TW201211691A - Photosensitive composition, photosensitive laminate, permanent pattern forming method and printed board - Google Patents

Abstract

The present invention provides a photosensitive composition which contains at leat a polyurethane resin, an elastomer, a polymerizable compound, a photopolymerization initiator, and a heat-crosslinking agent.

Description

201211691 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive composition suitable for use as a solder resist (s 01 derresist) material excellent in reliability test, particularly cold heat test resistance (TCT resistance). A laminated body, a permanent pattern forming method, and a printed substrate. [Prior Art] Conventionally, when a permanent pattern such as a solder resist pattern is formed, a photosensitive composition is applied or laminated in a dry film to form a photosensitive layer. In the method for producing the permanent pattern, for example, the photosensitive layer is formed on a substrate such as a copper clad laminate in which the permanent pattern is formed, and the photosensitive layer is exposed, and after the exposure, the photosensitive layer is developed to form a pattern. Thereafter, a hardening treatment or the like is performed to form the aforementioned permanent pattern. In the permanent pattern, a solder resist for use in a substrate in which stress is easily concentrated, such as a package substrate, is required to relieve stress in order to prevent cracks. Further, when a product is manufactured based on a package substrate, it is required to achieve high resistance to, for example, evaluation of cold and cold test resistance (TCT resistance) for -65 under consideration of the treatment under the condition of repeatedly applying heat or the actual use state. Resistance to the thermal history of °C~150°c. Therefore, for example, an acid-modified vinyl group-containing epoxy resin (A), an elastomer (B), a photopolymerization initiator (C), a diluent (D), and a hardener (E) are considered as essential components. A photocurable resin composition (refer to Japanese Laid-Open Patent Publication No. Hei 11-240930). 201211691 However, in this case, although the stress is relieved and the TCT resistance is also improved, it is not a problem that the performance of the insulation reliability can be sufficiently satisfied. Therefore, the current situation is strongly demanding the rapid development of photosensitive compositions which have excellent TCT resistance and insulation reliability. [Summary of the Invention] The object of the present invention is to provide a photosensitive composition excellent in TCT (thermal cycle test) resistance and insulation reliability, a photosensitive laminate, a permanent pattern forming method, and a printed substrate. The means for solving the above problems are as follows. In other words, the photosensitive composition of the present invention is characterized in that it contains at least a polyurethane resin, an elastomer, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent 0 &lt; 2 &gt;&lt;1&gt; The photosensitive composition described above, wherein the polyurethane resin is obtained by reacting a diisocyanate, a carboxylic acid having at least two hydroxyl groups, and a diol having no carboxylic acid group. The photosensitive composition described in any one of <1> to <2>, wherein the elastic system is selected from the group consisting of a styrene-based elastomer, an olefin-based elastomer, an urethane-based elastomer, and a poly At least one of an ester elastomer, a polyamine elastomer, an acrylic elastomer, and a polyoxynene elastomer. The photosensitive composition described in any one of <1> to <3>, wherein the polyurethane resin has an acid value of 20 mgKOH/g to 120 mgKOH/g. <5> The photosensitive composition according to any one of <1> to <4>, wherein the cross-linking density is from 0.05 mol/m3 to 3.0 mol/m3. The photosensitive composition described in any one of &lt;1&gt; to &lt;5&gt; of the above-mentioned &lt;6&gt; is in the form of a coating containing a decane coupling agent. The photosensitive composition described in any one of the above <1> to <6> is a urethane resin represented by the following formula (1).

In the above formula (1), η represents an integer of from 1 to 50. a, b, c, d, and e each represent the mass ratio of each comonomer of the polyurethane, a system 袠 20 20~70, b system 0 to 20, c system 0 to 40, d system Express 〇~4〇, c

The C system represents 0 ~ 3 0. &lt;8&gt; A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition described in any one of the above items to &lt;7&gt;. &lt;9&gt; - A method of forming a permanent pattern, comprising at least a step of exposing a photosensitive image formed by the photosensitive composition described in any one of the foregoing <1> to <7> . &lt;10&gt; A printed circuit board characterized in that a permanent pattern is formed by the permanent_pot forming method described in the above &lt;9&gt;. According to the present invention, various problems in the past can be solved, and TCT (thermal cycle test) resistance can be provided. And a photosensitive composition excellent in insulation reliability, a photosensitive laminate using the same, a permanent pattern forming method, and a printed substrate. [Embodiment] [Details of the Invention] 201211691 (Photosensitive Composition) The photosensitive composition of the present invention contains at least a polyurethane elastomer, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. Further, other ingredients are included as needed. &lt;Polyuric acid resin&gt; The polyurethane resin is obtained by reacting at least a diisocyanate, a hydroxy group-containing carboxylic acid, or a carboxylic acid group-free diol to obtain a diisocyanate. For example, a diisocyanate represented by the following (2) can be suitably used. 0 C N — X — N C 0 Formula (2) However, in the above formula (2), X represents an aliphatic or aromatic hydrocarbon group which may have a substituent. Further, the X system may have other functional groups reactive with a cyanate group, such as an ester group, a carbamate amine group, a urea group or the like, as needed. The above-mentioned diisocyanate may, for example, be an aromatic diester, an aliphatic diisocyanate, an alicyclic diisocyanate or a reactant diisocyanate of a diol cyanate. These may be used singly, but two or more of the above-mentioned aromatic diisocyanates may be used in terms of solubility in an organic solvent, and dimerization of, for example, 2 diisocyanate or 2,4-toluene diisocyanate may be mentioned. , 2,6-cyanate, p-xylene diisocyanate, m-xylene diisocyanate 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, resin, two To. The divalent lipid of the formula is not related to an iso-yl group, hydrazine isocyanate and diiso- isomer, hydrazine, 4-toluene benzoate, 3,3,- 201211691 dimethylbiphenyl-4,4' - Diisocyanate and the like. The aliphatic diisocyanate may, for example, be hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate diisocyanate or dimer acid diisocyanate. The alicyclic diisocyanate may, for example, be isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate) or methylcyclohexan-2,4 (or 2) 6) Diisocyanate, 1,3-(isocyanatemethyl)cyclohexane, and the like. The reactant diisocyanate of the above diol and diisocyanate may, for example, be an adduct of 1 mol of 1,3-butanediol and 2 mol of toluene diisocyanate. The carboxylic acid having at least two hydroxyl groups. For the carboxylic acid having at least two hydroxyl groups, a carboxylic acid represented by the following formula (3) can be suitably used. H0 - Y - 0H Formula (3) However, in the above formula (3), γ represents a divalent aliphatic or aromatic hydrocarbon group having a carboxylic acid group. The carboxylic acid compound having at least two hydroxyl groups is preferably a residual acid represented by the following general formulae (4) to (7). 201211691

R1 •匕’ _ ·Μ·&quot; L1^*—. H (booH formula (4)

R HO-L-C-L-OH L3 Formula (5)

COOH HO—L——Aff —L——OH L3 General formula (6)

COOH 2

HO—L—N—L—OH L3COOH General formula (7) In the above formulas (4) to (7), R 1 represents a hydrogen atom and may have a substituent (including, for example, a cyano group, a nitro group, a F, a CM′ Br , I, etc., halogen atom, -C〇NH2, -C00R2 '-OR3, -NHCONHR4, -NHCOOR5 ' -NHCOR6, -0C0NHR7 (here, R2, R3, R4, R5, R6 and R7 represent the number of carbon atoms 1~ Any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and an aryloxy group of each of the alkyl group of 10, the aralkyl group having 7 to 15 carbon atoms, and the like. Among these, an aryl group having a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and having 6 to 15 carbon atoms is preferred. In the above formula (6), Ar1 represents a trivalent aromatic hydrocarbon group which may have a substituent, and is preferably an aromatic group having 6 to 15 carbon atoms. 201211691 In the above formulae (4) to (7), L1, L2 and L·3 may be the same or different, and may represent a single bond or a substituent (for example, an alkyl group, an aralkyl group, an aryl group, a divalent aliphatic or aromatic hydrocarbon group of an alkoxy group or a halogen atom, preferably an alkylene group having 1 to 20 carbon atoms or an extended aryl group having 6 to 15 carbon atoms, more preferably 1 to 1 carbon atom. Further, in the case of L1, L2 and L3, other functional groups which do not react with isocyanate groups, such as a carbonyl group, an ester group, a carbamate group, a guanylamino group, a urea group, Ether based. Further, among the above-mentioned general formulae (4) and (5), R1, L1, L2 and L3, L1, L2 and L3 in the general formula (6), and L1, L2 and L3 in the general formula (7) Two or three can also form a ring. The carboxylic acid compound having at least two hydroxyl groups represented by the above formulas (4) to (7) may, for example, be 3,5-dihydroxybenzoic acid or 2,2-bis(hydroxymethyl)propane. Acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxypropyl)propionic acid, 2,2-bis(hydroxymethyl)butyric acid, bis(hydroxymethyl) Acetic acid, bis(4-hydroxyphenyl)acetic acid, 2,2-bis(hydroxymethyl)butyric acid, 4,4.-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, hydrazine, hydrazine-dihydroxy Ethylglycine, N,N-bis(2-hydroxyethyl)-3-carboxy-propionamide, and the like. These systems may be used alone or in combination of two or more. - a diol containing no decanoic acid - The urethane resin may contain two or more kinds of diols having no carboxylic acid group in addition to the solubility in the organic solvent. The linking group which bonds the two hydroxyl groups in the carboxylic acid group-free diol is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent hetero 201211691 sulfur atom (-S-), or a sub Amine (-NH-) substituted substituted imido group, and group

The hydrogen atom of the ring group, the carbonyl group (-CO-), the oxygen atom (-〇-), the sulfur and the imine group is a monovalent hydrocarbon group which is one of the groups. Glycol. The diol having no repeating unit may, for example, be ethylene glycol, propanol, butanediol, neopentyl glycol, cyclohexanedimethanol, dipyridyl xylene or bis(hydroxyethyl)benzene. a crosslinkable group such as a diol having no crosslinkable group, allyloxypropanediol, methacrylic acid propylene glycol, neopentyl glycol dimethacrylate, or dihydroxymethyl hydrazine Alcohol, etc. The polyether diol is exemplified by a compound represented by the following formulas (8) to (12), a random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal. -10- 201211691 HO-(CH2CHO)a-H General formula (8)

l 12 R HO—(CH2CH2CHO)bH General formula (9) R13 HO~(C HgC H2C H2C HO)c—H General formula (10) H〇—(CH2CH20)d-{CH2CH0)e-{CH2CH20)dH General formula (11) Ch3

0—(OX2)g—H General formula (12) However, R12 in the above formula (8) and R13 in the above formula (9) represent either a hydrogen atom or a methyl group. X1 and X2 in the above formula (12) each independently represent a group represented by the following (a) and a group represented by the following (b). (a) - (3) (10) Plant (b) - CH2CH - ch3 In the above formulae (8) to (12), a, b, c, d, e, f and g represent an integer of 2 or more, preferably 2 to 2. An integer of 100. Examples of the polyether diol represented by the above formulas (8) to (9) include exemplified by -11 to 201211691 such as diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol. Hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propanediol, tri-1,2-propanediol, tetra-1,2-propanediol, hexa-1,2-propanediol, di-1 , 3-propanediol, tri-1,3-propanediol, tetra-1,3-propanediol, di-1,3-butanediol, tri-1,3-butanediol, hexa-i,3-butanediol Wait. These systems may be used alone or in combination of two or more. In terms of the weight average molecular weight of the above polyether diol, for example, it is preferably from 200 to 10,000 &gt; more preferably from 200 to 5,000, particularly preferably from 400 to 4,000. The polyether diol having a weight average molecular weight of 200 to 10,000 may, for example, be a weight average molecular weight of 1, a polyethylene glycol of hydrazine, a polyethylene glycol having a weight average molecular weight of 1,500, and a weight average. Polyethylene glycol having a molecular weight of 2,000, polyethylene glycol having a weight average molecular weight of 3,000, polyethylene glycol having a weight average molecular weight of 7,500, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, and a weight average molecular weight of 1,000. Propylene glycol, polypropylene glycol having a weight average molecular weight of 2,000, polypropylene glycol having a weight average molecular weight of 3,000, polypropylene glycol having a weight average molecular weight of 4,000, and the like. These systems may be used alone or in combination of two or more. The commercially available product of the polyether diol represented by the above formula (10), for example, PTMG65 0, PTMG 1 000, PTMG2000, PTMG3000 (the above is manufactured by Sanyo Chemical Industries Co., Ltd.) and the like.

