JP2008106213A - Laser decomposable resin composition and pattern forming material using the same - Google Patents

Abstract

A laser-decomposable resin composition that can be used for thick films, has high engraving sensitivity, can be efficiently engraved with low laser energy, and has excellent stability, and a pattern forming material using the same To provide.
The heat-latent catalyst contains (a) a heat-latent catalyst and (b) a polymer represented by the following general formula (1), and (a) the heat-latent catalyst is decomposed by laser exposure. A pattern forming material comprising: a laser-decomposable resin composition characterized in that a bond between PBs is broken by an action and a depolymerization reaction proceeds, and a layer comprising the composition.
P-B (1)
In the formula, P represents an arbitrary polymer, and B represents a blocking group at the end of the main chain skeleton of the arbitrary polymer.
[Selection figure] None

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 addition, as a composition in which a depolymerization reaction proceeds by the action of a catalytically active species generated by heat in the presence of a light or heat latent catalyst, a depolymerization of a polymer compound having an acetal bond by an acid generated by an acid generator. Reactions (Non-patent Documents 1 and 4) and depolymerization of polyphthalaldehyde with a photoacid generator (Non-patent Document 2) are known. Although these disclose a depolymerization reaction and a resist composition, in a highly sensitive system, it is difficult to suppress a decomposition reaction during composition preparation or storage, so a highly sensitive and highly stable composition Things are desired.
Further, poly (α-methylstyrene), which has a low polymer ceiling temperature, is known as a polymer in which a depolymerization reaction of a polymer compound is likely to proceed (Non-patent Document 3). As a composition using a decomposition reaction by laser, a composition for laser marking containing an α-substituted styrene copolymer is known (Patent Document 5). However, a sufficient laser decomposition sensitivity cannot be obtained only by using poly (α-methylstyrene).
Japanese Patent Laid-Open No. 10-119436 Japanese Patent Laid-Open No. 10-244751 JP-A-8-258442 JP 2003-119281 A JP-A-11-228778 Konno, Y. et al. Polymer J., 36, 531-537 (2004). Ito. H. et al. J. Photopolym. Sci. Technol., 3, 219-233 (1990). Inoue Shohei, Polymer Synthetic Chemistry, p.89

  An object of the present invention is a laser-decomposable resin composition that can be used for thick films, has high engraving sensitivity, can be efficiently engraved with low laser energy, and has excellent stability, and a pattern using the same It is to provide a forming material.

The present invention is as follows.
(1) (a) a thermal latent catalyst and (b) a polymer represented by the following general formula (1), the (a) thermal latent catalyst is decomposed by laser exposure, and the action of the decomposed product The laser-decomposable resin composition, wherein the bond between P-B is cleaved by the step, and the depolymerization reaction proceeds.
P-B (1)
In general formula (1), P represents an arbitrary polymer, and B represents a blocking group at the end of the main chain skeleton of the arbitrary polymer.
(2) The laser-decomposable resin composition as described in (1) above, further comprising (c) a binder polymer.
(3) The laser-decomposable resin composition as described in (2) above, wherein the binder polymer (c) is an elastomeric binder polymer.
(4) The laser-decomposable resin composition as described in any one of (1) to (3) above, further comprising (d) a compound containing a polymerizable unsaturated double bond.
(5) A laser decomposable resin composition obtained by curing the laser decomposable resin composition according to (4).
(6) A pattern forming material comprising a layer made of the laser-decomposable resin composition according to any one of (1) to (5).
(7) The pattern forming material as described in (6) above, wherein the pattern forming material is a flexographic printing plate precursor for laser engraving.

  According to the present invention, a laser-decomposable resin composition that can be used for thick films, has high engraving sensitivity, can be efficiently engraved with low laser energy, and has excellent stability, and a pattern using the same A forming material is provided.

The laser-decomposable resin composition of the present invention contains (a) a thermal latent catalyst and (b) a polymer represented by the following general formula (1). It is characterized in that it decomposes, the bond between P-B is broken by the action of the decomposition product, and the depolymerization reaction proceeds.
P-B (1)
In general formula (1), P represents an arbitrary polymer, and B represents a blocking group at the end of the main chain skeleton of the arbitrary polymer.
Below, each component contained in a laser-decomposable resin composition will be described in detail.

