator used for this invention, the compound represented by following General formula (5) can be mentioned.

(Wherein R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be combined with each other to form a cyclic structure; Provided that at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group (Z ⁵ ) ⁺ represents an alkali metal cation or a quaternary ammonium cation.)
Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. Examples include compounds and those shown below.

(H) Azinium compounds Preferred (h) azinium salt compounds as radical initiators used in the present invention include those disclosed in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, and JP-A-63-142346. Examples include compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

(I) Metallocene Compound (i) Metallocene compounds preferred as the radical initiator used in the present invention include those disclosed in JP-A Nos. 59-152396, 61-151197, 63-41484, and JP-A-2. And titanocene compounds described in JP-A No.-249 and JP-A-2-4705, and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethylpentanoyla) ) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl) amino] phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3 6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoromethylsulfonyl) amino] phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (trifluoroacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (2-chlorobenzoyl) amino] phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-chlorobenzoyl) amino] phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylbenzoyl) Amino) phenyl] titanium, and the like.

(J) Active ester compound Preferred as the radical initiator used in the present invention (j) is an imide sulfonate compound described in JP-B-62-2223, JP-B-63-14340, JP-A-59-174831. Mention may be made of the active sulfonates described.

(K) Compound Having Carbon Halogen Bond Preferred examples of the compound (k) having a carbon halogen bond as the radical initiator used in the present invention include those represented by the following general formulas (6) to (12).

(Wherein X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —N
R ³⁸ and —OR ³⁸ are represented. Here, R ³⁸ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³⁷ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. )

(However, R ³⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group, or a cyano group, and X ³ is a halogen atom. And n is an integer of 1 to 3.)

(However, R ⁴⁰ is an aryl group or a substituted aryl group, R ⁴¹ is a group or halogen shown below, and Z ⁶ is —C (═O) —, —C (═S) — or —SO _2- , X ³ is a halogen atom, and m is 1 or 2.)

(R ⁴² and R ⁴³ are an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R ⁴⁴ is the same as R ³⁸ in the general formula (6).)

Wherein R ⁴⁵ is an optionally substituted aryl group or heterocyclic group, R ⁴⁶ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, p is 1, 2 or 3.)

(Equation (10), .L ⁷ which represents a carbonylmethylene heterocyclic compound having a trihalogenomethyl group is a hydrogen atom or the ^{formula: CO- (R 47) q (} C (X 4) 3) at r substituent Q ² is sulfur, selenium or oxygen atom, dialkylmethylene group, alkene-1,2-ylene group, 1,
2-phenylene group or NR group, M ⁴ is a substituted or unsubstituted alkylene group or alkenylene group, or 1,2-arylene group, and R ⁴⁸ is an alkyl group, aralkyl group or alkoxyalkyl group. R ⁴⁷ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, q = 0 and r = 1, or q = 1 and r = 1 or 2. )

(Formula (11) represents a 4-halogeno-5- (halogenomethylphenyl) oxazole derivative. X ⁵ is a halogen atom, t is an integer of 1 to 3, and s is an integer of 1 to 4. ,
R ⁴⁹ is a hydrogen atom or a CH _3-t X ⁵ _t group, R ⁵⁰ is s-valent optionally substituted unsaturated organic group. )

(Formula (12) represents a 2- (halogenomethylphenyl) -4-halogenoxazole derivative. X ⁶ is a halogen atom, v is an integer of 1 to 3, and u is an integer of 1 to 4. ,
R ⁵¹ is a hydrogen atom or a CH _3-v X ⁶ _v group, R ⁵² is an unsaturated organic group which may be substituted for u-valent. )
Specific examples of such a compound having a carbon-halogen bond include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), such as 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6 Bis (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho) 1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trick Rumethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples include compounds described in German Patent No. 3333724, such as bis-trichloromethyl-S-triazine, and the like. Or even more P. Hutt, E .; F. Elslager and L.L. M.M. The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Journalof Heterocyclic Chemistry”, Volume 7 (No. 3) by Herbel, page 511 et seq. (1970) Examples of the group include the following compounds.

(L) Azo-based compound Preferred as the radical initiator used in the present invention (l) As the azo-based compound, 2,2′-azobisisobutyronitrile, 2,2′-azobispropionitrile, 1, 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylpropionamide oxime) ), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxy Til] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 '-Azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (2,4,4- Trimethylpentane) and the like.