Commercial products of the polyether diol represented by the above formula (11) include, for example, NEWPOL PE-61, NEWPOL PE-62, NEWPOL PE-64, NEWPOL PE-68 'NEWPOL PE-71' NEWPOL PE-74 ' NEWPOL -12- 201211691 PE-75' NEWPOL PE-78, NEWPOL PE-108, NEWPOL PE-128, NEWPOL PE-6 1 (above the Sanyo Chemical Industry Co., Ltd.), etc. (12) Commercial products of the polyether diols include NEWPOL BPE-20, NEWPOL BPE-20F, NEWPOL BPE-20NK, NEWPOL BPE-20T, .NEWPOL BPE-20G, and NEWPOL BPE-40. NEWPOL BPE-60, NEWPOL BPE-100 ' NEWPOL BPE-180, NEWPOL BPE-2P ' NEWPOL BPE-23P, NEWPOL BPE-3P, NEWPOL BPE-5P (above, Sanyo Chemical Industry Co., Ltd.).

The commercial product of the above-mentioned random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal may, for example, be NEWPOL 50HB-100' NEWPOL 50HB-260, NEWPOL 50HB-400, NEWPOL 50HB-660, NEWPOL 50HB -2000, NEWPOL 50HB-5100 (the above is manufactured by Sanyo Chemical Industry Co., Ltd.) and the like. The specific compound of the above polyether diol may, for example, be as follows, but is not limited thereto.

The polyester diol is exemplified by the compounds represented by the general formulae (13) to (15). -13- 201211691 ο II A R — C—O- Lz- OH General formula (13)

I L3 HO-L^—(O-C-L3—C-O—L2)n1-〇H General formula (14) 9 General formula (15)

HO-L4—(〇-C~L5)n2-〇H In the above formulae (13) to (15), the L2, L3 and L4 systems may be the same or different, and represent a divalent aliphatic or aromatic hydrocarbon group. L5 represents a divalent aliphatic hydrocarbon group. L2 to L4 each represent an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and the L5 group preferably represents an alkyl group. Further, L2 to L5 may have other functional groups which do not react with an isocyanate group, such as an ether, a carbonyl group, an ester, a cyano 'olefin, a urethane, a guanamine group, a urea group or a halogen atom. Nl and n2 are each an integer of 2 or more, and preferably an integer of 2 to 100. In the case of the above polyurethane resin, a polyurethane resin having a crosslinkable group is preferred. In the method of introducing a crosslinkable group into the above-mentioned polyurethane resin, (i) a polyurethane resin obtained by reacting a diisocyanate having an ethylenically unsaturated bond in a side chain, ( Ii) a polyurethane resin obtained by reacting a diol having an ethylenically unsaturated bond in a side chain, (iii) a carboxyl group-containing polyurethane, an epoxy group in the molecule, and the like A polyurethane resin obtained by reacting a functional group of the reaction with a compound of a vinyl group. Among these, (ii) a polyurethane resin obtained by reacting a diol having an ethylenically unsaturated bond in a side chain, (iii) a carboxyl group-containing polyurethane, and a molecule A polyurethane resin obtained by reacting a functional group reactive with a carboxyl group such as an epoxy group with a compound of ethyl b-14 - 201211691 alkenyl group. - a polyurethane resin obtained by reacting a diol having a crosslinkable group in a side chain - preferably a diol compound of the aforementioned polyurethane having crosslinkability in a side chain Base diol compound. The diol compound having a crosslinkable group in the side chain may be, for example, a commercially available one like trimethylolpropane monoallyl ether, or may be a halogenated diol compound, a triol compound or an amine group. A compound which is easily produced by reacting a compound such as an alcohol compound with a compound containing an unsaturated group such as a carboxylic acid, an acid chloride, an isocyanate, an alcohol, an amine, a thiol or a halogenated alkyl compound. The diol compound having an unsaturated group in the side chain is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include paragraphs [0057] to [0060] of JP-A-2005-25 043 8 The compound described below and the following general formula (G) are represented by the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438. Among these, the compound described in paragraphs [0064] to [0066] of JP-A-2005-250438 is preferably represented by the following general formula (G).

In the above formula (G), R and R3 each independently represent a hydrogen atom or a monovalent -15-201211691 organic group 'A system represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or -N ( R12)-'The foregoing is a hydrogen atom or a valence organic group. Further, R^R3 and X in the above formula (G) are synonymous with R1 to R3 and X in the above formula (1), and preferred embodiments are also the same. By using the polyurethane resin from the diol compound represented by the above formula (G), the effect of suppressing the excess molecular motion of the polymer backbone of the secondary alcohol caused by the steric hindrance is considered to be Achieve the film strength of the lifting layer. A preferred specific example of the monomer derived from the diol compound represented by the above formula (G) is given, but the present invention is not limited thereto.

a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having a functional group reactive with a carboxyl group such as an epoxy group in a molecule, and a vinyl group The polyurethane resin obtained by reacting a urethane resin with a compound having a functional group reactive with a carboxylic acid and a vinyl group may, for example, be a cyclic ether group-containing polymerizable compound such as an acrylic ring. a glycidyl ester of an unsaturated fatty acid such as oxypropyl acrylate, glycidyl methacrylate or cinnamic acid, or an epoxy group having an alicyclic epoxy group (for example, an epoxy group such as cyclohexene oxide in the same molecule) (meth)acrylic acid-based compound, etc., such as a polyurethane resin having an epoxy-16-201211691 group and a vinyl compound, and the like, and addition of an isocyanate ethyl group. A polyurethane resin obtained by adding a compound having an isocyanate group and a vinyl group to a carboxyl group-containing polyurethane resin such as a methyl acrylate. In the above, the polyurethane resin is more preferably a part of the carboxyl group of the polyurethane resin to have a cyclic ether group (for example, a group having a partial structure having an epoxy group or a sulfhydryl group) Those with vinyl compounds. In this case, the addition reaction with a compound having a carboxyl group and a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from the group consisting of an acidic compound and a neutral compound. The above-mentioned polyurethane resin is synthesized by adding a known catalyst which is reactive according to the respective reactivity of the aprotic solvent and heating. The molar ratio of the diisocyanate to the diol of the diol is different from the weight average molecular weight of the polyurethane, preferably from 70:30 to 30:70, more preferably from 65:35 to 35:65. Preferably, the molar ratio of the carboxylic acid having at least two hydroxyl groups to the diol having no carboxylic acid group is 2:48 to 40:10, more preferably 5:45 to 35:15. Very good for 10:40-35:15. If the molar ratio is less than 2:4, it may not provide sufficient alkali developability and it is difficult to form a pattern. If it is more than 40:10, the solubility in an organic solvent is remarkably lowered. 'The carboxylic acid and the isocyanate may partially react. Gelatinization makes it difficult to synthesize. Further, when the isocyanate group remains at the end of the polymer, it is treated by an alcohol or an amine, and finally, it is synthesized in such a manner that no isocyanate group remains. -17-201211691 The compound represented by the following formula (1) can be exemplified as the above-mentioned polyurethane resin.

In the above formula (1), η represents an integer of from 1 to 50, and may be appropriately selected depending on the purpose. However, in terms of flexibility, it is preferably from 1 to 45, more preferably from 1 to 3 5 5 . Very good for 1 to 25. In the above formula (1), a, b, c, d, and e each represent a mass ratio of each comonomer of the polyurethane, preferably a to 20 to 70% by mass, and b to 0 to 20 Mass%, c system 〇~40 mass%, d system 0-40 mass%, e system 0~30 mass%, more preferably a system 35~70 mass%, b system 0-10 mass%, c system 0 ～20% by mass, d is 15 to 40% by mass, and e is 10 to 25% by mass. The acid value of the polyurethane resin is preferably from 20 mgKOH/g to 120 mgKOH/g, more preferably from 30 mgKOH/g to 110 mgKOH/g-partially from 35 mgKOH/g to 110 mgKOH/g. When the acid value is less than 20 mgKOH/g, sufficient alkali developability may not be provided and it is difficult to form a pattern. When the acid value is more than 120 mgKOH/g, the alkali developability is too high, and the pattern may not remain after development. Here, the acid value can be obtained by dissolving a quantitative amount of the polyurethane carboxylic acid in a solvent such as methoxypropanol, and calculating the amount of neutralization obtained by titrating the potassium hydroxide aqueous solution having a known titer. . The weight average molecular weight of the polyurethane resin is preferably 3,000 to 1,000,000, more preferably 4,500 to 70,000, particularly preferably 6,000 to 50,000 - -18 - 201211691, and if the weight average molecular weight is less than 3,500, The other constituent components cannot be held and the function as a binder may not be provided. If it is more than 100,000, the compatibility with other constituent components may be deteriorated and it is difficult to produce a composition. Further, the weight average molecular weight can be measured by GPC (gel permeation chromatography). The content of the polyurethane resin is preferably 30 parts by mass to 80 parts by mass, more preferably 35 parts by mass to 70 parts by mass, more preferably 100 parts by mass to 70 parts by mass, based on 100 parts by mass of the photosensitive composition. 40 parts by mass to 65 parts by mass. When the content is less than 30 parts by mass, the other constituent components may not be held and the function as a binder may not be provided. When the content is more than 80 parts by mass, sufficient photosensitivity may not be provided and it may be difficult to form a pattern. Further, in the photosensitive composition of the present invention, in addition to the above-mentioned polyurethane resin, other resin may be added in an amount of 50% by mass or less based on the mass of the polyurethane resin. The other resin may, for example, be a polyamide resin, an epoxy resin, a polyacetal resin, an acrylic resin, a methacrylic resin, a polystyrene resin or a novolac type phenol resin. &lt;Elastomer&gt; By adding the above-mentioned elastomer to the photosensitive composition, heat resistance, flexibility, and toughness can be imparted to the photosensitive composition. The elastomer is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, and a polyamide. Elastomer, acrylic -19- 201211691 Elastomer, polysiloxane elastomer, etc. These elastic systems are composed of a hard segment component and a soft segment component. Generally, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. Further, the nature of the elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, in terms of productivity in the development step, etc., alkali solubility or swelling property is preferred. The styrene-based elastomer is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a styrene-butadiene-styrene block copolymer and a styrene-isoprene-styrene block. Copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and the like. In addition to the above-mentioned styrene constituting the styrene-based elastomer, a styrene derivative such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene or 4-cyclohexylstyrene can be used. Specifically, as a commercial item, TUFPRENE, SOLPRENE Τ, ASAPRENE Τ, Tuftec (above), elastomer AR (manufactured by ARONKASEI Co., Ltd.), KRATON G, Califlex (above Shell) Japan company), JSR-TR, TSR-SIS, DYNARON (above, manufactured by Nippon Synthetic Rubber Co., Ltd.), DENKA STR (manufactured by Electric Chemical Industry Co., Ltd.), QUINTAC (manufactured by Nippon Paint Co., Ltd.), TPE-SB歹IJ (manufactured by Sumitomo Chemical Co., Ltd.), RABALON (manufactured by Mitsubishi Chemical Corporation), SEPTON, HYBRAR (manufactured by Kuraray Co., Ltd.), SUMIFLEX (manufactured by Sumitomo Bakelite Co., Ltd.), -20-201211691 LEOSTOMER, ACTYMER (the above is made by Riken vinyl indust 1.y company). The olefin-based elastomer is not particularly limited, and may be appropriately selected from the group consisting of, for example, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, and the like. Examples of the copolymer of the olefin include an ethylene-propylene copolymer (EPR), an ethylene-propylene-diene copolymer (EPDM), and the like, and examples thereof include dicyclopentadiene and 1,4-hexadiene. And a non-conjugated diene having a carbon number of 2 to 20, such as cyclooctadiene, methylene norbornene, ethylene norbornene, butadiene or isoprene, and an α-olefin copolymer. Further, a carboxyl-modified NBR in which methacrylic acid is copolymerized to a butadiene-acrylonitrile copolymer can be mentioned. Specific examples thereof include ethylene·α-olefin copolymer rubber, ethylene·α-olefin, non-conjugated diene copolymer rubber, propylene·α-olefin copolymer rubber, butene·α-olefin copolymer rubber, and the like. . Specific examples of the commercially available product include MILASTOMER (manufactured by Mitsui Chemicals, Inc.), EXACT (manufactured by Exxon Chemical Co., Ltd.), ENGAGE (manufactured by Dow Chemica 1 Co., Ltd.), and hydrogenated styrene-butadiene rubber (DYNABONHSBR). Nippon Synthetic Rubber Co., Ltd.), butadiene-acrylonitrile copolymer (NBR series, manufactured by Nippon Synthetic Rubber Co., Ltd.), or a two-terminal carboxyl modified butadiene-acrylonitrile copolymer having a crosslinking point ( XER series, made by Nippon Synthetic Rubber Co., Ltd.). The urethane elastomer is not particularly limited and may be appropriately selected depending on the purpose, for example, a hard segment composed of a low molecular weight diol and a diisocyanate and a polymer (long-chain) diol and a diisocyanate. The polymer (long-chain) diol composed of the structural unit of the soft zone-21-201211691 is composed of polypropylene glycol, polyoxytetramethylene, poly(1,4-butylene adipate). ), poly(ethylene·1,4-butyl adipate), polycaprolactone, poly(1,6-capped hexylene carbonate), poly(adipic acid 1,6-hexane di. neopentyl) Ester) and the like. The number average molecular weight of the polymer (long-chain) diol is preferably 500 to 10,000, and a short-chain diol such as propylene glycol, 1,4-butanediol or bisphenolphthalein may be used in addition to ethylene glycol. The number average molecular weight of the short-chain diol is preferably from 48 to 500. PANDEX T-2185, T-2983N (made by DIC Corporation), Miractran E790, etc. are mentioned as a commercial item of the said urethane elastomer. The polyester elastomer is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include those obtained by polycondensation of dicarboxylic acid or a derivative thereof, and a diol compound or a derivative thereof. The dicarboxylic acid may, for example, be an aromatic dicarboxylic acid such as citric acid, isophthalic acid or naphthalene dicarboxylic acid or a hydrogen atom of the aromatic nucleus via a methyl group, an ethyl group or a phenyl group. An aliphatic dicarboxylic acid having 2 to 20 carbon atoms such as an aromatic dicarboxylic acid, adipic acid, sebacic acid or decadiodicarboxylic acid, and an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, etc. . These systems may be used alone or in combination of two or more. The diol compound may, for example, be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol or 1,10-decanediol '1,4- An aliphatic diol such as cyclohexanediol or an alicyclic diol, a divalent phenol represented by the following structural formula, etc. 0 -22· 201211691

