TW201237101A - Resin composition, cured object, resin film, and wiring board - Google Patents

Abstract

Provided is a resin composition with which cure warpage can be mitigated and which has excellent heat resistance and is suitable for use as a material for the surface-protective film or interlayer dielectric of a semiconductor element or for a protective dielectric, interlayer dielectric, or the like for printed wiring boards. Also provided are a resin film obtained using the resin composition and a wiring board obtained using the composition or film. This resin composition is characterized by comprising (A) a polymer, (B) a polyfunctional hydroxylated compound having two or more hydroxy groups, and (C) a polyfunctional crosslinking compound having two or more crosslinking functional groups which form crosslinks between the crosslinking compound and the polymer and/or polyfunctional hydroxylated compound, the polyfunctional crosslinking compound being capable of forming three-dimensional crosslinks between the crosslinking compound and the polymer and/or polyfunctional hydroxylated compound.

Description

201237101 6. EMBODIMENT OF THE INVENTION The present invention relates to a material which can be used as a surface protective film for a semiconductor element, an interlayer insulating film, a semiconductor package substrate, a bonding sheet, and a protective insulating film for a printed wiring board. As the resin composition, a cured product of a resin composition, a resin film of a resin composition, and a wiring board using the same are used. [Prior Art] As a material of a surface protective film, an interlayer insulating film, and a protective insulating film for a printed wiring board of a semiconductor device, a polyilylimine-based resin composition excellent in heat-generating property is used. In particular, when the polyimine-based resin composition is used as an insulating material for a flexible printed wiring board, it is required to have less warpage after hardening in addition to heat resistance. A polyamidene-based ink containing a vinegar-end polymer and an amine-terminated oligomer is proposed as a polyimine-based resin composition which is excellent in heat resistance and can reduce warpage after curing (for example, refer to Patent Document 1) ). The polyimide-based ink described in Patent Document 1 is applied to a flexible wiring circuit and then heat-treated at a temperature of 250 ° C or higher to imidize the ruthenium. In the brewing imidization step, the shrinkage caused by the de-solvent or the imidization reaction of the oligomerization of the oligomer causes shrinkage of the formed polyimide resin. Therefore, the suppression of the buckling is not necessarily sufficient. Also, in the case where the circuit material uses copper swash, there are also the following problems: due to 250. (: The above heat treatment causes the carboxyl group to react with the wiring material, thereby causing oxidation of the wiring material. Also, 'the yttrium imidation at low temperature is developed, and the hardening can be reduced. 158118.doc 201237101 An imine precursor. Examples of such a polyimide precursor include a non-polyoxynene polyimine precursor using a daunic acid diamine (for example, refer to Patent Document 2), or a diamine. A polyoxynitride-based polyimine precursor which is used as a diamine component (for example, refer to Patent Document 3 and Patent Document 4). [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Application Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] However, the polyimine precursor described in Patent Document 2 has a polyamic acid structure derived from a diamine derived from a hospital group, and a polycondensation derived from an aromatic diamine. The quinone imine structure acts as a structural unit. When the polyimine-based resin composition is used in an insulating material of a flexible printed wiring board, there is a problem in that the polyamidene derived from the aromatic diamine shrinks and does not necessarily sufficiently inhibit hardening. In the case of the polyimine precursor described in Patent Document 3 and Patent Document 4, the polyoxyimide precursor is a polyamidene resin composition. When it is applied to a circuit board to imidize it to form a protective film of the circuit, in the subsequent prepreg or bonding step, the polyoxygenated portion is segregated on the surface to make the surface of the protective film low. The surface tension and the high repulsion 158118.doc 201237101 are water-based, and thus there is a case where they are repelled from the adhesive component. Therefore, there is a problem in that the adhesive force between the protective film and the adhesive sheet is insufficient, and sufficient performance is not necessarily obtained as a protective film. In view of the above, an object of the present invention is to provide a surface protective film, an interlayer insulating film, a printed wiring board which can be used as a semiconductor element, which is excellent in warpage and heat resistance at the time of hardening. A resin composition which is suitable for use as a material for protecting an insulating film, such as an interlayer insulating film, is a resin film of a resin composition, and a wiring board using the same. [Technical means for solving the problem] The resin composition of the present invention is characterized in that A polyfunctional hydroxyl group-containing compound having (A) a polymer compound and (B) having two or more hydroxyl groups, and having two or more crosslinks formed between the polymer compound and/or the polyfunctional hydroxyl group-containing compound The polyfunctional crosslinkable compound of the functional group and the polyfunctional crosslinkable compound can form a three-dimensional crosslink between the above polymer compound and/or the above polyfunctional hydroxyl group-containing compound. In the resin composition of the invention, the polymer compound has a quinone imine group and/or a guanamine group, and the three-dimensional crosslinks include c=mercapto group and/or NH group. In the resin composition of the present invention, the polyfunctional permeation-containing compound and/or the polyfunctional crosslinkable compound is preferably a trifunctional or higher functional group. Preferably, in the resin composition of the present invention, the polymer compound has a hydroxyl group and/or a carboxyl group. Preferably, in the resin composition of the present invention, the polyfunctional hydroxyl group-containing compound comprises a phenol-modified polyfluorene selected from the two ends, polybutadiene 158118.doc 201237101, and hydrogenated polybutadiene. At least one of a polyol and a polycarbonate polyol. It is preferred that in the resin composition of the present invention, the aforementioned polyfunctional hydroxyl group-containing compound has an aliphatic structure. Preferably, in the resin composition of the present invention, the polyfunctional hydroxyl group-containing compound is a polycarbonate polyol. In the resin composition of the present invention, a polyfunctional isocyanuric acid compound having two or more isocyanate groups is preferably contained as the polyfunctional crosslinking compound. Preferably, in the resin composition of the present invention, the polyfunctional crosslinkable compound contains two or more blocked isocyanate groups. Preferably, in the resin composition of the present invention, the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound and the molar ratio hydroxyl group/crosslinking of the parent functional group contained in the polyfunctional crosslinkable compound are preferably Sex functional group ~ 丄. In the resin composition of the present invention, the content of the polyfunctional permeation-containing compound is from 5 parts by mass to 60 parts by mass based on the mass% of the above-mentioned molecular compound. In the resin composition of the present invention, the content of the polyfunctional crosslinkable compound is from 5 parts by mass to 60 parts by mass based on the mass of the polymer compound (10). It is preferred that in the resin composition of the present invention, the polyfunctional content-containing compound has a number average molecular weight of 500 Å. Preferably, in the resin composition of the present invention, the polymer compound has a repeating structure represented by the following formula (1); ϋ 158118.doc 201237101 [Chemical Formula 1] Formula (1)