(A) Thermal latent catalyst The thermal latent catalyst of the present invention temporarily suppresses an active acidic group, basic group, or radical by a chemical method such as blocking, and cleaves it when heated, The compound group which can be converted into the compound which shows activity again is shown. Specifically, it can be classified into the following compounds that generate an acid (acid generator), compounds that generate a base (base generator), and compounds that generate a radical (radical generator).

<Compound that generates acid>
The acid generator used in the present invention is a compound that generates an acid by light or heat, and examples thereof include compounds described in JP-A-10-282644, [0039] to [0063]. it can.
Specifically, the diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TS Bal et al, Polymer, 21, 423 (1980), etc., US Pat. No. 4,069,055 No. 4,069,056, JP-A-3-140,140, etc., ammonium salts, DC Necker et al, Macromolecules, 17, 2468 (1984), CS Wen et al, Teh , Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, etc., JV Crivello et al , Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, US Pat. No. 339,049, No. 410,201, JP-A-2-150,848, JP-A-2-296,514, etc., iodonium salts, JV Crivello et al, Polymer J. 17, 73 (1 985), JV Crivello et al. J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivello et al , Polymer Bull., 14, 279 (1985), JV Crivello et al, Macromolecules, 14 (5), 1141 (1981), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 ( 1979), European Patent No. 370,693, US Patent No. 3,902,114, European Patent Nos. 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 410,201, 339,049, 4,760,013, 4,734,444, 2 , 833, 827, Korean Patent 2,904,626, 3,604,580, 3,604,581, etc., Selenonium salts described in V Crivello et al, Macromolecules, 10 (6), 1307 (1977), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), etc., CS Wen et onium salts such as arsonium salts described in al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605 JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62. Organohalogen compounds described in JP-A-58241, JP-A-62-221401, JP-A-63-70243, JP-A-63-298339, etc., K. Meier et al, J. Rad. Curing , 13 (4), 26 (1986), TP Gill et al, Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-161445, S. Hayase et al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1973), DHR Barton et al, J. Chem Soc., 3571 (1965), PM Collins et al, J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron Lett. , (17), 1445 (1975), JW Walker et al, J. Am. Chem. Soc., 110, 7170 (1988), SC Busman et al, J. Imaging Technol., 11 (4), 191 (1985) ), HM Houlihan et al, Macromolecules, 21, 2001 (1988), PM Collins et al, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase et al, Macromolecules, 18, 1799 ( 1985), E. Reichmanis et al, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan et al, Macromolecules, 21, 2001 (1988), EP 0290,750 , 046,0 No. 3, No. 156,535, No. 271,851, No. 0,388,343, US Pat. No. 3,901,710, No. 4,181,531 M. TUNOOKA et al, Polymer Preprints Japan, 35 (8), an acid generator having an o-nitrobenzyl type protecting group described in the specification, JP-A-60-198538, JP-A-53-133022 and the like. ), G. Berneret al, J. Rad. Curing, 13 (4), WJ Mijs et al, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, U.S. Pat. No. 618,564, No. 4,371,605, No. 4,431,774, JP-A-64. Compounds which decompose to generate sulfonic acid by decomposition, such as iminosulfonate described in JP-A-18143, JP-A-2-245756, JP-A-4-365048, etc., JP-A-61-166544 Disulfone compounds described in JP-A-50-36209 (US Pat. No. 3,969,118), o-naphthoquinonediazide-4-sulfonic acid halide, JP-A-55-62444 (UK Patent No. No. 2038801 specification) or the O-naphthoquinonediazide compound described in Japanese Patent Publication No. 1-1935.

  Examples of other acid generators include sulfonic acid alkyl esters such as cyclohexyl citrate, p-acetaminobenzenesulfonic acid cyclohexyl ester, p-bromobenzenesulfonic acid cyclohexyl ester, and alkylsulfonic acid esters represented by the following structural formula. Can be used.