However, in the above structural formula, Y represents any one of an alkylene group having 1 to 1 ring of carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, -0-, -S-, and -SO". Or means that the benzene rings are directly bonded to each other. R1 and R2 represent a halogen or an alkyl group having 1 to 12 carbon atoms. 1 and m represent an integer of 〇~4, ρ is 〇 or 1. The aforementioned polyester elastomer Specific examples thereof include bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, resorcin, and the like. One type may be used alone or two or more types may be used. Further, in the above polyester elastomer, an aromatic polyester (for example, polybutylene terephthalate) portion may be used as a hard segment component. A portion of an aliphatic polyester (for example, a polybutanediol) is used as a multi-block copolymer of a soft segment component. The above-mentioned multi-block copolymer may be exemplified by a hard segment and a soft segment. Specific examples of the various grades, ratios, and molecular weights include Hytrel (manufactured by Dupont-Toray Co., Ltd.), PELPRENE (manufactured by Toyobo Co., Ltd.), and ESPEL (for example). The polyamine-based elastomer is not particularly limited, and may be appropriately selected depending on the purpose, and can be roughly classified into, for example, polyamine using a hard phase and polyether in a soft phase. Or polyester polyether blocking guanamine type and polyether ester blocking guanamine type -23- 201211691 two, in the case of polyamide, using polyamide-6, 1 1, 12, etc., with polyether In particular, 'polyoxyethylene, polyoxypropylene, polybutylene glycol, etc. are used. As a commercial item, UBE polyamide elastomer (made by Ube Industries Co., Ltd.) and DAIAMID (Daicel Hiils) are mentioned. Co., Ltd.), PEBAX (manufactured by Toray Co., Ltd.), GRILON ELY (manufactured by EMS JAPAN Co., Ltd.), Novamide (manufactured by Mitsubishi Chemical Corporation), GRILUX (manufactured by DIC Corporation), etc. The elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, an acrylate as a main component may, for example, be ethyl acrylate, butyl acrylate, methoxyethyl acrylate or ethoxyethyl acrylate. , Examples of the crosslinking point monomer include glycidyl methacrylate and allyl epoxidized propyl ether. Further, acrylonitrile or ethylene may be copolymerized. Specifically, acrylonitrile-butyl acrylate may be mentioned. Copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile/butyl acrylate-glycidyl methacrylate copolymer, etc. The polyfluorene-based elastomer is not particularly limited, and is visible. For the purpose of selection, for example, an organic polyoxymethane as a main component may, for example, be a polydimethyl siloxane, a polymethylphenyl siloxane or a polydiphenyl siloxane. Specific examples of the products to be sold include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, and SH series (all manufactured by Dow Corning Toray Silicone Co., Ltd.). Further, in addition to the above elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin can be obtained, for example, by the above-mentioned bisphenol-24-201211691 F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolak type epoxy resin. Or some or all of the epoxy groups of the cresol novolac type epoxy resin are modified by a two-terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amine-based modified polyoxyxene rubber or the like. Among these elastomers, a two-terminal carboxyl group-modified butadiene-acrylonitrile copolymer and a hydroxyl group-containing polyester elastomer ESPEL (ESPEL1612, manufactured by Hitachi Chemical Co., Ltd.) are preferable in terms of shear adhesion. 1,620). The content of the elastomer is preferably from 1 part by mass to 50 parts by mass, more preferably from 2 parts by mass to 20 parts by mass, even more preferably from 3 parts by mass to 10 parts by mass per 100 parts by mass of the photosensitive composition. Parts by mass. When the content is less than 1 part by mass, the modulus of elasticity of the cured film in the high temperature region tends to be low, and if it is more than 50 parts by mass, the unexposed portion tends not to be eluted by the developer. &lt;Polymerizable compound&gt; The polymerizable compound is appropriately selected depending on the purpose, and is preferably a compound having one or more ethylenically unsaturated bonds, for example. The vinyl unsaturated bond may, for example, be a vinyl group, an allyl group or the like. The vinyl group may, for example, be a (meth) acrylonitrile group, a (meth) acrylamide group, a styryl group, a vinyl ester or a vinyl ether. The allyl group may, for example, be an allyl ether or an allyl ester. In the case of the above compound having one or more ethylenically unsaturated bonds, '-25-201211691 is not particularly limited and may be appropriately selected depending on the purpose, but may, for example, be at least selected from monomers having a (meth) acrylonitrile group. One. The monomer having a (meth) acrylonitrile group is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a monofunctional acrylate or a monofunctional methacrylate or an urethane acrylate. , polyester acrylates, polyfunctional acrylates or methacrylates. Examples of the monofunctional acrylate or monofunctional methacrylate include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxy group (meth)acrylate. Ethyl ester and the like. Examples of the urethane acrylates include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylethane triacrylate, and trishydroxyl. Methyl propane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tetra(meth)acrylate, neopentyl glycol tri(meth)acrylate Ester, dipivalaerythritol hexa(meth)acrylate, penta (meth) acrylate of dipentaerythritol, hexanediol di(meth)acrylate, trimethylolpropane tris(propylene decyloxy) Propyl)ether, tris(propylene decyloxyethyl) isocyanate, tris(propylene decyloxyethyl) cyanate, glycerol tri(meth) acrylate, After the addition reaction of ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin or bisphenol, the (meth) acrylated product is disclosed in Japanese Patent Publication No. 48-4 1 708 Japanese Patent Publication No. Sho 50-6034, and Japanese Laid-Open No. 5 1 -37 1 93 and other publications. The above-mentioned polyester acrylates are described in, for example, Japanese Laid-Open Patent Publication No. -26-201211691, No. 48-64183, and Japanese Patent Publication No. Sho 49-43191 No. 5 2-3 0490. The above-mentioned polyfunctional acrylate or methacrylate such as a reaction product of an epoxy resin and (meth)acrylic acid C and the like. Among these, 'extra good is tris(hydroxymethylpropyl) propyl tris(A|tetrakis(meth)acrylic acid pentaerythritol ester, hexa(methyl)propionic acid, penta (meth)acrylic acid dipivaloerythritol In the content of the polymerizable compound, the phase composition is preferably 10 parts by mass or more, more preferably 5 parts by mass or less, more preferably 10 parts by mass to 40 parts by mass. When the amount is less than or equal to the mass, development may be deteriorated, and if it is more than 50% by mass, the photosensitive layer may become too strong. &lt;Photopolymerization Initiator&gt; The photopolymerization initiator is not particularly limited as long as it has a function of polymerization of a primer compound, but is preferably selected from, for example, an ultraviolet region to a photosensitive one. An active agent which generates a living radical with a photo-excited sensitizer, and an initiator which can be polymerized depending on the type of the monomer. Further, in the case of the above photopolymerization initiator, a preferred species wavelength is in the range of about 300 nm to 800 nm, and at least, it is exemplified by bismuth exemplified by an olefinic acid ester ester S) acrylate or dioxon. The tetraol ester has a certain effect on the above-mentioned photosensitivity and exposure of 50 parts by mass and exposure sensitivity adhesion, and the light is appropriately caused to cause cation separation to contain at least about 50 molecules.消-27- 201211691 The composition of the light coefficient. More preferably, it is 3 30 nm - 500 nm in terms of the aforementioned wavelength. In the case of the aforementioned photopolymerization initiator, a neutral photopolymerization initiator is used. Further, other photopolymerization initiators may be included as needed. The neutral photopolymerization initiator is not particularly limited and may be appropriately selected depending on the purpose, but is preferably a compound having at least an aromatic group, more preferably (bis) fluorenylphosphine oxide or an ester thereof. An acetophenone-based compound, a diphenylketone-based compound, a benzoin-ether compound, a ketal derivative compound, and a thioxanthone compound. The above-mentioned neutral photopolymerization initiator may be used singly or in combination of two or more. Examples of the photopolymerization initiator include (bis) fluorenylphosphine oxide or an ester thereof, an acetophenone-based compound, a diphenylketone-based compound, a benzoin-ether compound, and a ketal derivative compound. , thioxanthone compounds, anthraquinone derivatives, organic peroxides, sulfur compounds, and the like. Among these, from the viewpoints of sensitivity and storage stability of the photosensitive layer, and adhesion between the photosensitive layer and the substrate for forming a printed wiring board, an anthracene derivative, (bis) fluorenylphosphine oxide or an ester thereof is preferred. A acetophenone-based compound, a diphenyl ketone-based compound, a benzoin-ether compound, a ketal derivative compound, and a thioxanthone compound. The (bis) fluorenylphosphine oxide may, for example, be 2 , 6: dimethylbenzimidyl diphenylphosphine oxide, 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, 2,4,6-trimethylbenzimidylphenyl Methyl phosphonate, 2,6-dichlorobenzhydrylphenylphosphine oxide, 2,6-dimethoxybenzimidyl diphenylphosphine oxide, bis(2,6-'dimethoxybenzene Mercapto)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, and the like. -28-201211691 The acetophenone-based compound may, for example, be acetophenone, methoxyacetophenone, phenyl-2-hydroxy-2-methylpropan-1-one or 1-hydroxyl group. Cyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, i_(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1·one Wait. Examples of the diphenyl ketone compound include diphenyl ketone, 4-phenyl diphenyl ketone, methyl benzyl benzoyl benzoate, 4-phenyl diphenyl ketone, and hydroxy diphenyl. Ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone, diphenoxydiphenyl ketone, and the like. The benzoin ether compound may, for example, be benzoin ethyl ether or benzoin propyl ether. The ketal derivative compound may, for example, be a benzyl dimethyl ketal or the like. The aforementioned thioxanthone compound may, for example, be 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or 2,4-diisopropyl. Thioxanthone, isopropyl thioxanthone, and the like. The photopolymerization initiator may be used singly or in combination of two or more. The solid content of the photosensitive composition is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, even more preferably 0.5% by mass, based on the total amount of the photopolymerization initiator. 15% by mass. &lt;Hot cross-linking agent&gt; The thermal cross-linking agent is not particularly limited, and may be appropriately selected depending on the purpose, and the film strength after curing of the photosensitive layer is improved, and it is not suitable for -29-201211691. The range in which the adverse effect is generated may be, for example, a compound containing an epoxy compound (for example, an epoxy compound having at least two fluorenyl groups in one molecule) and a compound having at least two oxime groups in one molecule. An epoxy compound having an anthracene group as described in JP-A-2007-47729, an epoxy compound having an alkyl group at the yS position, a nozzle compound having a oxime group, a polyisocyanate compound, and the like A compound obtained by reacting a blocking agent with an isocyanate group, such as an isocyanate or a derivative thereof. Further, a melamine derivative can be used as the aforementioned thermal crosslinking agent. The melamine derivative may, for example, be methylol melamine or alkylated methylol melamine (a compound obtained by etherifying a methylol group with a methyl group, an ethyl group or a butyl group). These systems may be used alone or in combination of two or more. Among these, the storage stability is good, and the surface hardness of the photosensitive layer or the film strength of the cured film itself is improved. Preferably, the alkylated methylol melamine and the hexamethylated group are particularly preferred. Hydroxymethyl melamine. The content of the thermal crosslinking agent is preferably from 1% by mass to 50% by mass, more preferably from 3% by mass to 30% by mass, based on the solid content of the photosensitive composition. When the content is less than 1% by mass, the film strength of the cured film may be weak. When the content is more than 50% by mass, the developability and the exposure sensitivity may be poor. For example, the epoxy compound may be, for example, 1 An epoxy compound having at least two anthracene groups in the molecule - an epoxy compound having at least two epoxy groups having an alkyl group at a cold position in at least one molecule. -30-201211691 In the case of having at least two fluorenyl groups in one molecule, for example, a bixylenol type or a biphenol, or a mixture thereof, or an oxygen resin having a trimeric isocyanate skeleton may be mentioned. , bisphenol A type epoxy resin, novolak type epoxy F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenolic fat, phenol novolak type epoxy resin, cresol novolac, halogenated epoxy resin Allyl-containing bisphenol A epoxy methane type epoxy resin, diphenyl dimethanol type epoxy resin, base type epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin, ring Oxypropyl acrylate type epoxy resin, propylene glycol type epoxy guanidine type epoxy resin, alicyclic epoxy resin, quinone imine type resin 'trihydroxyphenylmethane type epoxy resin, bisphenol A phenol oxygen Resin, tetrahydroxyphenylethane type epoxy resin, decanoic acid epoxy tetraepoxypropyl xylene decyl ethane resin, naphthyl containing ring from phenol compound and divinyl benzene or dicyclopentadiene The addition of the polyphenol compound to the epichlorohydrin 4-vinylcyclohexene-:[ _Oxide open-loop polymer as an epoxy resin having a linear phosphorus-containing structure, having a cyclic epoxy resin, an α-methylstilbene type liquid crystal epoxy resin, an oxybenzene type liquid crystal ring Oxygen resin, azobenzene type liquid crystal epoxy «methine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal ring type 1 epoxy resin, glycidyl methacrylate copolymerized cyclohexylpentene Heterocyclic ring resin of bisphenol imine and propylene glycol methacrylate epoxy resin type epoxy resin, bisphenol S type epoxy resin epoxy resin, phenol phenol phenanthrene epoxy resin , a beta-epoxy aldehyde varnish-type cyclopropyl ester resin, an oxy-resin, an olefin compound reactant, an epoxidized phosphorus-containing structure of a benzoic acid-based resin, an azo-oxygen resin, a oxime resin, Ring copolymerized epoxy tree-31 - 201211691 Fat, bis(epoxypropyloxyphenyl)-type epoxy resin, bis(epoxypropyloxyphenyl)adamantane type epoxy resin, and the like. These systems may be used alone or in combination of two or more. The bisphenol type epoxy resin may, for example, be YX4000 (manufactured by Japan Epoxy Resin Co., Ltd.) or the like which is commercially available. The heterocyclic epoxy resin having a trimeric isocyanate skeleton or the like is, for example, a commercially available product of TEPIC (manufactured by Nissan Chemical Industries Co., Ltd.), Araldite PT810 (manufactured by Ciba Special Chemicals Co., Ltd.), or the like. Examples of the halogenated epoxy resin include a low brominated epoxy resin, a highly halogenated epoxy resin, and a brominated phenol novolak epoxy resin. The above-mentioned dicyclopentadiene type epoxy resin may, for example, be HP-7200 or HP-7200H (manufactured by DIC Co., Ltd.) which is commercially available. The epoxy propylamine type epoxy resin may, for example, be a diaminodiphenylmethane type epoxy resin, a diepoxypropyl aniline or a triepoxypropylaminophenol. Examples of the above-mentioned glycidyl ester type epoxy resin include diglycidyl citrate, diglycidyl adipate, diglycidyl hexahydrophthalate, and di-acid epoxide. Propyl ester and the like. In the above-mentioned alicyclic epoxy resin, for example, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, bis(3,4-ring) In the case of a commercially available product, oxycyclohexylmethyl) adipate or bis(cyclopentadienyl dicyclopentadiene) is GT-300, GT-400, and ZEHPE 3150 (manufactured by Daicel Chemical Industries, Ltd.). -32- 201211691 For the above-mentioned naphthyl group-containing epoxy resin, for example, a naphthol aralkyl type epoxy resin, a naphthol novolak type epoxy resin, and a tetrafunctional naphthalene type epoxy resin are commercially available. ESN-190, ESN-360 (the above is manufactured by Nippon Steel Chemical Co., Ltd.), HP-403 2, EXA-4750, and EXA-470CK or higher are manufactured by DIC Corporation. The epoxy methacrylate-based propylene glycol copolymer-based epoxy resin may, for example, be CP-50S or CP-50M (manufactured by Shiramoto Oil Co., Ltd.). Further, in addition to the above epoxy compound having at least two mercapto groups in one molecule, an epoxy compound having two epoxy groups having an alkyl group at /3 positions in at least one molecule may be used, particularly preferably A compound having an epoxy group substituted at the A position with an alkyl group (more specifically, an alkyl-substituted epoxypropyl group, etc.). The epoxy compound containing at least the epoxy group having an alkyl group at the /3 position may be one or more epoxy groups contained in one molecule, and all of the epoxy groups may be /3-alkyl-substituted epoxypropyl groups. The epoxy propyl group may be substituted with at least one epoxy group. The above-mentioned compound of the nozzle may, for example, be a compound having at least two nozzle groups in one molecule. Specifically, for