(In the formula (1), Y1 represents a divalent organic group, Z represents an tetravalent organic group; and a represents an integer of 1 to 50). Preferably, in the resin composition of the present invention, the polymer compound is a polyienimine. Preferably, in the resin composition of the present invention, the polymer compound has a repeating structure represented by the following formula (2); [Chemical Formula 2] Formula (2)

(In the formula (2), Z1 and Z2 represent a tetravalent organic group, and Y!, Y2, Y3, 丫4 and Ys each independently represent an alkylene group having a carbon number of 5 and a branched alkyl group; b, C and d each independently represent an "integer". Preferably, in the resin composition of the present invention, the polymer compound has a polyimine structure represented by the following formula (3) and The general formula (4) is 158118.doc 201237101 [Chemical 3] The polyhexamic acid structure of the general formula (3) = as a repeating structural unit

(In the formulas (3) and (4), m, mRlQ R", R13 and r14 each independently represent a hydrogen atom or an organic group having a carbon number of 24 carbon atoms, R3, R6, R9, Ri2& RM independently represents an organic group having a number of 1 to a carbon number of 4, and 4 to independently represent an integer of 100 or more; R, 6 represents a tetravalent organic group, and Ri7 represents the present number. It is an organic group having 1 to a carbon number of 90 valence. Preferably, in the resin composition of the present invention, the diamine component constituting the polyimine represented by the above-mentioned (3) includes a diamine represented by the following formula; (5) 1581I8.doc -8 - 201237101 h2n 1=) 'Ri, R2, R4, R5, ~, mR, ^ «:!Rl:" ^ n P is independent of 0 or more, and Satisfies 1 g (m+n+p)g 30). Preferably, in the resin composition of the present invention, the polymerized phase-structure represented by the following formula (6) is a repeating unit; [Chemical Formula 5] Formula (6) 4 ο ΟΛ-ΪΟ f 3 s 4Η, ?1-I^-R1 资?4^-r. /Γ> ΟΑ to I/O ·Ν 3 6 4 0-2 1ψη