Of the acid generators, those that are particularly effective are exemplified below.
(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).

In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or —CY ₃ . Y ₃ represents a chlorine atom or a bromine atom.

  Specific examples include the following compounds, but are not limited thereto.

  (2) An iodonium salt represented by the following general formula (PAG3), a sulfonium salt represented by the general formula (PAG4), or a diazonium salt.

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include alkyl groups, haloalkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, nitro groups, carboxyl groups, alkoxycarbonyl groups, hydroxy groups, mercapto groups, and halogen atoms.
R ³ , R ⁴ and R ⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an aryl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group, and a halogen atom. Is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group. Two of R ³ , R ⁴ and R ⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.
Z ⁻ represents a counter anion, such as BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ^{− and the} like. Examples include, but are not limited to, bonded polynuclear aromatic sulfonate anions such as fluoroalkanesulfonate anion, pentafluorobenzenesulfonate anion, naphthalene-1-sulfonate anion, anthraquinonesulfonate anion, and sulfonate group-containing dyes. Is not to be done.

  Specific examples include the following compounds, but are not limited thereto.

  The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapczyk et al, J. Am. Chem. Soc., 91, 145 (1969), AL Maycok et al, J. Org. Chem., 35, 2532, (1970), B. Goethas et al, Bull. Soc. Chem. Belg., 73, 546, (1964), HM Leicester, J. Am. Chem. Soc., 51,3587 (1929), JV Crivello et al, J. Polym. Chem. Ed., 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, JP-A-53- It can be synthesized by the method described in Japanese Patent No. 101331.

  (3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.

  Specific examples include the following compounds, but are not limited thereto.

  The usage-amount of the said acid generator is 0.1-50 mass% normally with respect to the total solid in a composition, More preferably, it is 1-40 mass%. Within the above range, sensitivity and stability are good.

<Compound generating base>
Examples of the base generator used in the present invention include compounds described in JP-A-2-166450, page 6, upper left column, second row to same page upper column, right row 15, line, specifically heating. Preferred are those that cause some reaction by heating to release a base, such as a salt of an organic acid and a base that are decarboxylated by an acid, a compound that releases amines by a reaction such as intramolecular nucleophilic substitution reaction, Lossen transfer, Beckmann transfer, etc. Used.

  Specific examples include base acid salts. Examples of the base include guanidine, triphenylguanidine, tricyclohexylguanidine, piperidine, morpholine, p-toluidine, and 2-picoline. Examples thereof include acetic acid, trichloroacetic acid, phenylsulfonylacetic acid, 4-methylsulfonylphenylsulfonylacetic acid, 4-acetylaminomethylpropionic acid, succinic acid, maleic acid, succinic acid, fumaric acid, carbonic acid, and bicarbonate.

  These base generators may be introduced in the form of particles in a pattern forming material described later, or may be introduced in a state of being encapsulated in microcapsules described later.

  Specific examples include the following compounds, but are not limited thereto.

  Moreover, the addition amount of a base generator is 0.1-50 mass% normally with respect to the total solid in a composition, More preferably, it is 1-40 mass%. Within the above range, sensitivity and stability are good.

<Compound that generates radicals>
The radical generator used in the present invention can be appropriately selected from known polymerization initiators and compounds having a bond with small bond dissociation energy. Two or more compounds that generate radicals may be used in combination.
A compound that generates radicals is described in JP-A-2004-306582. Examples of compounds that generate radicals are halogenated organic compounds, carbonyl compounds, organic peroxides, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oximes. Includes ester compounds and oxime salt compounds. Most preferred are hexaarylbiimidazole compounds and onium salts.

  Specific examples include the following compounds, but are not limited thereto.

  Moreover, the addition amount of a radical generator is 0.1-50 mass% normally with respect to the total solid in a composition, More preferably, it is 1-40 mass%. Within the above range, sensitivity and stability are good.