  Still more preferred examples of the radical initiator in the present invention include the above-mentioned (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (e) hexaarylbiimidazole compounds, (i) ) Metallocene compounds, (k) compounds having a carbon halogen bond, and the most preferred examples include aromatic iodonium salts, aromatic sulfonium salts, titanocene compounds, and trihalomethyl represented by the general formula (6) -S-triazine compounds can be mentioned.

An initiator is 0.1-50 mass% with respect to the total solid of the decomposable resin composition containing a polymerizable compound, preferably 0.5-30 mass%, particularly preferably 5-20 mass%. It can be added in proportions.
The initiator in the present invention is preferably used alone or in combination of two or more.

Other Components Other components suitable for the use, production method and the like can be appropriately added to the degradable resin composition of the present invention. Hereinafter, preferred additives will be exemplified.

<Sensitizing dye>
In the present invention, when a laser (YAG laser, semiconductor laser, etc.) emitting infrared rays of 760 to 1,200 nm is used as a light source, an infrared absorber is usually used. The infrared absorber absorbs laser light and generates heat to promote thermal decomposition. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.

  Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

  Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Moreover, as another example preferable as a dye, the near-infrared absorptive dye described as the formula (I) and (II) in US Patent 4,756,993 can be mentioned.

  Other preferable examples of the infrared absorbing dye of the present invention include specific indolenine cyanine dyes described in JP-A-2002-278057.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Furthermore, cyanine dyes and indolenine cyanine dyes are preferred.

  Specific examples of cyanine dyes that can be suitably used in the present invention include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969 and paragraph numbers [0012] to [0038] of JP-A No. 2002-40638. And those described in paragraph numbers [0012] to [0023] of JP-A No. 2002-23360.

  The dye represented by the following general formula (d) or general formula (e) is preferable from the viewpoint of photothermal conversion.

In general formula (d), R ²⁹ to R ³¹ each independently represents a hydrogen atom, an alkyl group, or an aryl group. R ³³ and R ³⁴ each independently represents an alkyl group, a substituted oxy group, or a halogen atom. n and m each independently represents an integer of 0 to 4. R ²⁹ and R ³⁰ , or R ³¹ and R ³² may be combined to form a ring, and R ²⁹ and / or R ³⁰ may be R ³³ and R ³¹ and / or
R ³² may be bonded to R ³⁴ to form a ring, and when there are a plurality of R ³³ or R ³⁴ , R ³³ or R ³⁴ may be bonded to each other to form a ring. Good. X ² and X ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of X ² and X ³ represents a hydrogen atom or an alkyl group. Q is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure together with a divalent organic group. Zc ⁻ represents a counter anion. However, Za ⁻ is not necessary when the dye represented by formula (d) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of storage stability of the photosensitive layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

  In the present invention, specific examples of the dye represented by the general formula (d) that can be suitably used include those exemplified below.

In the general formula (e), R ³⁵ ~R ⁵⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carbonyl group, thio group, sulfonyl group, sulfinyl When a group, an oxy group, an amino group, or an onium salt structure is shown and a substituent can be introduced into these groups, it may have a substituent. M represents two hydrogen atoms or metal atoms, a halometal group, and an oxymetal group, and the metal atoms contained therein are IA, IIA, IIIB, IVB group atoms of the periodic table, first, second, second Three-period transition metals and lanthanoid elements can be mentioned, among which copper, magnesium, iron, zinc, cobalt, aluminum, titanium, and vanadium are preferable.

  In the present invention, specific examples of the dye represented by formula (e) that can be suitably used include those exemplified below.

Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. When the particle diameter of the pigment is 0.01 μm or more, the stability of the dispersion in the coating liquid increases, and when it is 10 μm or less, the uniformity of the resin composition layer is improved.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

<Co-sensitizer>
By using a certain kind of additive (hereinafter referred to as a co-sensitizer), the sensitivity at the time of photocuring the resin composition layer can be further improved. These mechanisms of action are not clear, but many are thought to be based on the following chemical processes. That is, a co-sensitizer reacts with various intermediate active species (radicals and cations) generated in the process of a photoreaction initiated by a photopolymerization initiator and a subsequent addition polymerization reaction to generate new active radicals. It is estimated to be. These can be broadly divided into (a) those that can be reduced to generate active radicals, (b) those that can be oxidized to generate active radicals, and (c) radicals that are more active by reacting with less active radicals. Can be categorized as those that act as chain transfer agents, but often there is no generality as to which of these individual compounds belong.