Η"··01 ffcro-αΓ In the formula (9), R, r2, r4, Rs, R7, &, Ri. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The organic group, m, η, and P each independently represent an integer of 0 or more and 30 or less. R16 represents a tetravalent organic group 'Rn represents a divalent diorgano group having a carbon number of 1 to a carbon number of 90, A, B, and C. Indicates the mol% of each unit, and is full of 0.10S (A+B)/(A+B+c)S 0.85). Preferably, in the resin composition of the present invention, the polymer compound 4 has a poly(indenylene) structure represented by the following formula (7) and a formula (8): 158118.doc 201237101 Polylysine structure as a structural unit; [Chemical 6] General formula (7)

General formula (8)

(In the formulae (7) and (8), Z3 and Z4 are derived from the tetravalent organic group of the carboxylic acid dianhydride of the following formula (9), and may be the same or τ π not four. J is different; Ri _ has a carbon number of 1 to an organic group having a carbon number of 30, Rl9 represents ^ an sigh of 1 to an organic group having a carbon number of 30, and e represents an integer of 1 or more and 20 or less) [ 7] General formula (9)

Preferably, in the resin composition of the present invention, (D) a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, (E) light • 10·158118.doc

S 201237101 Polymerization initiator. It is preferable that the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds in the resin composition of the present invention contains a (meth) acrylate having three or more double bonds. Compound. Preferably, in the resin composition of the present invention, the (fluorenyl) acrylate compound having three or more double bonds includes a compound represented by the following formula (1〇); (10)

(In the formula (10), R2〇 represents a hydrogen atom or a fluorenyl group, and plural plurals each independently represent a carbon number of 2 to an alkyl group having a carbon number of 5, which may be the same or different; f is 1 to 10 The integer). It is preferred that the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds in the resin composition of the present invention contains a (fluorenyl) acrylate compound having two double bonds. And a (fluorenyl) acrylate compound having three or more double bonds. It is preferred to contain (F) a phosphorus compound in the resin composition of the present invention.

158118.doc 201237101 The article 'comprising a phosphate compound and/or a phosphazene compound. The resin composition of the present invention is characterized in that the interlayer insulation resistance in the insulation reliability test at a temperature of 85 ° C, a humidity of 85%, and an hour is 1 〇 9 or more '120 ° C to 220 ° C The film has a viscosity of 5,000 Pa·s to 100,000 Pa.s, and an elastic region having an elongation of less than 20% and a plastic region having an elongation of 5% or more. The thickness of the interlayer insulating layer is 4 μm or less. The cured product of the present invention is characterized in that the resin composition is heated at 100 ° C to 130 ° C for 5 minutes to 60 minutes, and then at 160. (:~200. Obtained by heating under the underarm for 15 minutes to 60 minutes. The resin film of the present invention is characterized by comprising: a substrate, and the above resin composition on the substrate. In the resin film of the invention, the substrate is a carrier film. Preferably, the resin film of the present invention comprises a cover film provided on the resin composition. Preferably, in the resin film of the present invention, The substrate-based copper foil is characterized in that the wiring board of the present invention includes the resin composition provided with a wiring and covering the wiring. [Effects of the Invention] Provided by the present invention It is suitable for use in materials such as a surface protective film for a semiconductor element, an interlayer insulating film, a protective insulating film for a printed wiring board, and an interlayer insulating film, which can be used for the purpose of reducing the warpage at the time of hardening, and is excellent in heat resistance. A resin film using a resin composition and a wiring board using the same. [Embodiment] 158118.doc