(B) Polymer represented by general formula (1) The polymer represented by general formula (1) used in the present invention (hereinafter referred to as a polymer depolymerized by the action of a thermal latent catalyst) will be described. .
PB (1)
The above P is an arbitrary polymer, and may be a copolymer of different types of monomers. From the viewpoint of depolymerization, P is preferably a polymer structure having a low ceiling temperature. Specifically, the ceiling temperature of bulk polymerization is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 100 ° C. or lower. The ceiling temperature of the polymer indicates a temperature at which the rate of the polymerization reaction and the depolymerization reaction are equal in a polymerization reaction of a vinyl compound or the like. Preferable specific examples include poly (α-methylstyrene) s, poly (atropic acid esters), poly (α-acetoxystyrenes), poly (o-methoxystyrenes) polyaldehydes, and lowered ceiling temperature. Poly ((meth) acrylic acid esters), poly (tetrahydrofuran) s, poly-δ-caprolactams that are polymers of 2-piperidone monomers, poly-γ-caprolactams that are polymers of 2-pyrrolidone monomers, poly Examples include allyl acetates, polyallyl alcohols, polyallyl ethers, polybutenes, polyhexenes, polyoxepanes, polyoxyalkylene polymers, and the like. Poly (α-methylstyrene) s and polyphthalaldehydes are laser-decomposed. It is preferable from the viewpoints of sensitivity and stability.

In addition, any blocking group may be used as long as B is a terminal blocking group in which the bond between PBs is cleaved by an acid, base, or radical generated from the thermal latent catalyst and the depolymerization reaction proceeds.
Among them, preferable examples of the structure contained in the block group B decomposable by an acid include a substituted methyl group such as a benzyl group, a 1-substituted ethyl group such as a 1-methoxyethyl group and a 1-benzyloxyethyl group, t- 1-branched alkyl group such as butyl group, silyl group such as trimethylsilyl group, germyl group such as trimethylgermyl group, tertiary alkoxycarbonyl group, tertiary carbonate group, acyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydro Examples thereof include a block group containing a cyclic acid-decomposable group such as a thiopyranyl group and a tetrahydrothiofuranyl group, a disubstituted allyl group such as a 2-phenylallyl group, and the like. Among them, a blocking group containing a 2-substituted allyl group and a tertiary alkoxycarbonyl group is more preferable.
Moreover, as a preferable structure contained in the blocking group B decomposable by a base, there can be mentioned a blocking group containing a substituted benzyl group, a tertiary carbamate group, a tertiary ester group, a tertiary carbonate group, etc. A blocking group containing a benzyl group or a tertiary carbamate group is more preferable.
Furthermore, preferred examples of the structure contained in the blocking group B that can be decomposed by radicals include blocking groups containing a substituted alcohol group, a substituted thiol group, a dialkyl-substituted dithiocarbamate group, a peroxy group, a substituted amino group, etc. A blocking group containing an alcohol group, a dialkyl-substituted dithiocarbamate group, and a substituted amino group is more preferable.

  Specific examples include the following compounds, but are not limited thereto.

  Moreover, the addition amount of the polymer depolymerized by the action of the heat latent catalyst is usually 1 to 90% by mass, more preferably 20 to 80% by mass, based on the total solid content in the composition. Within the above range, sensitivity and stability are good.

In general, in image formation using a laser-decomposable resin composition, laser light is absorbed by an additive such as a polymer compound or a dye, which will be described later, to generate heat, and the heat causes the polymer to melt, evaporate, decompose, or burn. As a result, an uneven image is formed. Since many polymers and crosslinking agents are covalently bonded, their evaporation / decomposition temperature is high. On the other hand, in the compound group of the present invention, the polymer that is depolymerized by the action of the thermally decomposable catalyst is depolymerized by the cleavage of the heat latent catalyst by heat, and is decomposed to monomer units, which is a laser decomposition mechanism. Since it can assist evaporation, decomposition, and combustion, it is considered that high sensitivity has been achieved.
In the present invention, the coexistence of the thermal latent catalyst and the polymer that is depolymerized by the action of the thermal latent catalyst in the binder polymer described below is not clear in details of the action. We have found that the contradictory performance of storage stability and laser decomposition sensitivity can be achieved at a higher level.