(A) Compound which is reduced to produce an active radical Compound having a carbon-halogen bond: It is considered that an active radical is generated by reductive cleavage of the carbon-halogen bond. Specifically, for example, trihalomethyl-s-triazines and trihalomethyloxadiazoles can be preferably used.

  Compound having nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is reductively cleaved to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used.

Compound having oxygen-oxygen bond: It is considered that an oxygen-oxygen bond is reductively cleaved to generate an active radical. Specifically, for example, organic peroxides are preferably used.

Onium compound: An active radical is considered to be generated by reductive cleavage of a carbon-hetero bond or oxygen-nitrogen bond. Specifically, for example, diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used. Ferrocene and iron arene complexes: An active radical can be reductively generated.
(B) Compound which is oxidized to produce an active radical Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to produce an active radical. Specifically, for example, triarylalkyl borates are preferably used.

  Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines, and the like.

  Sulfur-containing and tin-containing compounds: Compounds in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. Further, a compound having an SS bond is also known to be sensitized by SS cleavage.

  α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl] -2-morpholinopronone-1 and these and a hydroxylamine were reacted, and then N—OH was etherified. Oxime ethers can be listed.

Sulfinic acid salts: An active radical can be reductively generated. Specific examples include arylsulfin sodium.
(C) Compounds that react with radicals to convert to highly active radicals or act as chain transfer agents: For example, compounds having SH, PH, SiH, GeH in the molecule are used. These can generate hydrogen by donating hydrogen to a low-activity radical species to generate radicals, or after being oxidized and deprotonated. Specific examples include 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 2-mercaptobenzimidazoles and the like.

  More specific examples of these co-sensitizers are described, for example, in JP-A-9-236913 as additives for the purpose of improving sensitivity, and these are also applied in the present invention. be able to. Some examples are shown below, but the present invention is not limited thereto. In the following formulae, -TMS represents a trimethylsilyl group.

  Regarding the co-sensitizer, similarly to the above-described sensitizing dye, various chemical modifications for improving the properties of the resin composition layer can be performed. For example, bonds with sensitizing dyes, initiator compounds, addition polymerizable unsaturated compounds and other parts, introduction of hydrophilic sites, compatibility improvement, introduction of substituents for suppressing crystal precipitation, substituents for improving adhesion Methods such as introduction and polymerization can be used.

  A co-sensitizer can be used individually or in combination of 2 or more types. The amount used is 0.05 to 100 parts by mass, preferably 1 to 80 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated double bond.

<Polymerization inhibitor>
In the present invention, in addition to the above components, a small amount of a thermal polymerization inhibitor is used to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage of the composition. It is desirable to add. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide are added to prevent polymerization inhibition due to oxygen, and the layer surface is coated in the drying process after application to a support. It may be unevenly distributed. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Colorant>
Furthermore, a coloring agent such as a dye or a pigment may be added for the purpose of coloring the resin composition layer. Thereby, properties such as the visibility of the image portion and the suitability of the image density measuring device can be improved. As the colorant, it is particularly preferable to use a pigment. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of the colorant added is preferably about 0.5% to about 5% by weight of the total composition.

<Other additives>
Furthermore, known additives such as fillers and plasticizers may be added to improve the physical properties of the cured film.

  The filler may be an organic compound, an inorganic compound, or a mixture thereof. For example, examples of the organic compound include carbon black, carbon nanotube, fullerene, and graphite. Examples of the inorganic compound include silica, alumina, aluminum, and calcium carbonate.

  Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

<Pattern forming material>
The pattern forming material of the present invention is characterized by having a layer comprising the laser-decomposable resin composition according to the present invention on a support. The layer made of a laser decomposable resin composition (hereinafter also referred to as a pattern forming layer) contains a composite of a layered inorganic compound and an organic compound and (B) a binder polymer. The pattern forming layer may further contain the above-described polymerizable compound, initiator, and other components as necessary.
Here, the pattern forming material means a pattern forming material that becomes an uneven pattern when the exposed portion forms a recess compared to the non-exposed portion due to laser exposure. Therefore, not only a pattern forming material that forms a recess directly by laser exposure (for example, by ablation), but also a pattern that forms a recess by performing a heat treatment or a development treatment with an alkaline aqueous solution after laser exposure. Also includes forming materials. The pattern forming material of the present invention can be suitably used particularly as the former type of pattern forming material.
The pattern forming material suitably used in the present invention is not particularly limited as long as it has the above-mentioned properties, and printing plate precursors such as lithographic plates, gravure plates, letterpress plates and screens, printed wiring boards, semiconductors It can be used in a wide variety of fields, such as photoresist materials for optical disks and recording materials for optical disks. In the present invention, a direct engraving plate making using a laser, that is, a printing plate used for so-called “laser engraving” is preferably used. In particular, a flexographic printing plate is preferably used, and a flexographic printing plate precursor for laser engraving is most suitable as the pattern forming material of the present invention.