example, bis[(3-methyl-3·fluorenylmethoxy)methyl]ether, bis[(3-ethyl-3·fluorenylmethoxy)methyl]ether, I,4-bis[(3-methyl-3-indolylmethoxy)methyl]benzene, I,4-bis[(3-ethyl-3-indolylmethoxy)methyl] Benzene, (3-methyl-3-Df-based) methacrylate, (3-ethyl-3-indolyl) methacrylate, methacrylic acid (3-methyl-3-indole) Methyl ester, methyl-33-201211691 methacrylic acid (3-ethyl-3-indolyl) methyl ester or the like of these polyfunctional oximes, which may have a thiol group, poly (pair) a hydroxystyrene), a cardo type calixarene, a cupid resorcinol (silsesquioxane), and the like, and may also have a sputum ring. Unsaturated〗) Acrylate copolymers and the like. Further, the polyisocyanate cyanate compound described in JP-A No. 5-9407 may be a compound containing at least two isocyanide, a cyclic aliphatic or an aromatic substituted aliphatic compound. The difunctional isocyanate, the adduct of the bifunctional isocyanate of a polyfunctional alcohol, a cyclic trimer, etc., and the said bifunctional isocyanate is a mixture of a cyanate ester and a 1,4-phenyl diisocyanate, 2, 4 cyanate ester, 1,3- and 1,4-dimethylbenzene diisocyanate 'base only) methane, bis(4-isocyanate cyclohexyl)methane, isohexamethylene diisocyanate, diisocyanate Examples of the methyl group-mentioned polyfunctional alcohol include trihydric alcohol, glycerin, and the like. The above-mentioned cyclic trimer may, for example, be an ester, hexamethylene-1,6-diisocyanate or a derivative thereof, and the above-mentioned compound may be used as a blocking agent for reacting a polyisocyanic oligomer or copolymerization. And acid anhydride monomers such as novolac resin phenols, calixenes, and other alkyl groups (methyl' can be used for the sulfonium compound, which is derived from the aliphatic group of the polyisoate group. And the alkylene oxide adduct and hydrazine such as 1,3 - benzene diiso- and 2,6-toluene diiso I (4-isocyanate - benzophenone diisocyanate methylene ester, etc.. methyl propane, new U diisocyanide Acid hexamethylene, etc., the compound obtained by the acid ester, -34-201211691, and even the isocyanate group blocking agent in the compound obtained by reacting the blocking agent with the isocyanate group of the polyisocyanate and its derivative, an alcohol And a phthalic acid, a phenol, a heterocyclic hydroxy compound, an active methylene compound, etc., which are described in JP-A-6-295060, and have at least one molecule in the molecule. Any of a polymeric double bond and at least one blocked isocyanate group Examples of the above-mentioned alcohols include, for example, isopropyl alcohol and tertiary butanol. Examples of the intrinsic amines include ε-caprolactam and the like. For example, phenol, cresol, p-tertiary butyl phenol, p-secondary butyl phenol, p-second pentyl phenol, p-octyl phenol, p-nonyl phenol, etc. may be mentioned. Examples of the active methylene compound include, for example, dialkyl malonate, methyl ethyl ketone oxime, and ethyl hydrazino group. Acetone, acetonitrile acetate oxime, acetone oxime, cyclohexanone oxime, etc. The melamine derivative may, for example, be methylol melamine or alkylated methylol melamine (methanol methyl group) a compound which is etherified with an ethyl group, a butyl group, etc.). These may be used singly or in combination of two or more. Among them, the storage stability is good, and the surface hardness of the photosensitive layer is Or the film strength of the cured film itself is effectively increased, preferably alkylated methylol melamine Particularly preferred is hexamethylated methylol melamine. -35- 201211691 - Tanning material - the photosensitive composition is preferably further containing a tanning material. The tanning material can increase the surface hardness of the permanent pattern or depressurize the line. The coefficient or the dielectric constant or the dissipation factor of the cured film itself is exemplified by the above-mentioned pigment, for example, an inorganic pigment, an organic fine particle, etc. The inorganic pigment may, for example, be exemplified. Kaolin, barium sulfate, barium titanate, barium oxide powder, fine powdered barium oxide, gas phase cerium oxide, amorphous cerium oxide, crystalline cerium oxide, lanthanum oxide, spherical cerium oxide, talc, clay, carbonic acid Magnesium, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, etc. The commercially available product of the above-mentioned barium sulfate is, for example, B-30 (manufactured by Nippon Chemical Industry Co., Ltd.). In the case of the above-mentioned dip, it is preferred to use a coating which is coated with a decane coupling agent in terms of improvement in low water absorption or impact resistance. The broth coupling agent is not particularly limited, and examples thereof include vinyl trichloromethane, vinyl triethoxy decane, 7-aminopropyl triethoxy decane, and N-( 0 -amine Benzyl)-r-aminopropyltrimethoxydecane, Ν-(Θ-aminoethyl)-r-aminopropylmethyldimethoxydecane, r-mercaptopropyltrimethoxy Decane, 7-glycidoxypropyltrimethoxydecane, 7-glycidoxypropylmethyldimethoxydecane, methacryloxypropyltrimethoxydecane, r-methyl Acryloxypropylmethyldimethoxydecane, vinyltriethoxydecane, and α-[[3-(trimethoxy) described in Japanese Patent Publication No. 7-68256-36-201211691 Mercapto)propoxy]methyl]-imidazol-1-ethanol, 2-ethyl-4-methyl-α·[[3-(trimethoxyindolyl)propoxy]methyl]-imidazole- 1-ethanol, 4-vinyl-α-[[3-(trimethoxyindolyl)propoxy]methyl]-imidazol-1-ethanol, 2·ethyl-4-methylimidazopropyltrimethyl Oxy decane' and such salts, intramolecular condensates, intermolecular condensates, and the like may be used alone. You can also use more than two types. In the case of the above-mentioned coating with a decane coupling agent, the coating may be preliminarily carried out only (hereinafter referred to as "pretreatment" in the present case), or may be part of other components in the photosensitive composition or All together. The method for carrying out the above pretreatment is not particularly limited, and examples thereof include a dry method, an aqueous solution method, an organic solvent method, and a spray method. The temperature at which the pretreatment is carried out is not particularly limited, but it is preferably at room temperature to 2 〇〇〇c. In the case of the above-mentioned purpose, it is also preferable to add a catalyst. The catalyst is not particularly limited. For example, an acid, a base, a metal compound, an organometallic compound, etc. The amount of the above-mentioned decane coupling agent to be used for the pretreatment is not particularly limited, but is 100 parts by mass relative to the dip. It is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.05 part by mass to 50 parts by mass. If the amount added is less than 质量·〇1 part by mass, the surface treatment is insufficient, and the desired effect may not be obtained. 50 parts by mass, the mash is likely to be agglomerated, and the workability may be lowered. The average particle diameter of the above-mentioned kneading material is preferably 'g 以下#m or less, and more preferably -37 to 201211691 is 3 μm or less. When the average particle diameter is more than 10 μrn, the resolution may be deteriorated by light scattering. The amount of the above-mentioned pigment is preferably 1 part by mass or more based on 100 parts by mass of the photosensitive composition. Less than 50 parts by mass, more preferably 5 masses The amount is preferably 40 parts by mass, particularly preferably 1 part by mass to 30 parts by mass. If the amount added is less than 1 part by mass, the linear expansion coefficient may not be sufficiently lowered, and if it is 50 parts by mass or more, it is photosensitive. When a cured film is formed on the surface of the layer, the film quality of the cured film becomes brittle, and when a wiring is formed using a permanent pattern, the function as a protective film for wiring may be impaired. &lt;Other components&gt; The other components are not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and a coloring agent (coloring pigment or dye). Alternatively, a adhesion promoter for the surface of the substrate and other auxiliary agents (for example, conductive particles, a chelating agent, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant) may be further used. , spices, surface tension modifiers, chain transfer agents, etc.). By appropriately containing these components, properties such as stability, photographic properties, and film properties of the intended photosensitive layer can be adjusted. The thermal polymerization inhibitor is described in detail in, for example, paragraphs [0101] to [0102] of JP-A-2008-250074. The thermosetting accelerator is described in detail in, for example, JP-A-2008 Paragraph [0093] of the Japanese Patent Publication No. -250074. -38-201211691 The plasticizer is described in detail in paragraphs [〇1〇3] to [0104] of Japanese Laid-Open Patent Publication No. 2008-250074, for example. The coloring agent is described in detail in, for example, paragraphs [〇1〇5] to [0106] of JP-A-2008-250074. The adhesion promoter is described in detail in, for example, paragraphs [〇1〇7] to [0109] of JP-A-2008-25 0074. The crosslinking density of the photosensitive composition of the present invention is preferably from 0.05 mol/m3 to 3_Omol/m3, more preferably from 0.5 mol/m3 to 2.7 mol/m3, particularly preferably from 0.75 mol/m3 to 2_4 mol/ M3. When the cross-linking density is less than 0.05 mol/m3, the glass transition temperature of the cured product may be lowered. If it is more than 3.0 mol/m3, the hardened material may become brittle. The aforementioned crosslinking density can be measured by, for example, a titration method. (Photosensitive Laminate) The photosensitive laminate system has at least a substrate and a photosensitive layer provided on the substrate, and is laminated with another layer appropriately selected depending on the purpose. &lt;Substrate&gt; The substrate to be processed in which the photosensitive layer of the base system is formed or the transfer target to which at least the photosensitive layer of the photosensitive film of the present invention is transferred is not particularly limited, and may be appropriately selected depending on the purpose, for example, It is arbitrarily selected from those having a high surface smoothness to a surface having irregularities. A plate-like substrate is preferred, and a so-called substrate is used. Specifically, a -39-201211691 substrate (printed substrate), a glass plate (soda glass plate, etc.), a synthetic resin film, paper, a metal plate, etc., which are known for producing a printed wiring board, are mentioned. &lt;Photosensitive layer&gt; The photosensitive layer is not particularly limited as long as it is a layer composed of a photosensitive composition, and can be appropriately selected depending on the purpose. In addition, the number of layers of the photosensitive layer is not particularly limited, and may be appropriately selected depending on the purpose, and may be, for example, one layer or two or more layers. In the method of forming the photosensitive layer, the photosensitive composition of the present invention may be prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent to prepare a photosensitive composition solution. The solution is dried and coated by a method such as a screen coater, a bar coater, a spin coater, or the like, and then the photosensitive resin composition is transferred from the dry film without a drying step. Printing, a method of directly forming a photosensitive layer, and the like. &lt;&lt;DryFilm&gt;&gt; The dry film system has a support and a photosensitive layer comprising the photosensitive composition of the present invention on the support, and further has other layers as needed. - Supporting body - The support is not particularly limited and may be appropriately selected depending on the purpose. However, it is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and it is more preferable that the smoothness of the surface is further improved. The support system is preferably made of a synthetic resin and is transparent, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethyl b--40-201211691, and cellulose triacetate. Cellulose diacetate, alkyl poly(meth)acrylate, poly(meth)acrylate copolymer 'polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, celecin, polyvinylidene chloride (P〇lyvinylidene chloride) copolymer, polyamide, polyimine, vinyl chloride, ethyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, nylon film and other plastic film Among these, it is particularly preferred to be polyethylene terephthalate. These systems may be used alone or in combination of two or more. The thickness of the support is not particularly limited and may be appropriately selected depending on the purpose, but is preferably, for example, more preferably 5 &quot;m~100//m, particularly preferably 8&quot;m~50&quot; m. If the thickness is less than 2 /z m, the collapse may become a problem. If it is larger than 150 / m, the embedding property at the time of lamination may become a problem. The shape of the support body is not particularly limited and may be appropriately selected depending on the purpose, but is preferably elongated. The length of the elongated support is not particularly limited, and may be, for example, about 10 m to 2 0,0 0 m. &lt;Other layers&gt; The other layers are not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a protective layer, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, and surface protection. Layer and other layers. The photosensitive film system may have one of these layers, or may have two or more types. &lt;&lt;Protectivelayer&gt;&gt; The photosensitive film may form a protective layer on the photosensitive layer. The protective layer may, for example, be used in the above-mentioned support, -41 - 201211691, paper, laminated polyethylene, polypropylene paper, etc., among which polyethylene film and polypropylene film are preferable. . The thickness of the protective layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably, for example, 5 #m to 1 0 〇μm, more preferably 8//m to 50# m, particularly preferably 10# m~3〇ν m. The combination of the support and the protective layer (support/protective layer) may, for example, be polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polyvinyl chloride/race.珞凡, polyimine / polypropylene, polyethylene terephthalate / polyethylene terephthalate. Further, the interlayer adhesion force can be adjusted by subjecting at least one of the support and the protective layer to surface treatment. The surface treatment of the support may be carried out in order to increase the adhesion to the photosensitive layer, and examples thereof include coating of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, and glow discharge. Irradiation treatment, active plasma irradiation treatment, laser irradiation treatment, and the like. Further, the static friction coefficient of the support body and the protective layer is preferably from 0.3 to 1.4, more preferably from 0.5 to 1.2. When the coefficient of static friction is 0.3 or more, it is possible to prevent curl unevenness in the form of a roll due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. The photosensitive film is preferably wound into a cylindrical core, for example, and is wound into a roll in a long shape. The length of the above-mentioned elongated photosensitive film is not particularly limited, and can be appropriately selected, for example, from the range of from 10 m to 20,000 m. Further, the elongated material in the range of 100 m to 1,000 m -42 to 201211691 can be cut into a roll shape so that the user can easily use it. Further, in this case, the support body is made the outermost side. Further, the aforementioned film may be cut into a sheet shape. In the case of storage, from the viewpoint of protection and prevention of the end faces, it is preferable to provide a separator (particularly for preventing the desiccant) on the end surface, and it is preferable to use a low moisture permeability in the package. The protective layer may be subjected to surface treatment in order to adjust the adhesion between the protective layer and the layer. In the above surface treatment, as described above, a method of forming a coating layer formed of a polymer such as polyorganosiloxane, fluorine, polyvinyl fluoride or polyvinyl alcohol is formed on the surface of the protective layer, After the polymer is applied to the surface of the protective layer, it is formed by drying at 30 ° C to 150 ° C. In the case of the temperature at the time of the drying, the temperature of the drying is particularly preferably 50 ° C, and the solvent of the photosensitive composition solution is appropriately selected, and examples thereof include alcohols, ketones, and aromatic hydrocarbons. , halogenated hydrocarbons, halogenated hydrocarbons, ethers, dimethyl dimethyl acetamide, dimethyl amide, cyclobutyl hydrazine and the like. These may be one type or two or more types may be used in combination. Further, a known agent can be added. The alcohol may, for example, be methanol, ethanol, isopropanol, n-butanol, secondary butanol or n-pentanol. Examples of the ketones include acetone, methyl ethyl ketone butyl ketone, cyclohexanone, and diisobutyl ketone. The esters include, for example, ethyl acetate and vinegar, which are preferably roll-on roll-shaped photosensitive edge-welding materials. For the aforementioned sensitization, a polyolefin is exemplified. Apply the cloth solution for 1~30 minutes~12 (TC ° is not limited, ester, aryl carbamide, interface n-propanol, methyl methacrylate, -43 · 201211691 Ester, methyl sulfate, ethyl propionate, dimethyl decanoate, ethyl benzoate, methoxypropyl acetate, etc. Examples of the aromatic hydrocarbons include, for example, toluene and xylene. Benzene, ethylbenzene, etc. The halogenated hydrocarbons include, for example, carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane'methylene chloride, monochlorobenzene, and the like. Examples of the ethers include tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, and the like. In addition, it is not particularly limited, and may be appropriately selected depending on the purpose, and may be, for example, a method of directly applying to the support by using a spin coater, a slit rotator, a roll coater, a die coater, a curtain coater or the like. The drying conditions vary depending on the components, the type of solvent, the ratio of use, etc., but are usually 60 ° c to 1 10 ° c. The thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably, for example, more preferably 2 β m to 50 /zm &gt;&lt;Manufacturing Method of Photosensitive Laminates&gt; The method for producing the photosensitive layered body may be at least one of heating and pressurizing at least the photosensitive layer of the photosensitive film of the present invention. The method of transferring the layers on one side. In the method of producing a photosensitive laminate, at least one of -44 to 201211691 of the photosensitive film of the present invention is laminated on the surface of the substrate. Further, when the photosensitive film has the protective layer, it is preferable to peel off the protective layer and to laminate the photosensitive layer on the substrate. The apparatus for carrying out the above-mentioned layering is not particularly limited, and may be appropriately selected depending on the purpose, and for example, a laminator (for example, VP-II manufactured by Daisei Lammator Co., Ltd., VP130 manufactured by Nichigo-Morton Co., Ltd., VP130) can be suitably used. Wait. The temperature of the above heating is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably from 15 ° C to 180 ° C, more preferably from 60 ° C to 140 ° C. When the temperature of the heating is less than 15 ° C, the adhesion to the underlying substrate may be poor, and if it is greater than 180 ° C, the residual film may be easily formed by the pressure of the pressurization. It is not particularly limited, and may be appropriately selected depending on the purpose, for example, preferably O.IMPa~l.OMPa, more preferably 0.2MPa~0_8MPa. If the pressure of the above pressurization is less than 0.1 MPa, the embedding of the underlying pattern may be It becomes unsatisfactory. If it is greater than 1. 