(C) Binder polymer The binder polymer is preferably a resin that is easily liquefied or easily decomposed. As a resin that is easily decomposed, monomer units that are easily decomposed in a molecular chain include styrene, α-methylstyrene, α-methoxystyrene, acrylic esters, methacrylic esters, ester compounds, ether compounds, nitro compounds, It is preferable that carbonate compounds, carbamoyl compounds, hemiacetal ester compounds, oxyethylene compounds, aliphatic cyclic compounds, and the like are included. In particular, polyethers such as polyethylene glycol, polypropylene glycol, polytetraethylene glycol, aliphatic polycarbonates, aliphatic carbamates, polymethyl methacrylate, polystyrene, nitrocellulose, polyoxyethylene, polynorbornene, hydrogenated polycyclohexadiene A polymer having a molecular structure such as a product or 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 containing a carbonate group, a carbamate group, or a methacryl group in the polymer main chain is preferable because of its high thermal decomposability. For example, polyesters and polyurethanes synthesized from polycarbonate diol and polycarbonate dicarboxylic acid as raw materials, polyamides synthesized from polycarbonate diamine as raw materials, and the like can be given as examples of polymers having good thermal decomposability. These polymers may contain a polymerizable unsaturated group in the main chain or 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.

  Further, the binder polymer is preferably a polymer compound having elastomeric properties. Although it does not specifically limit as a polymer which has elastomer property, A urethane-type elastomer, ester-type elastomer, an amide-type elastomer, and a silicone-type elastomer can be mentioned. In order to further improve the thermal decomposability, 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 can also be used. It may be mixed with a polymer having higher degradability. When a thermoplastic elastomer is used, it is fluidized by heating, so that it can be well mixed with each component used in the present invention. The molecular structure consists of soft segments such as polyether or rubber molecules, and hard segments that prevent plastic deformation in the same way as vulcanized rubber near normal temperature. The hard segments include frozen layers, crystal layers, hydrogen bonds, There are various types such as ionic bonds.

  The type of elastomer can be selected depending on the use of the resin composition. For example, urethane-based, ester-based, amide-based, and fluorine-based elastomers are preferable in fields where solvent resistance is required, and urethane-based, olefin-based, ester-based, and fluorine-based elastomers are preferable in fields where heat resistance is required. . Moreover, hardness can be changed with the kind of elastomer.

  Among these, as a more preferable binder polymer, a binder polymer having a carbon-carbon unsaturated bond in at least one of a main chain and a side chain is preferable, and an olefin (carbon-carbon double bond) and carbon-carbon are included in the main chain. A polymer containing at least one of triple bonds is more preferable in view of high mechanical strength of the formed film, and a polymer containing olefin in the main chain is particularly preferable.

  Examples of the polymer having at least one olefin and carbon-carbon triple bond in the main chain include SB (styrene-butadiene), SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), and SEBS (styrene). -Polyethylene / polybutylene-styrene) 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 10,000 to 1,000,000, the mechanical strength of the formed film can be ensured. Here, 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 1-90% by mass, preferably 5-80% by mass, based on the total solid content of the composition.

(Other ingredients)
To the composition of the present invention, other components suitable for its use, production method and the like can be added as appropriate. Hereinafter, the additive will be exemplified.

(D) Compound containing polymerizable unsaturated double bond The composition of the present invention preferably contains (d) a compound containing a polymerizable unsaturated double bond (hereinafter referred to as a polymerizable compound or 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 Preferred (e) hexaarylbiimidazole compounds as radical initiators 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 Nilbiimidazole, 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, Y ¹ is _{^{-C (X 2) 3, -NH}} 2, -NHR 38, -NR 38, represent -OR ^38. Wherein R ³⁸ represents an alkyl group, a substituted An alkyl group, an aryl group, or a substituted aryl group, and 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 a sulfur, selenium or oxygen atom, dialkylmethylene group, alkene-1,2-ylene group, 1,2-phenylene group or N—R group, and M ⁴ is a substituted or unsubstituted alkylene group or An alkenylene group or a 1,2-arylene group; R ⁴⁸ is an alkyl group, an aralkyl group or an alkoxyalkyl group; and R ⁴⁷ is a carbocyclic or heterocyclic divalent aromatic group. And X ⁴ is a chlorine, bromine or iodine atom and 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.