(Support)
In the present invention, the support for the pattern forming material is preferably a flexible material having excellent dimensional stability. For example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polybutylene terephthalate film, or A polycarbonate film can be mentioned. The thickness of the support is preferably from 50 to 350 μm, more preferably from 100 to 250 μm, from the mechanical properties, shape stability, handleability, etc. of the pattern forming material. If necessary, a known adhesive layer conventionally used for this kind of purpose may be provided on the surface of the support in order to improve the adhesion between the support and the pattern forming layer.
Further, by performing physical and chemical treatment on the surface of the support used in the present invention, the adhesion with the pattern forming layer or the adhesive layer can be improved. Examples of the physical treatment method include a sand blast method, a wet blast method in which a liquid containing fine particles is jetted, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation treatment method, and the like. Examples of the chemical treatment method include a strong acid treatment method, a strong alkali treatment method, an oxidant treatment method, and a coupling agent treatment method.

(Formation of film)
In order to form the decomposable resin composition of the present invention into a sheet, roll or cylinder, an existing resin molding method can be used. For example, a casting method, a method of extruding the resin composition from a nozzle or a die with a machine such as a pump or an extruder, adjusting the thickness with a blade, and adjusting the thickness by calendaring with a roll, etc. In that case, it is also possible to perform the molding while heating the resin composition within a range that does not deteriorate the performance. Moreover, you may perform a rolling process, a grinding process, etc. as needed. Usually, it is often formed on an underlay called a back film made of a material such as PET or nickel. A cylindrical substrate made of fiber reinforced plastic (FRP), plastic, or metal can also be used. The cylindrical substrate can be hollow with a constant thickness for weight reduction. The role of the back film or the cylindrical substrate is to ensure the dimensional stability of the pattern forming material. Therefore, it is necessary to select one having high dimensional stability. Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used. For example, a sheet or the like in which layers of polyethylene terephthalate having a thickness of 50 μm are laminated on both surfaces of a 4.5 μm thick wholly aromatic polyamide film may be used. In addition, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as a back film. When a porous sheet is used as the back film, the photosensitive resin cured product layer is integrated with the back film by photocuring after impregnating the photosensitive resin composition into the pores, so that high adhesion is obtained. be able to. The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, inorganic fibers such as sapphire fibers, natural materials such as cotton and hemp Examples thereof include semi-synthetic fibers such as fibers, rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. Further, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material capable of producing a thin nonwoven fabric with high dimensional stability.

The laser-decomposable resin composition of the present invention is preferably cured by crosslinking (polymerization) before being decomposed by a laser from the viewpoint of improving the strength of the coating film to be formed. In order to cure the composition, it is preferable to contain the polymerizable compound as described above in the composition. This is generally used as a technique for increasing the strength of a film in a negative (polymerization type) photosensitive material, and it is considered that the same effect is exhibited in the present invention.
This method is particularly effective when the pattern forming material is a flexographic printing plate precursor for laser engraving. By curing before laser engraving, there is an advantage that the relief formed after laser engraving becomes sharp and the sticking of engraving residue generated during laser engraving is suppressed.

The method of curing the composition causes a polymerization reaction of the polymerizable compound, such as heating the composition, irradiating light, adding light or a thermal polymerization initiator to the composition, and irradiating or heating the composition. Any means can be used without particular limitation.
Among them, as a method for curing, heating of the composition is preferable from the viewpoint of easy work. Any heating method such as an oven, a thermal head, a heating roll, or a laser beam can be applied to the heating for causing crosslinking (polymerization) with respect to the composition before laser decomposition. When temperature control is necessary, it can be carried out by controlling the temperature of an oven, a thermal head, a heating roll, or the like, or adjusting the intensity of the laser beam or the spot diameter. The heating temperature is preferably 40 to 250 ° C., more preferably 60 to 220 ° C., and still more preferably 80 to 200 ° C. from the viewpoint of the thermal stability of the coexisting organic compound.