〇 MPa, the photosensitive resin may ooze out to the periphery. (Permanent pattern forming method) The permanent pattern forming method of the present invention contains at least an exposure step, and further includes other steps such as a development step which is appropriately selected as needed. &lt;Exposure Step&gt; The above-described exposure step is a step of pattern-exposed the photosensitive layer to the photosensitive layer -45 to 201211691 in the photosensitive laminate of the present invention. The above sense and base system are as described above. In the above-mentioned exposure, it is not particularly limited, and may be, for example, a digital exposure, an analog exposure, or the like, and specific examples thereof include IP-3000 (made by Fujifilm Co., Ltd.) and EXP-2001B (1) RC. . &lt;Other Steps&gt; The other steps described above are not particularly limited, and may be selected as desired, and examples thereof include a surface treatment step of a substrate, a development step treatment step, a post exposure step, and the like. &lt;&lt;DevelopingStep&gt;&gt; In the development described above, the removal of the photosensitive layer is carried out. The method of removing the unhardened portion is appropriately selected without particular limitation. The removal can be carried out, for example, by using a developing solution. The developer is not particularly limited and may be selected depending on the intended purpose, and examples thereof include an alkaline aqueous solution, a water-based developing solution, and the like. Among them, a weakly alkaline aqueous solution is preferred. The alkali component of the weak alkali aqueous solution may, for example, be lithium, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate or potassium phosphate. Sodium, potassium pyrophosphate, borax, and the like. The light layer may be appropriately selected from the INPREX production facility and the hardened exposure portion may be formed by a suitable solvent potassium hydroxide or carbon pyrophosphate-46-201211691. For example, the pH of the weakly alkaline aqueous solution is preferably 8 -12, more preferably 9 to 1 1. The aqueous solution of the weakly basic solution may, for example, be a sodium carbonate aqueous solution or a potassium carbonate aqueous solution of 0.1% by mass to 5% by mass. The temperature of the developer may be appropriately selected in accordance with the developability of the photosensitive layer. For example, it is preferably about 25 ° C to 4 (TC). In the case of the developer, it may be combined with a surfactant or a solvent. A foaming agent, an organic base, an organic solvent for promoting development, etc. The developing solution may be a water-based developing solution in which water or an aqueous alkali solution is mixed with the organic solvent. For example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, sulphate, triethanolamine, etc., in the above-mentioned organic solvent for promoting development, for example, an alcohol, Ketones, esters, ethers, guanamines, lactones, and the like. &lt;&lt;Hardening treatment step&gt;&gt; The hardening treatment step is a step of subjecting the photosensitive layer in the formed pattern to a hardening treatment after performing the above-described development step. The hardening treatment step is appropriately selected depending on the purpose without particular limitation, but may be, for example, a full exposure treatment, a total heat treatment or the like. In the method of the above-described face exposure treatment, for example, a method of exposing the entire laminate to the above-mentioned permanent pattern on the laminated body after the development is carried out is exemplified. The apparatus for promoting the hardening of the resin in the photosensitive composition of the photosensitive layer by the full exposure and hardening the surface 0 of the permanent pattern to perform the above-described overall exposure is not particularly limited, and may be appropriately selected depending on the purpose. However, a UV exposure machine such as an ultrahigh pressure water, a silver lamp, or the like can be suitably used. In the above-described method of the overall heat treatment, a method of heating the entire layered body on which the permanent pattern is formed after the development is exemplified. By this overall heating, the film strength of the surface of the aforementioned permanent pattern is increased. The heating temperature in the above overall heating is preferably from 120 ° C to 250 ° C, more preferably from 120 ° C to 200 ° C. When the heating temperature is less than 1 20 ° C, the film strength may not increase. If it is more than 205 °, the decomposition of the resin in the photosensitive composition may occur, and the film quality may become weak and brittle. In the above heating time in the overall heating, it is preferably from 10 minutes to 120 minutes, more preferably from 15 minutes to 60 minutes. The apparatus for performing the above-described overall heating is not particularly limited, and may be appropriately selected from known apparatuses, and examples thereof include a dry oven, a hot plate, and an IR heater. When the permanent pattern forming method is a permanent pattern forming method of forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern forming method can be formed on the printed wiring board by the aforementioned permanent pattern forming method. - 201211691 Pattern, further soldered as described below. That is, the hard layer is formed by the development of the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. The portion of the metal layer exposed on the surface of the printed wiring board is gold-plated and then soldered. Next, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer functions as a protective film or an insulating film (interlayer insulating film) and a solder resist to prevent conduction from the outside or the electrodes adjacent to each other. (Printed substrate) The printed circuit board such as the package substrate of the present invention has at least a base and a permanent pattern formed by the permanent pattern forming method, and further has other configurations as needed. The other configuration is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a build-up substrate in which an insulating layer is further provided between the substrate and the permanent pattern. [Examples] The examples of the invention are described below, but the invention is not limited by the examples. (Synthesis Example 1) - Synthesis of acid-modified vinyl group-containing polyurethane resin U1 _ In a 500 mL three-neck round bottom flask equipped with a condenser and a stirring machine, 22. bis(hydroxymethyl)propionic acid ( DMPA) 10.86 g (〇.〇8i Moule) and monomethyl acrylate glycerin (GLM) 16.82 g (0-105 mol) were dissolved in propylene glycol monomethyl ether mono-49-201211691 acetate 79 mL. 4,4'-diphenylmethane diisocyanate (MDI) 37.54g (0.15 mole), 2,6-di-tertiary butylhydroxytoluene O.lg, and the trade name: NEOSTANN U-600 Nitto Chemical Co., Ltd.) 2 g was used as a catalyst and heated and stirred at 75 ° C for 5 hours. Thereafter, it was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 145 g of a polymer solution. The obtained acid was modified with a vinyl group-containing polyurethane resin U1 solution (solid content concentration: 45 mass%), and the solid content acid value was 70 mgKOH/g, and the weight average molecular weight measured by gel permeation chromatography (GPC) ( Polystyrene standard) is 8,000, and the base equivalent is 1.5 mmol/g. Further, the acid-modified urethane-containing polyurethane resin U1 is represented by the above formula (1), and in the formula (1), a is 57, b, and c is 0, d is 17, and the e is 26. The aforementioned acid value is measured in accordance with JIS K0070. However, when the sample is not dissolved, dioxane or tetrahydrofuran or the like is used as a solvent. The weight average molecular weight was measured using a high-speed GPC apparatus (HLC-802A, manufactured by Toyo Soda Co., Ltd.). Namely, 0.5% by mass of a THF solution was used as a sample solution, and a column of TSKgelGMH 62 was injected, and a 200 / z L sample was injected, and the solution was extracted with the above THF solution, and measured at 25 ° C by a refractive index detector. Next, the weight average molecular weight was determined by a molecular weight distribution curve corrected by standard polystyrene. The above vinyl equivalent is determined by measuring the bromine number in accordance with JIS K2605. (Synthesis Example 2) - Synthesis of acid-modified vinyl group-containing polyurethane resin U2 · -50- 201211691 In Synthesis Example 1, 'except 4,4'-diphenylmethane diisocyanate (MDI) 37.54 g (0.15 mol) is replaced by 4,4'-diphenyl-methyl diisocyanate (MDI) 30.03 g (0.12 mol) and diammonium diisocyanate (HMDI) 5.05 g (0.03 a combination of 2,2-bis(hydroxymethyl)propionic acid (DMPA) 10.86 g (0.081 mol) and a combination of monoglyceryl methacrylate (GLM) I6.82 g (0.105 mol) Is 2,2-bis(transmethyl)butyric acid (DMBA) 10.22g (0.069 moles), monomethyl propylene glyceride (GLM) 1 2 · 9 7 g (0 · 0 8 1 molar In the same manner as in Synthesis Example 1, except that a combination of polypropylene glycol (molecular weight: 400, PPG400) of 4.80 g (0.012 mol) and propylene glycol monomethyl ether monoacetate (79 mL) was replaced by 77 mL, the acid-modified vinyl group was synthesized. Polyurethane resin (U2) solution (solid content concentration of 45 % by mass). The obtained acid-modified vinyl-containing polyurethane resin U2 has a solid content acid value of 65 mgKOH/g and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 15,000. Vinyl equivalent weight 1.26 mmol/g 〇 (Synthesis Example 3) - Synthesis of acid-modified vinyl group-containing polyurethane resin U3 - In Synthesis Example 1, 'except 4,4'-diphenylmethane diisocyanate (MDI) 37.54g (0.15 mole) instead of 4,4'-diphenylmethane diisocyanate (MDI) 30.03g (0-12 moles) and hexamethylene diisocyanate (HMDI) 5.05g (0_03 Mo a combination of 2,2-bis(hydroxymethyl)propionic acid (DMPA) 10.86 g (0.081 mol) and glyceryl monomethacrylate-51-201211691 (GLM) 16.82 g (0.105 mol) The combination substitution is 2,2-bis(hydroxymethyl)propionic acid (DMPA) 7.24 g (0.054 mol), monoglyceryl glyceride (GLM) 10.09 g (0.06 3 mol) and polypropylene glycol (molecular weight 400, The synthesis of acid-modified vinyl-containing polyamine A was carried out in the same manner as in Synthesis Example 1 except that a combination of 15.60 g (0.039 mol) and propylene glycol monomethyl ether monoacetate (79 mL) was replaced by 83 mL. Acid ester resin U3 solution (solid content concentration: 45 mass%). The obtained acid is modified with a vinyl-containing polyurethane resin U3, the solid content acid value is 45 mgKOH/g, and the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) is 20,000, ethylene. The base equivalent system is 9.9 mmol/g. Further, the acid-modified vinyl group-containing polyurethane resin U3 is represented by the above formula (1), and in the formula (1), a system 44, b system 7, c system 23, d system 11, e Department 1 5. (Synthesis Example 4) - Synthesis of Polyurethane Resin U4 - 500 mL three-neck round bottom flask equipped with a condenser and a stirrer, and 22.2 bis(hydroxymethyl)propionic acid (DMBA) 32.00 g (0.216 mol) And 9.00 g (0.009 mol) of polypropylene glycol (molecular weight 1,000, PG 1000) was dissolved in 118 mL of propylene glycol monocarboxylic acid monoacetic acid vinegar. Add 4,4'-diphenyl-a-isochlorite (MDI) 37.5 4g (0-15 mol), 2,6-di-n-butyl butyl-based toluene O.lg, NEOSTANN ϋ-600 (Nitto Chemical Co., Ltd. product) 〇 2g, and stirred at 75 ° C for 5 hours, added 9.6 lg of methyl alcohol. Thereafter, a methyl propylene succinic acid propylene glycol-52-201211691 (GMA) 17.91 g (0.126 mol) and a catalyst triphenyl phosphine 5,000 ppm were added as a vinyl group-containing epoxy group. After stirring at 10 ° C for 5 hours, it was cooled to room temperature to obtain 214 g of a polymer solution. The obtained acid was modified with a vinyl group-containing polyurethane resin U4 solution (solid content concentration: 45 mass%), a solid content acid value of 75 mgKOH/g, and a weight average molecular weight measured by gel permeation chromatography (G PC). (Polystyrene standard) was 12,000, and the Ethylene group equivalent was 1.3 mmol/g. (Synthesis Example 5) - Synthesis of Polyurethane Resin U5 - In Synthesis Example 4, except that 4,4'-diphenylmethane diisocyanate (MDI) 3 was replaced by 7.54 g (0.15 mol) to 4, 4 '-Diphenylmethane diisocyanate (MDI) 30.03 g (0.12 mol) combined with hexamethylene diisocyanate (HMDI) 5.05 g (0.03 mol), 2,2-bis(hydroxymethyl) The combination of propionic acid (DMBA) 32.00g (0.216 moles) and polypropylene glycol (molecular weight 1, 〇〇0, PPG 1 000) 9.00g (0.009 moles) is replaced by 2,2-bis(hydroxymethyl)propyl A combination of acid (DMPA) 28.17g (0.21 mole) and polypropylene glycol (molecular weight 400) (PPG400) 6.00g (〇.〇15 mole), which will be used as a vinyl-containing epoxy group. The ester (GMA) 17.91 g (0.126 mol) was replaced by the trade name: Cy cl omer Ml 00, manufactured by Daicel Chemical Co., Ltd.), and the propylene glycol monomethyl ether monoacetate 1 18 mL was replaced by 1 12 mL. The acid-modified vinyl group-containing polyurethane resin U5 was synthesized in the same manner as in Synthesis Example 4. The obtained acid is modified with a vinyl-containing polyurethane resin U5 solution (solid-53-201211691 body composition concentration: 45% by weight), and the solid content acid value is 9〇mgK〇H/g, by gel permeation chromatography. The weight average molecular weight (polystyrene standard) measured by GPC was 1 5,000 and the ethylene equivalent system 丨/g. (Synthesis Example 6) - Polyurethane resin Synthesis Example 4, except that 4,4,-diphenylmethane diisocyanate (MDI) 3 7.54 g (0.15 mol) was replaced with 4,4,diphenyl a combination of 30.03 g (0.12 mol) of methane diisocyanate (MDI) and 5.05 g (0_03 mol) of hexamethylene diisocyanate (HMDI), 22 bis(hydroxymethyl)propionic acid ( DMBA)3 2.00g (0.216 mole) combined with polypropylene glycol (molecular weight (^(10), PPG1000) 9.00g (0. 〇〇9 mole) instead of 22 bis(hydroxymethyl)propionic acid (DMPA) 22.13g (〇.i65 Moer) in combination with polypropylene glycol (molecular weight 4 〇〇, PPG400) 12.00 g (0.03 mol), will be used as a vinyl group-containing epoxy group of glycidyl methacrylate (GMA) 17.91 g In the same manner as in Synthesis Example 4, except that the product name: Cyclomer A400 (manufactured by Daicel Chemical Co., Ltd.) was replaced by i8 lin L. Acid-modified vinyl-containing polyurethane resin U6. The obtained acid was modified with a vinyl group-containing polyurethane resin U6 solution (solid content concentration: 45 mass%), and the solid content acid value was 6 〇 mg KOH/g, and the weight average was measured by gel permeation chromatography (GPC). The molecular weight (polystyrene standard) is 9,000, and the ethyl group equivalent system is 88 mm〇i/g. (Synthesis Example 7) -54-201211691 - Synthesis of polyester elastomer - 699 parts by mass of dimethyl phthalate, 24 parts by mass of dimethyl isononanoate, 226 parts by mass of dimethyl adipate, hydrazine 553 parts by mass of dimethyl diacid, 417 parts by mass of 2,2-dimethylpropanediol, 324 parts by mass of butanediol, 769 parts by mass of ethylene glycol, and 2 parts by mass of Irganox 1330 (manufactured by Ciba Japan Co., Ltd.) as an antibiotic 9 parts by mass of oxidizing agent and tetrabutyl titanate were mixed in a reactor, and the temperature was raised from room temperature to 260 ° C for 2 hours while stirring, and then heated at 260 ° C for 1 hour to carry out a transesterification reaction. Next, the inside of the reactor was gradually decompressed and heated, and the initial polycondensation reaction was carried out by taking it to 245 ° C and 0.5 to 2 torr for 30 minutes. Further, after the polymerization reaction was carried out for 4 hours at 245 ° C and 0.5 to 2 torr, it took 30 minutes to return to normal pressure while introducing dry nitrogen, and the polyester was taken out in a nine shape to obtain a polyester. The obtained polyester was diluted and dissolved in propylene glycol monomethyl ether acetate to have a solid content concentration of 15% by mass to obtain a polyester elastomer solution. Further, the weight average molecular weight (polystyrene standard) of the obtained polyester elastomer measured by gel permeation chromatography was 34,000. (Example 1) - Production of photosensitive film -