The initiator is added in a proportion of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 5 to 20% by mass, based on the total solid content of the composition containing the polymerizable compound. can do.
The initiator in the present invention is preferably used alone or in combination of two or more.
In addition, although the illustration of the said initiator or the illustration of the following co-sensitizer is partially overlapped with (a) thermal latent catalyst, when using such a component, this component and (a) thermal latent It is desirable that the total amount of use of the catalyst be within the range of the preferred use amount of the (a) thermal latent catalyst shown above.

<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 bonded to each other to form a ring, and R ²⁹ and / or R ³⁰ is R ³³ and R ³¹ and / or R ³² is R ³⁴ taken together, may form a ring, further, when R ³³ or R ³⁴ there are a plurality, R ³³ or between R ³⁴ each other may be bonded to each other to form a ring. 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 is increased, 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 decomposable resin composition according to the present invention on a support. A layer made of a decomposable resin composition (hereinafter also referred to as a pattern forming layer) contains the above-mentioned (A) specific compound and (B) resin. The pattern forming layer may further contain the above-described polymerizable compound, initiator, and other components as necessary.

The pattern forming material characterized by having a layer composed of a laser-decomposable resin composition as referred to in the present application refers to all materials in which a laser exposure portion becomes a concave portion of a concave-convex pattern. Although the recess may be formed by performing a heat treatment or a development treatment with an alkaline aqueous solution after the laser exposure, the pattern forming material of the present application is particularly suitable for forming a recess directly (ablationally) by laser exposure. Used for.
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 cured product layer and the back film are integrated by photocuring after impregnating the composition with the pores, so that high adhesion can be obtained. 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.
The laser-decomposable resin composition containing the above-described polymer compound according to the present invention further improves the removability of residue generated during laser engraving by performing such curing. 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.

<Model decomposition experiment>
[Examples 1-8 and Comparative Examples 1-2]
A pattern forming layer was formed using the following composition.
<Examples 1-8 and Comparative Examples 1-2 Sample Formulation>
Polymethyl methacrylate (number average molecular weight 100,000) 50% by mass
Thermal latent catalyst: 20% by mass described in Table 1 below
Polymer depolymerized by action of thermal latent catalyst: listed in Table 1 below 30% by mass

  Polymethylmethacrylate, thermal latent catalyst, and polymer depolymerized by the action of the thermal latent catalyst are dissolved in THF (with a solid content of 10% by mass solution), and 10 g each in an aluminum cup dish. Cast. These were dried in the atmosphere at room temperature for 24 hours to obtain model decomposition experimental samples (before heating).

  These samples were heated using an oven at 200 ° C. for 2 minutes to obtain model decomposition samples (after heating). The model decomposition sample (before heating) and the model decomposition sample (after heating) were redissolved in THF, and the molecular weight (mass average molecular weight) was measured using GPC (manufactured by Tosoh Corporation: high-speed GPC system “HLC-8220GPC”). .

  The results are shown in Table 1.

In the above, “decomposition” indicates that the polymer has been decomposed into monomer units.
As shown in Table 1, when a heating experiment was performed in a sample of a combination of the thermal latent catalyst of the present invention and a polymer that is depolymerized by the action of the thermal latent catalyst, examples 1 to 8 are shown. As can be seen, a decrease in molecular weight was observed. On the other hand, in Comparative Example 1 in which no thermal latent catalyst was added and in Comparative Example 2 in which the terminal was not blocked with a decomposable group, no molecular weight reduction was observed. This suggests that molecular weight reduction occurs in a sample of a combination of a thermal latent catalyst and a polymer that is depolymerized by the action of the thermal latent catalyst.