12-201237101 In recent years, with the increase in the functionality and weight of electronic devices such as mobile phones, the flexibility of flexible printed circuit boards used in various electronic devices has been increasing. In the step of producing a flexible printed circuit board, an epoxy resin or a polyimide resin is used. However, when an epoxy resin is used as the protective film, it is not always necessary to sufficiently reduce the thickness of the flexible printed circuit board. It must have high insulation reliability or softness, low repulsion, and the epoxy resin is reactive, so it lacks storage stability. Further, in the case of using the prior polyilylimine-based resin, the polyimide resin having a reduced warpage or heat resistance is expensive, and it is desired to obtain warpage of the cured product with yttrium. Reducing or heat-resistant resin bismuth. The inventors of the present invention have focused on a polyfunctional crosslinkable compound capable of forming a three-dimensional crosslink between a polymer compound or a polyfunctional hydroxyl group-containing compound. Further, the present inventors have conceived that a polyfunctional crosslinkable compound and a polyfunctional hydroxyl group are provided by heating a resin composition containing a polymer compound and/or a polyfunctional permeation-containing compound and a polyfunctional crosslinkable compound. The 3-dimensional crosslinks formed between the compounds form a 3-dimensional network. Furthermore, the inventors of the present invention have found that a resin composition capable of reducing the interest in curing and having excellent heat resistance can be realized by the three-dimensional network, and the present invention has been completed. That is, the resin composition of the present invention contains (A) a polymer compound, (B) a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups, and (c) a polymer compound and/or a polyfunctional hydroxyl group-containing compound. a polyfunctional crosslinkable compound having two or more crosslinkable functional groups, and a polyfunctional crosslinkable compound may be formed between a polymer compound and/or a polyfunctional hydroxyl group-containing compound 158118.doc •13-201237101 3D cross-linking. In the resin composition, a 3-dimensional crosslink is formed between the crosslinkable functional group of the polyfunctional crosslinkable compound and the hydroxyl group of the polyfunctional hydroxyl-containing compound by heating, and the 3D crosslinks form 3 Dimensional mesh. Thereby, the shrinkage of the polymer compound during curing of the resin composition can be suppressed, and the compatibility between the polymer compound, the polyfunctional hydroxyl group-containing compound, and the polyfunctional crosslinkable compound can be improved, and the result can be achieved by reducing the warpage at the time of hardening. A resin composition which is excellent in heat resistance and which can be suitably used as a surface protective film for a semiconductor element, an interlayer insulating film, a protective insulating film for a printed wiring board, and an interlayer insulating film, is preferably used in the present invention. In the resin composition of the invention, the polymer compound has a quinone imine group and/or a guanamine group, and the 3-dimensional crosslink formed between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound includes a thiol group and / or NH base. Hydrogen bond-based interaction between the c=mercapto group and/or the NH group contained in the three-dimensional crosslink and the quinone imine group and/or the mercaptoamine group of the polymer compound by the constitution Therefore, the compatibility between the polymer compound, the polyfunctional permeation-containing compound, and the polyfunctional crosslinkable compound is further improved. In this way, the curvature of the hardening can be further reduced, and the financial property is further improved. In the resin composition of the present invention, the polymer compound, the polyfunctional hydroxyl group-containing compound, and the polyfunctional crosslinkable compound are polymerized with a polymer compound and/or a polyfunctional hydroxyl group-containing compound by heating or the like. When a three-dimensional crosslinker is formed between the linked compounds, various compounds can be used in combination within the range of the effects of the present invention. Hereinafter, the aspect of the resin composition of the present invention will be described in detail. -14· 158118.doc

S 201237101 (first aspect) In the resin composition of the first aspect of the invention, the polyfunctional permeation-containing compound and/or the polyfunctional crosslinkable compound is a trifunctional or higher functional group, as described above, and if the polyfunctional content is When at least one of the base compound or the polyfunctional crosslinkable compound is a trifunctional or higher functional group, a plurality of crosslinkable functional groups (for example, isocyanate groups, a plurality of hydroxyl groups of the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound, The cross-linking reaction between the oxazoline groups forms a 3-dimensional crosslink comprising a plurality of C=0 groups and/or NH groups, so that a 3-dimensional network can be formed. In this case, the three-dimensional network between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound which is not formed by the polymer compound can suppress the shrinkage of the polymer compound and exhibit sufficient Reduced warpage and excellent heat resistance. In the resin composition of the first aspect of the present invention, the shrinkage of the polymer compound is suppressed by the three-dimensional network formed between the polyfunctional permeation-containing compound and the polyfunctional crosslinkable compound, and thus The effect of the present invention can be achieved without being limited to the molecular structure of the polymer compound. Therefore, for example, even when an inexpensive polymer compound having a complicated molecular structure is used, warpage at the time of curing of the resin composition can be reduced, and excellent heat resistance can be exhibited. (Second aspect) In the resin composition of the second aspect of the invention, the polymer compound has a hydroxyl group and/or a carboxyl group. As described above, since the polymer compound has any one of a hydroxyl group and a carboxyl group, a crosslinkable energy group of a hydroxyl group and/or a carboxyl group of the polymer compound and a polyfunctional crosslinkable compound (for example, isocyanic acid 158118.doc) Crosslinking bonds are also formed between -15-201237101 base, oxazoline group). Thereby, a three-dimensional network via a south molecular compound is formed between the polymer compound, the polyfunctional hydroxyl-containing compound, and the polyfunctional crosslinkable compound, so that the polymer compound, the multi-B month b 3 radical compound, and the polyfunctional compound The compatibility of the crosslinkable compound is improved, and the shrinkage of the polymer compound can be suppressed, and in particular, the warpage of the resin composition at the time of curing can be reduced, and excellent heat resistance can be exhibited. In the resin composition of the second aspect of the invention, the three-dimensional cross-linking is formed by the polymer compound. Therefore, at least one of the polyfunctional hydroxyl group-containing compound and the polyfunctional cross-linking compound is trifunctional or more. A 3-dimensional mesh can be formed. Further, since a three-dimensional network via a polymer compound is formed, the compatibility of the local molecular compound with the polyfunctional permeation-containing compound and the polyfunctional crosslinkable compound is further improved. Therefore, even when a polymer compound having low compatibility with a polyfunctional permeation-containing compound and a polyfunctional crosslinkable compound is used, 'a practical use can be obtained in a manufacturing step of a flexible printed wiring board or the like. Resin composition. In the following, each of the constituent elements will be described in detail. (A) Polymer compound As the polymer compound, various polymer compounds can be used within the range in which the effects of the present invention are exerted. Examples of the polymer compound include polyamidamine, polyamidamine, polylysine, and polyamidene which are imidized by hydrazine. Further, in the present invention, the term "polyimine" refers to a polyamidene precursor comprising a part of polylysine which is imidized by hydrazine, and all of the polyamidino acid are imidized by imidization. The two kinds of polyimine. In the resin composition of the first aspect, as a polymer compound, it can be used for •16-158118.doc