On the polyethylene terephthalate film (16 FB50, manufactured by Toray Co., Ltd.) having a thickness of 16 μm as a support, a photosensitive composition solution composed of the following composition was applied and dried to the above support. A photosensitive layer having a thickness of 25/m was formed thereon. On the photosensitive layer, a polypropylene film (April Special Paper Co., Ltd., ALPHAN-55-201211691 E-200) having a thickness of 20 μm was laminated as a protective layer to produce a photosensitive film. - Composition of the photosensitive composition solution - • Polyurethane resin U1 of Synthesis Example 1 (solid content: 45 mass%) 1 0 3 .1 parts by mass of a polymerizable compound (DC PA, manufactured by Shin-Nakamura Chemical Co., Ltd. 1 9 · 0 parts by mass of thermal crosslinking agent (EpoTohto YDF-170, manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin) 10_4 parts by mass of melamine 0.60 parts by mass of IRGACURE 907 (manufactured by Ciba Special Chemicals Co., Ltd.) 2. 1 part by mass of diethyl thioxanthone (manufactured by Nippon Kayaku Co., Ltd.) 0.020 parts by mass of EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.069 parts by mass of the polyester elastomer of Synthesis Example 7 (solid content) 15 mass%) 29.3 parts by mass of copper phthalocyanine 0.067 parts by mass of cerium oxide treated with methacrylate decane (SC-2500SMJ, manufactured by Ronson (average particle size 0.5 V m)) 16.1 parts by mass of methyl ethyl ketone (solvent) 40.0 parts by mass - a laminate of a pair of substrates - As the above-mentioned substrate, a surface of a copper clad laminate (without perforation, copper thickness of 12 μm) was subjected to chemical honing treatment to prepare. On the copper clad laminate, a vacuum laminator (Nichigo-Morton Co., Ltd.) is used while the photosensitive layer of the photosensitive film is attached to the copper clad laminate to peel off the protective layer in the photosensitive film of -56-201211691. Co., Ltd., VP130) laminates the copper-clad laminate, the photosensitive layer, and the laminate of the polyethylene terephthalate film (support) in this order. The lamination conditions were a vacuuming time of 40 seconds, a temperature of 70 ° C, a pressure of 0.2 MPa, and a pressurization time of 10 seconds. The obtained laminate was evaluated for minimum opening diameter, TCT resistance, and insulation reliability as described below. The results are shown in Table 1. &lt;Minimum opening diameter&gt; The photosensitive laminate was allowed to stand at room temperature (23 ° C, 55 % RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the above-mentioned photosensitive laminate, a parallel exposure apparatus was used, and a mask pattern in which a circular pit pattern was formed from a diameter of 30 #m to ΙΟΟμη at intervals of 5 μm was used. Exposure. The exposure amount at this time is set such that the number of steps of the 31-step step guide becomes 20 segments. After standing at room temperature for 10 minutes, a polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. The entire photosensitive layer on the copper-clad laminate is sprayed as a solution of sodium carbonate (30 ° C, 1% by mass) as a spray solution at a spray pressure of 0.15 MPa at a time four times the shortest development time to dissolve and remove the hardened layer. region. The thus-obtained pit pattern was observed by SEM, and it was confirmed that there was no development residue or undercut, and it was a circular cone pattern of a forward taper, and it was set as the minimum opening diameter. &lt;TCT resistance&gt; A comb-shaped substrate having a copper thickness of 18/zm and L/S = 75#m/125//m was used as the substrate of -57-201211691. The surface of the photosensitive layer of the laminate produced in the same manner as the laminate is exposed to a pattern of a circular pit pattern having a diameter of 200, a diameter of 300, and a diameter of 400 μm by an optimum exposure amount for a parallel exposure machine. After 10 minutes, the support was peeled off from the photosensitive laminate, and the entire surface of the photosensitive layer on the copper clad laminate was sprayed with a 1% by mass aqueous solution of sodium carbonate at 30 ° C at a spray pressure of 0.15 MPa for the shortest development time. 4 times, dissolve and remove the unhardened area. Thereafter, heat treatment (post-baking) was carried out at 15 ° C for 1 hour, and further exposure was performed by an ultrahigh pressure mercury lamp at 1,000 ml/cm 2 to form a solder resist layer. The TCT test was carried out using the test sample formed as described above at -65 ° C (5 minutes) to 150 ° C (5 minutes). After the test, the number of pit patterns in which cracks were generated from the contact portion between the pit pattern and the copper pattern was counted, and the number of cycles in which the crack generation ratio was 10% with respect to the total number of the pit patterns was calculated. &lt;Insulation reliability (HAST test)&gt;