<Laser decomposition experiment>
[Examples 9 to 25 and Comparative Examples 3 to 7]
A pattern forming layer was formed using the following composition.
<Pattern forming layer composition>
Binder polymer: listed in Table 2 below X mass%
Thermal latent catalyst: listed in Table 2 below Y mass%
Polymer depolymerized by the action of the heat latent catalyst: listed in Table 2 below Z mass%
Polymerizable compound: described in Table 2 below W mass%
Laser absorber: Fine carbon black 2.00% by mass
Additive (ozone decomposition preventing wax): 1,4-benzoquinone 1.00% by mass

  Binder polymer, polymerizable compound, polymer depolymerized by the action of thermal latent catalyst, additives and laser absorber are mixed in a laboratory kneader at a temperature of 100 ° C. for 15 minutes to uniformly disperse the laser absorber. did. The resulting mixture was then dissolved in methylene chloride (DMAc if not dissolved) at 60 ° C. with a thermal latent catalyst, cooled to 40 ° C. and 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 obtained pattern forming layer (thickness 1000 μm) was laminated (laminated) on a 125 μm thick PET film provided with an adhesive layer. As a result, the pattern forming layer was transferred to a 125 μm thick PET film provided with an adhesive layer. When a polymerizable compound was added, the sample was heated at 150 ° C. for 3 minutes to obtain a sample subjected to a thermal polymerization reaction.

For the evaluation of the engraving depth with a laser, in the case of a carbonic acid (CO ₂ ) laser, the line speed is 20 cm / sec at 12 W using a “high-quality CO ₂ laser marker ML-9100 series (manufactured by KEYENCE)”, Nd -In the case of a YAG laser, after engraving at 10 W / 10 cm / sec line speed using “MARKER ENGINE 3000 (Laser Front Technologies Co., Ltd.)”, the height of the laser irradiation part (concave part) and the laser non-irradiation part The difference was measured by measuring with an ultradeep shape measuring microscope (VK-8500; manufactured by Keyence Corporation). In addition, regarding the stability during thick film formation, “◎” indicates that a thick film can be formed, and there is stickiness, but “○” indicates that a film can be formed. Those that cannot be formed are designated as “×”. The results are shown in Table 2.

TR-2000: Styrene-butadiene block copolymer (manufactured by JSR Corporation)
The numerical values in parentheses below each component in Table 2 are mass%.

  As shown in Table 2, in Examples 9 to 25 which are examples of the present invention, the combination of the thermal latent catalyst of the present invention and the polymer depolymerized by the action of the thermal latent catalyst is not added. It can be seen that the sculpture depth, which is an index of resolvability in the laser decomposition experiment, is deeper than the comparative example. Considering from the data of the model experiment, this is because the active species generated by the decomposition of the thermal latent catalyst cleaves the main chain of the polymer that is depolymerized by the action of the thermal latent catalyst. It is thought that the molecular weight decreased and the degradability improved. In addition, stability is improved by introducing a compound containing a polymerizable unsaturated double bond, and further by adding a binder polymer and reducing the concentration in the film of the polymer to be depolymerized by the action of a thermal latent catalyst. Also improved.

Claims (7)

(A) a thermal latent catalyst and (b) a polymer represented by the following general formula (1), the (a) thermal latent catalyst is decomposed by laser exposure, and P- A laser-decomposable resin composition, wherein a bond between B is cut and a depolymerization reaction proceeds.
P-B (1)
In general formula (1), P represents an arbitrary polymer, and B represents a blocking group at the end of the main chain skeleton of the arbitrary polymer.   The laser-decomposable resin composition according to claim 1, further comprising (c) a binder polymer.   The laser-decomposable resin composition according to claim 2, wherein the binder polymer (c) is an elastomeric binder polymer.   The laser-decomposable resin composition according to claim 1, further comprising (d) a compound containing a polymerizable unsaturated double bond.   A laser decomposable resin composition obtained by curing the laser decomposable resin composition according to claim 4.   It has a layer which consists of a laser decomposable resin composition in any one of Claims 1-5, The pattern formation material characterized by the above-mentioned.   The pattern forming material according to claim 6, wherein the pattern forming material is a flexographic printing plate precursor for laser engraving.