The thickness of the decomposable resin composition layer is generally 0.0005 to 10 mm, preferably 0.005 to 7 mm.
The thickness when used for laser engraving (especially a flexographic printing plate precursor for laser engraving) can be arbitrarily set according to the purpose of use, but is preferably in the range of 0.05 to 10 mm, more preferably 0.1 to 7 mm. Range. In some cases, a plurality of layers having different compositions may be stacked.

  As a combination of a plurality of layers, for example, a layer that can be engraved using a laser having an oscillation wavelength in the near-infrared region such as a YAG laser, a fiber laser, or a semiconductor laser is formed on the outermost surface. It is also possible to form a layer capable of laser engraving using an infrared laser such as a carbon dioxide laser or a visible / ultraviolet laser. When laser engraving is performed in this way, engraving can be performed using separate laser engraving equipment equipped with infrared laser and near infrared laser, and laser engraving equipment equipped with both infrared laser and near infrared laser can be used. It is also possible to use.

  In the present invention, a cushion layer made of a resin or rubber having cushioning properties can be formed between the support and the pattern forming layer or between the pattern forming layer and the adhesive layer. When a cushion layer is formed between the support and the pattern forming layer, a method of attaching a cushion layer with an adhesive layer on one side with the adhesive layer side facing the support is simple. After the cushion layer is applied, the surface can be cut and polished for shaping. A simpler method is a method in which a liquid adhesive composition is applied on a support with a constant thickness and cured using light to form a cushion layer. In order to have cushioning properties, the hardness of the photocured cured product is preferably low. Moreover, you may contain a bubble in the photosensitive resin hardened | cured material layer which has cushioning properties.

<Laser engraving>
In laser engraving, an image to be formed is converted into digital data, and a laser device is operated using a computer to create a relief image on the pattern forming material.
As described above, the pattern forming material used for laser engraving is not particularly limited, but a flexographic printing plate precursor for laser engraving is particularly preferably used.
As the laser used for laser engraving, any material can be used as long as the pattern forming material can be patterned by laser ablation. A laser having an oscillation wavelength in the infrared or near-infrared region, such as a carbon dioxide laser, a YAG laser, a semiconductor laser, or a fiber laser, is preferable. In addition, ultraviolet lasers having an oscillation wavelength in the ultraviolet region, such as excimer lasers, YAG lasers converted to the third or fourth harmonic, and copper vapor lasers, can also be ablated to break the bonds of organic compound molecules. Yes, suitable for fine processing. A laser having an extremely high peak output such as a femtosecond laser can also be used. The laser may be continuous irradiation or pulse irradiation. In the flexographic printing plate precursor for laser engraving, a carbon dioxide laser and a YAG laser are preferably used.

  Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out in the presence of carbon dioxide or nitrogen gas. After engraving, the powdered or liquid substance (scum) generated on the relief image surface is irradiated with an aqueous cleaning agent by an appropriate method, for example, a method of washing with water containing a solvent or a surfactant, or a high pressure spray. It can be removed using a method, a method of irradiating with high-pressure steam, a method of wiping with a cloth or the like.

  In addition to relief images, the resin composition of the present invention includes stamps and seals, design rolls for embossing, relief images for patterning insulators, resistors, and conductor pastes used in the production of electronic components, reliefs for mold materials for ceramic products. It can be used for various applications such as images, relief images for displays such as advertisements and display boards, and prototypes and mother molds of various molded products.

  In addition, the surface tack can be reduced by forming a modified layer on the surface of the pattern image after laser engraving. Examples of the modified layer include a film treated with a compound that reacts with the surface hydroxyl group of a pattern image such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles. A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the hydroxyl group on the surface of the pattern image. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group. Further, at least one of these functional groups exists in the molecule and is immobilized on the surface by reacting with the surface hydroxyl group of the pattern image. Further, the compound constituting the silane coupling agent of the present invention includes, as a reactive functional group in the molecule, an acryloyl group, a methacryloyl group, an active hydrogen-containing amino group, an epoxy group, a vinyl group, a perfluoroalkyl group, and a mercapto group. Those having at least one selected functional group or those having a long-chain alkyl group can also be used. When the coupling agent molecule immobilized on the surface has a polymerizable reactive group, the film should be made stronger by immobilizing on the surface and then irradiating with light, heat or electron beam to crosslink. You can also.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