A comb-shaped substrate having a copper thickness of 15 μm and L/S = 25/x 1×1/25 μm was used as a substrate. The surface of the photosensitive layer of the laminate produced in the same manner as the laminate was subjected to an optimum exposure amount by a parallel exposure machine. After full exposure, after standing at room temperature for 1 minute, the support is peeled off from the photosensitive laminate, and the entire surface of the photosensitive layer on the copper-clad laminate is 3 (TC 1% by mass aqueous sodium carbonate solution is sprayed) Pressing 0.1 5 MPa spray development for 4 times of the shortest development time, dissolving and removing the unhardened area. Thereafter, heat treatment (post-baking) at 150 ° C for 1 hour, further by ultra-high pressure mercury lamp at 1,000 m / cm 2 Full exposure, formation of a solder resist layer. Using the test sample formed as described above, the HAST test was carried out under the conditions of 1 3.(TC -58 - 201211691 /85%/30V/200 hours. [Evaluation Criteria] ◎: No short circuit.晶: Although no short circuit was observed, dendrites were slightly generated from the anode wiring. Δ: Although no short circuit was observed, dendrites were generated from the anode wiring. X: There was a short circuit. (Example 2) In Example 1 In addition to the polyurethane resin U i of Synthesis Example 1. A laminate was produced in the same manner as in Example 1 except that the polyurethane resin U2 solution of Synthesis Example 2 was used. The obtained laminate was subjected to the minimum opening diameter, TCT resistance, and insulation in the same manner as in Example 1. Evaluation of reliability. The results are shown in Table 1. (Example 3) In Example 1, except that the polyurethane resin ui solution of Synthesis Example 1 was replaced with the polyurethane resin U3 solution of Synthesis Example 3. In the same manner as in Example 1, a laminate was produced in the same manner as in Example 1. The minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 4) In the same manner as in Example 1, except that the polyurethane resin U i solution of Synthesis Example 1 was replaced with the polyurethane resin U 4 solution of Synthesis Example 4, the same procedure as in Example 1 was carried out. The laminate obtained was evaluated for the minimum opening diameter -59 - 201211691, TCT resistance, and insulation reliability in the same manner as in Example 1. The results are shown in Table 1. (Example 5) In Example 1, 'In addition to the synthetic urethane The resin ui solution was produced in the same manner as in Example 1 except that the resin ui solution was replaced with the polyurethane resin U5 solution of Synthesis Example 5. The obtained laminate body was subjected to the minimum opening diameter and TCT in the same manner as in Example 1. Evaluation of the resistance and the reliability of the insulation. The results are shown in Table 1. (Example 6) In Example 1, except that the polyurethane resin of Synthesis Example 1 was replaced with a solution as the polyamic acid of Synthesis Example 6. In the same manner as in Example 1, except that the ester resin U6 solution was used, a laminate was produced. The laminate obtained was evaluated for minimum opening diameter, TCT resistance, and insulation reliability in the same manner as in Example 1. The results are shown in the table [. (Example 7) In the same manner as in Example 1, except that the polyester-based elastomer was replaced with a urethane-based elastomer (T-5205LL, manufactured by DIC Corporation), a laminate was produced. . With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. The results are shown in Table 1. ^ (Example 8) In the example 2, except that the polyester elastomer was replaced with a urethane-based elastomer (T-5205 LL, manufactured by DIC Corporation), 2 was carried out in the same manner to produce a laminate. -60-201211691 The obtained laminate, the implementation, the TCT resistance, and the insulation reliability (Example 9) In Example 3, except that the polyester elastomer (T-5205LL, DIC shares 3 was carried out in the same manner, The laminate was produced. The obtained laminate, the TCT resistance, and the insulation reliability (Example 10) In Example 4, except for the Polycarbonate (T-5 205 LL, DIC shares 4 were similarly The laminate was produced, and the obtained laminate, the TCT resistance, and the insulation reliability (Example 11). In Example 5, except for the polyester elastomer (T-5205LL, DIC shares were similarly 5) The layered body was produced, and the obtained laminate, the TCT resistance, and the insulation reliability (Example 12) were the same as in Example 6 except that the polymerized elastomer (T-5205LL, DIC shares was the same as in Example 1). The minimum opening diameter was evaluated in the same manner. The results are shown in Table 1. The minimum opening diameter evaluation was performed in the same manner as in Example 1 except that the elastomer was replaced by the urethane-based company. The results are shown in Table 1. Elastomeric elastomer is replaced by a carbamate limited company The evaluation of the minimum opening diameter was carried out in the same manner as in Example 1. The results are shown in Table 1. The i-based elastomer was replaced by the same procedure as in Example 1 except that the i-based elastomer was replaced by the urethane-based company. The minimum opening diameter was evaluated. The results are shown in Table 1. The laminate was produced in the same manner as in Example-61 to 201211691, except that the lanthanide elastomer was replaced by the urethane-based company. Evaluation of the obtained laminate, Example 1, TCT resistance, and insulation reliability (Example 13) In Example 1, except that the synthesis example was a styrene elastomer (AS APRENE T-System) The laminate obtained in the same manner as in Example 1 was evaluated in the same manner as in Example 1, TCT resistance, and insulation reliability (Example 14). In Example 1, except that the synthesis example was an olefin-based elastomer. The same procedure as in Example 1 was carried out except for the body (BAC-45, Osaka), and the obtained laminate was evaluated in Example 1, TCT resistance, and insulation reliability (Example 15). The laminate obtained in the same manner as in Example 1 except that the synthesis example was a polyoxynene elastomer (X22-9002, manufactured by Shinshin Co., Ltd.), and Example 1, TCT resistance, and insulation. Evaluation of Reliability (Example 16) In Example 1, except that the minimum opening diameter was similarly performed in the synthesis example. The results are shown in Table 1. 7 Synthetic Polyester Elastomers For the 4 1 2, Asahi Kasei Co., Ltd. is a limited company to manufacture laminates. The minimum opening diameter is also performed in the same manner. The results are shown in Table 1. 7 Synthetic Polyester Elastomers are manufactured by Die Chemical Co., Ltd. to manufacture laminates. The minimum opening diameter is also performed in the same manner. The results are shown in Table 1. 7 Synthetic Polyester Elastomers for the manufacture of laminates for g Silicon Co., Ltd. The minimum opening diameter is also performed in the same manner. The results are shown in Table 1. The synthetic polyester elastomer was produced in the same manner as in Example 1 except that the acrylic elastomer (LA-2250, manufactured by Kuraray Co., Ltd.) was used to produce a laminate. With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. The results are shown in Table 1. (Example 1 7) In the example 1, except that the polyester elastomer synthesized in Synthesis Example 7 was replaced by a polyamine-based elastomer (TPAE-6 17 or manufactured by Fuji Chemical Co., Ltd.), 1 was carried out in the same manner to produce a laminate. With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. The results are shown in Table 1. (Example 18) A laminate was produced in the same manner as in Example 1 except that ruthenium oxide was replaced by untreated ruthenium oxide (SO-C 2 , manufactured by Admatech Co., Ltd.). With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. Show the results on the table! . (Example 19) Example 1 was carried out in the same manner as in Example 1 except that cerium oxide was replaced by untreated cerium oxide (S0_C1 'average particle diameter 〇·2//m manufactured by Admatech Co., Ltd.). Make a laminate. The obtained laminate body was evaluated in the same manner as in Example 1 in terms of minimum opening diameter, TCT resistance, and insulation reliability. The results are shown in Table 1. (Example 20) -63-201211691 In the same manner as in Example 1, except that cerium oxide was replaced by untreated cerium oxide (UFP-80, manufactured by DENKA Co., Ltd., average particle diameter: 40 nm). , manufacturing laminates. With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. The results are shown in Table 1. (Example 21) A laminate obtained by producing a laminate in the same manner as in Example 1 except that the cerium oxide treated with methacrylate decane was not contained in Example 1, and Example 1 The evaluation of the minimum opening diameter, TCT resistance, and insulation reliability was performed in the same manner. The results are shown in Table 1. (Comparative Example 1) In the first embodiment, except that the polyurethane resin U1 of Synthesis Example 1 was replaced by an acid-modified epoxy acrylate resin (ZFR-1401H, manufactured by Nippon Kayaku Co., Ltd.) The laminate was produced in the same manner as in Example 1. With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. The results are shown in Table 1. (Comparative Example 2) In Example 7, except that the polyurethane resin U1 of Synthesis Example 1 was replaced by an acid-modified epoxy acrylate resin (ZFR-1401H, manufactured by Nippon Kayaku Co., Ltd.) The laminate was produced in the same manner as in Example 1. -64-201211691 The evaluation of the minimum opening diameter, the TCT resistance, and the insulation reliability was carried out in the same manner as in the first embodiment. The results are shown in Table 1. (Comparative Example 3) In the first embodiment, a laminate was produced in the same manner as in Example 1 except that the elastomer was removed. With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. The results are shown in Table 1. (Comparative Example 4) In Example 4, a laminate was produced in the same manner as in Example 1 except that the elastomer was removed. With respect to the obtained laminate, the minimum opening diameter, the TCT resistance, and the insulation reliability were evaluated in the same manner as in the first embodiment. The results are shown in Table 1. -65- 201211691 [Table 1] Minimum opening diameter TCT test Insulation reliability Acid value Crosslinking density Example 1 60 1350 ◎ 70 1.5 Example 2 65 1300 ◎ 65 1.26 Example 3 55 1020 〇 45 0.9 Example 4 65 1350 ◎ 75 1.3 Example 5 60 1100 Δ 90 1.1 Example 6 60 1000 〇 60 0.8 Example 7 60 1420 ◎ 70 1.5 Example 8 55 1350 ◎ 65 1.26 Example 9 65 1030 〇 45 0.9 Example 10 65 1400 ◎ 75 1.3 Example 11 60 1100 Δ 90 1.1 Example 12 60 1050 〇 60 0.8 Example 13 65 1010 ◎ 70 1.5 Example 14 65 1100 ◎ 70 1.5 Example 15 65 1050 ◎ 70 1.5 Example 16 65 1020 ◎ 70 1.5 Implementation Example 17 65 1020 ◎ 70 1.5 Example 18 60 1300 ◎ 70 1.5 Example 19 65 1350 ◎ 70 1.5 Example 20 65 990 〇 70 1.5 Example 21 55 1020 〇 70 1.5 Comparative Example 1 60 550 X 100 - Comparative Example 2 65 600 X 100 - Comparative Example 3 60 850 ◎ 70 1.5 Comparative Example 4 60 900 ◎ 75 1.3 (In Table 1, the unit of acid value is mgKOH/g, and the unit of crosslinking density is mol/m3. Titration method.) [Industry use can be Resistance] The photosensitive composition of the present invention based on the minimum opening diameter, TCT resistance, and insulation reliability is excellent, it can be suitably used for solder resist. -66 - 201211691 The photosensitive composition of the present invention has improved TCT resistance and insulation reliability, and can form a highly accurate permanent pattern efficiently, so that it can be suitably used for BGA (Ball Grid IJ), CSP (Crystal) Manufacturing of semiconductor liquid crystal structural members such as semiconductor package formation, color filter, column, rib, spacer, and partition wall, such as square scale structure) and TCP (tape-wrap package), full-image, micro-machine, and proofing ( In particular, it can be suitably used for the formation of a semiconductor package such as a BGA (Ball Grid Array), a CSP (Crystal Scale Package), or a TCP (Tape Tape Package) for the permanent pattern formation of a printed substrate. Since the pattern forming method of the present invention uses the photosensitive composition described above, it can be suitably used for forming a semiconductor package such as a BGA (Ball Grid Array), a CSP (Crystal Scale Package), or a TCP (Tape Tape Package). Manufacturing of a liquid crystal structural member such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar, a rib, a spacer, and a partition, and a whole image, a micromachine, The manufacture of proofs, etc., can be suitably used for the formation of a semiconductor package such as permanent pattern formation of a printed substrate, BGA (Ball Grid Array), CSP (Crystal Scale Mounting), and TCP (Tape Tape Package). [Simple description of the diagram].