S 201237101 The polymer structure is not limited, and various polymer compounds such as the above polyimine are used. Among these, polycarbonitrile is preferably used as the polymer compound from the viewpoint of heat resistance and moisture absorption resistance. In the resin composition of the second aspect, 'as a south molecular compound, it is used for having a hydroxyl group and/or a carboxyl group in a molecular chain. As such a polymer compound, polylysine or a polyimine having a hydroxyl group or a carboxyl group in a molecular chain can be used. Polyimine can be obtained by reacting an acid dianhydride with a diamine. In the case of using a polyimine as a molecular compound, for example, a polyimine having a polyimine structure as a repeating structural unit may be used, or a polyimine structure and a poly-proline structure may be used. Repeating the structural unit of the polyimine. As the polymer compound, for example, a repeating structural unit represented by the following formula (1) can be used. [Chemical Formula 9] Formula (1)

(In the formula (1), Y1 represents a divalent organic group, & represents a tetravalent organic group. & represents an integer of 1 to 50.) 158118.doc 201237101 Further, as a polymer compound, a base can be obtained. _Diamine = the obtained non-(tetra) fluorene imine, and the polyamine oxide polyimine obtained by reacting diamine (tetra) = with acid anhydride can also be used. As the polymer compound, those having a repeating structure represented by the following formula (7) are preferably used. In the polymer compound, the molecular chain is imparted with flexibility by imparting oxygen oxyalkylene group, and the polymer compound: solubility is improved. w [Chemical 10] General formula (2)

(In the formula (2), 'Z丨 and Z2 represent a tetravalent organic group, and Υι, γ2, γ3, \ and Υ5 each independently represent an alkylene group having a carbon number of 5 and a branched alkyl group. And c and d each independently represent an integer of 丨~5〇.) Further, as the polymer compound, it is preferred to use a polyimine structure having the following general formula (3) and the following formula ( 4) The polyamic acid structure represented as a repeating structural unit. In the polymer compound, an alkyl ether structure is contained in the polyanilin structure, and the polyglycolic acid structure is contained. Therefore, the molecular chain is imparted with flexibility without impairing molecular weight stability, and thus development stability is improved. Further, in the polymer compound, a crosslinkable functional group (for example, an isocyanate group or an oxazoline group) of a polycarboxyl acid structure-containing carboxyl group and a polyfunctional crosslinkable compound contained in the following formula (4); The reaction thus forms a crosslink between the molecular compound and the polyfunctional crosslinkable compound at a high 158118.doc δ -18·* 201237101, which further suppresses the shrinkage of the polyimine at the time of hardening. Further, since the carboxyl group reacts with the crosslinkable functional group, the sulfhydryl group in the cured product is reduced, so that a cured product excellent in insulating properties can be obtained. • [化11]式通J^LRefRS /ί^[\ Cf-R3lR2 .ΙΎ

4V 4 — R—RIR

< ΟΗΛ YMO N 3 - 5 4 Formula (4) -Ri7*N-^ - (In the formulas (3) and (4), R!, R2, R4, r5, &, &,