The synthesis example of the composite body of the layered inorganic compound and organic compound used for this invention is shown.
(1) Synthesis of complex (CP-1-2) of montmorillonite and cationic polymer (1-1) Synthesis of cationic polymer (P-1) 300 ml three-necked flask equipped with a condenser, stirring blades and thermometer In addition, methyl methacrylate (41.95 g, manufactured by Wako Pure Chemical Industries), methacrylic acid (6.54 g, manufactured by Wako Pure Chemical Industries), [2- (methacryloyloxyethyl)] trimethylammonium chloride 75% by mass aqueous solution (1. 39 g, manufactured by Aldrich), polymerization initiator V-65 (1.24 g, manufactured by Wako Pure Chemical Industries), and 1-methoxy-2-propanol (120 g, manufactured by Wako Pure Chemical Industries) were added at 75 ° C. under a nitrogen stream. The mixture was heated and stirred for 4.5 hours. Thereafter, a polymerization initiator V-65 (1.24 g, manufactured by Wako Pure Chemical Industries, Ltd.) was further added, followed by heating and stirring at 85 ° C. for 2.5 hours. The reaction solution was allowed to cool to obtain a polymer solution of about 30% by mass. The polymer was identified by gel permeation chromatography, and its weight average molecular weight was 10,000.

(1-2) Synthesis of Complex (CP-1-2) In a 100 ml beaker, 33.33 g of the polymer solution obtained in (1-1) above and 10.00 g of ion-exchanged water were vigorously stirred. Then, N, N-dimethylaminoethanol (1.36 g, manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added, and then 15.59 g of ion-exchanged water was further added, followed by stirring at room temperature for 15 minutes. 4% by weight of Lucentite SWN (0.9 g, manufactured by Co-op Chemical, synthetic smectite) and 21.07 g of ion-exchanged water were mixed and slowly stirred for 35 minutes at room temperature). By stirring for a time, a solution of (CP-1-2) was obtained.
The identification is based on CMC publication “Latest technology of nanohybrid materials”, published on March 1, 2005, 1st edition, F. Ciardelli et al., POLYMER, Volume 35, No. 15, 3296 pages, 1994. This was performed by permeation chromatography and X-ray diffraction. As a result, the weight average molecular weight was 11,000, and the peak derived from X-ray diffraction between the silicate unit crystal layers constituting the raw material Lucentite SWN disappeared after the above synthesis operation. The point was confirmed, and it was identified that smectite and the cationic polymer were complexed.

(2) Synthesis of Mica and Cationic Monomer Complex (CM-1-2) In a 1000 ml beaker, [2- (methacryloyloxyethyl)] trimethylammonium chloride (M-1) 75 mass% aqueous solution (13. N, N-dimethylaminoethanol (13.6 g, manufactured by Wako Pure Chemical Industries, Ltd.) is slowly added to a vigorously stirred solution containing 90.00 g of Aldrich) and 100.00 g of ion-exchanged water, and then further ion-exchanged water. 155.9 g was added and stirred at room temperature for 15 minutes. To this was slowly added 4% by weight aqueous mica solution (Somasif ME (manufactured by Co-op Chemical (8.78 g) and 210.7 g of ion-exchanged water and then stirred for 35 minutes at room temperature) and stirred at room temperature for 3 hours. By stirring, a solution of (CM-1-2) was obtained.Identification was performed by X-ray diffraction, which was derived from X-ray diffraction between silicate unit crystal layers constituting the raw material Somashif ME (mica). It was confirmed that the peak disappeared after the above synthesis operation, and it was identified that the mica and the cationic monomer were complexed.

  The composite of the layered inorganic compound-cationic polymer was synthesized according to (1) above, and the composite of the layered inorganic compound-cationic organic low molecular weight compound was synthesized according to (2) above, and composites shown in Table 1 were synthesized. Among the layered inorganic compounds in Table 1, micromica MK-100 is a non-swellable layered inorganic compound, and the others are swellable layered inorganic compounds.

  The structures of M-2 to M-4 are as follows. P-1, P-3, P-6, and P-12 are described as specific examples of the polymeric cationic organic compound.