/INN [Description of main component symbols] and. J\\\ -67-

Claims (1)

201211691 VII. Patent Application Range: 1 . A photosensitive composition comprising at least a polyurethane resin, an elastomer, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. The photosensitive composition of claim 1, wherein the polyurethane resin is obtained by reacting a diisocyanate, a carboxylic acid having at least two hydroxyl groups, and a diol having no carboxylic acid group. 3. The photosensitive composition of claim 1, wherein the elastic system is derived from a styrene-based elastomer, an olefin-based elastomer, an urethane-based elastomer, a polyester-based elastomer, and a polyamine-based elastomer. At least one of a body, an acrylic elastomer, and a polyoxynene elastomer. 4. The photosensitive composition of claim 1, wherein the polyurethane resin has an acid value of from 20 m£KOH/g to 120 mgKOH/g. 5 _ The photosensitive composition of the first application of the patent scope, wherein the crosslinking density is 0.05 mol/m 3 to 3.0 mol/m 3 . 6. The photosensitive composition of claim 1, further comprising a coating coated with a decane coupling agent. 7. The photosensitive composition of claim 1, wherein the polyurethane resin is represented by the following formula (1); Thief 1) However, in the general formula (1), the 'η series is not an integer from 1 to 50; a, b' c, d, and e each represent the mass ratio of each comonomer of the polyurethane, The a system indicates that 20 to 70, b indicates 〇 20, c indicates 0 to 40, d indicates -68 - 201211691 indicates 0 to 40, and e indicates 0 to 30. 8. A photosensitive laminate comprising a photosensitive layer comprising a photosensitive composition containing at least a polyurethane resin, an elastomer, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent on a substrate . A permanent pattern forming method comprising at least a step of exposing a photosensitive layer by containing at least a polyurethane resin, an elastomer, a polymerizable compound, a photopolymerization initiator, and thermal crosslinking The formation of the photosensitive composition of the agent. 10. A printed substrate formed by a permanent pattern forming method comprising at least a step of exposing a photosensitive layer, the photosensitive layer comprising at least a polyurethane resin, an elastomer, and a polymerizable property A compound, a photopolymerization initiator, and a photosensitive composition of a thermal crosslinking agent. -69- 201211691 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the symbol of the representative figure: 〇 J\\\ V. If there is a chemical formula in this case, please disclose the chemistry that best shows the characteristics of the invention.