[Examples 1 to 10 and Comparative Examples 1 to 3]
<Preparation of resin composition>
As shown in Table 2, the resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared by mixing 10 g of the polymer and 1 g of the composite in a laboratory kneader at a material temperature of 100 ° C. <Evaluation of water dispersibility>
Under the following conditions, the turbidity of the resin composition was measured and used as an index for water dispersibility evaluation.

(measuring equipment)
・ Integral sphere turbidimeter (Mitsubishi Chemical)
・ Measurement range: 1-1000ppm
(Measurement condition)
0.1 g of each resin composition prepared above was weighed into a sample bottle with a lid, and after adding 10 g of distilled water, it was shaken vigorously by hand 20 times. This was directly placed in a turbidity measuring cell and the turbidity was measured.

  From the results of Table 2, the resin composition containing the composite of the layered inorganic compound and the organic compound according to the present invention of Examples 1 to 10 and the binder polymer constitutes Comparative Example 1 and the composite that do not use the composite. Compared with the resin composition of Comparative Example 2 using only the polymer and Comparative Example 3 using only the layered inorganic compound constituting the composite, it can be seen that the turbidity is significantly lower and the water dispersibility is very good. .

[Examples 11 to 20 and Comparative Examples 11 to 13]
<Preparation of pattern forming material>
The composite, polymer, additive and laser absorbent shown in Table 3 below were mixed in a laboratory kneader at a material temperature of 180 ° C. for 20 minutes to uniformly disperse the laser absorbent. Subsequently, the obtained mixture was dissolved in toluene at 80 ° C. together with the polymerizable compound and the initiator, cooled to 60 ° C., and then cast onto a 125 μm thick PET film. It was dried in the atmosphere at room temperature for 24 hours and then at 60 ° C. for 3 hours. The resulting relief layer (thickness 1000 μm) was laminated (laminated) on a 125 μm thick PET film coated with the adhesive component mixture. Thus, the relief layer was transferred to a 125 μm thick PET film coated with the adhesive component mixture. Next, the entire surface was irradiated with UVA light for 15 minutes to prepare a pattern forming material.

<Evaluation of residue removal property>
For engraving with a laser, a carbon dioxide (CO ₂ ) laser, a high-quality CO ₂ laser marker ML-9100 series (manufactured by KEYENCE Co., Ltd.) and a line speed of 20 cm / second at 12 W, for an Nd-YAG laser, Using a MARKER ENGINE 3000 (manufactured by Laser Front Technologies Co., Ltd.) at 10 W and a line speed of 10 cm / sec, a pattern forming material with engraving residue attached was obtained. The pattern forming material with the engraving residue adhered was immersed in distilled water for 30 seconds, and then left to dry in a dark place at room temperature, normal pressure and no wind. The surface of the pattern forming material after drying was observed with an optical microscope, and the number of debris adhered and remaining per unit area (1 cm ² ) was counted. The above operation was performed three times for each pattern forming material, and the average value was adopted as the number of scum. The smaller the number, the better the residue removal property.

  From the results of Table 4, the decomposable resin composition containing the composite of the layered inorganic compound and the organic compound according to the present invention has a small number of debris and a pattern forming material (degradable resin composition) having excellent debris removability. It can be seen that the product can be provided.

Claims (8)

  A laser decomposable resin composition comprising (A) a composite of a layered inorganic compound and an organic compound, and (B) a binder polymer. The laser-decomposable resin composition according to claim 1, wherein the layered inorganic compound in the composite of (A) the layered inorganic compound and the organic compound is swellable with respect to water and / or an organic solvent. .   The laser-decomposable resin composition according to claim 1 or 2, wherein the organic compound in the composite of (A) the layered inorganic compound and the organic compound is cationic.   The composite of (A) the layered inorganic compound and the organic compound is a composite formed by a step of mixing the layered inorganic compound and the organic compound in a medium. The laser-decomposable resin composition according to any one of the above.   The laser-decomposable resin composition according to any one of claims 1 to 4, wherein the laser-decomposable resin composition further contains (C) a polymerizable compound.   A laser-decomposable resin composition obtained by curing the laser-decomposable resin composition according to claim 5.   It has a layer which consists of a laser-decomposable resin composition of any one of Claims 1-6, The pattern formation material characterized by the above-mentioned.   The pattern forming material according to claim 7, wherein the pattern forming material is a flexographic printing plate precursor for laser engraving.