Ru, Ru and RM each independently represent a hydrogen atom or a monovalent organic group having a carbon number of 丨 to a carbon number of 2 Å. R3, Re R9, Rl2 & Rls each independently represent a tetravalent organic group having a carbon number of 1 to a carbon number of 20, and m, n, and p independently represent an integer of 100 or less. The base represents an organic group having a carbon number of 1 to a carbon number of 90. Further, the polymer compound preferably contains a diamine represented by the following formula (5) as a monoamine component constituting the polymer compound represented by the above formula (3). 158118.doc -19- 201237101 [Chemical 12J General formula (5) ?13 ?15^NH2 into 4

K (In the formula (5), Ri, &, &, heart, r~ respectively represent a hydrogen atom or a carbon number M 8^°'R", a machine base. R3, R6, R-Rl5 respectively The number is 2. The organic group of the 4th valence, m,: the ground indicates that the carbon number is an integer of 1 to 1, and satisfies one coffee and two independently. The above 3. The second table is used as the polymer compound'. It has the following structure: (6) The structure represented as a repeating unit. I encounter - [Chemical 13] General formula (6)

Sound R«->-R»

ο .2 1 91-lflR. ψ R*_yR*

R8 ' Rio ' R, Ri R. (in the formula (6), R, R2, r4, : 4: independently represent a hydrogen atom or a carbon number of 1 to a carbon number of the divalent right ^3, R6, R9, and Rl^Rl5 represent an organic group having a carbon number of 1 to a carbon number of 2 Å, and m, n, and P independently represent 整 above 3 〇 整 ^ 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 , , Money is i ~ carbon: machine base. A, B, C represent each unit..., and full. i〇s(a+b)/(a+b+c)s〇.85.) 158118.doc -20 201237101 In the polymer compound represented by the above formula (6), the alkyl ether structure in the molecular chain is increased by satisfying 0.10S (a+b)/(a+b + c). The molecular chain of the molecular compound is improved in flexibility, so that the warpage after hardening can be reduced. Further, by satisfying (A+B)/(A+B + C)s 0.85, the carboxyl group in the molecular chain is increased, thereby exhibiting solubility of the cured product with respect to the alkaline developing solution, and developability It is getting better. Further, as the polymer compound, it is preferred to use a polyaminic acid structure represented by the following formula (7) and a polyamic acid structure represented by the following formula (8) as a repeating structural unit. In the polymer compound, a polyoxyalkylene moiety is contained in the polyimine structure to impart a moderate flexibility to the polyimine structure. Therefore, the molecular chain of the polymer compound can be inhibited from shrinking, and the post-hardening warp can be suppressed. song. Further, since the polycyclic amino acid structure contains an aromatic ring, the molecular weight of the polyamic acid structure can be suppressed from decreasing i, and the storage stability of the resin composition and the development time stability of the dry film obtained from the resin composition are improved. . Further, since the polyienimine structure and the polystyrene structure contain a tetravalent organic group derived from tetrazoic acid dianhydride, the molecular chain is imparted with a moderate rigidity, and the heat resistance is improved to improve the insulation reliability. General formula (7)

158118.doc -21 - 201237101

In the formula (7) and the formula (8), Z3 and Z4 are derived from the tetravalent organic group of the carboxylic acid dianhydride represented by the following formula (9), and may be the same or not. R1 8 represents an organic group having a carbon number of 1 to a carbon number of 30, and Rm represents an organic group having a number of disks of 丨 to a carbon number of 30, and e represents an integer of 1 or more and 20 or less. 15] General formula (9)

Further, when the polymer compound represented by the above formula (7) and the polyphthalic acid structure represented by the above formula (8) are used as a repeating structural unit, the polymerization is carried out. The slow group contained in the structure of the proline is reacted with a crosslinkable functional group (for example, isocyanate group) of the polyfunctional crosslinkable compound. Thereby, the molecular compound is embedded in the three-dimensional network between the polyfunctional group-containing compound and the polyfunctional crosslinkable compound, and segregation to the surface of the cured product at the polyoxo site can be suppressed. Thereby, the reduction in surface tension and the expression of water repellency can be suppressed, so that even in the case of forming a protective film, a good adhesion is obtained. 158118.doc -22- 201237101 (B) Polyfunctional hydroxyl group-containing compound As the polyfunctional hydroxyl group-containing compound, a common polyfunctional hydroxyl group-containing compound can be used in the resin composition of the first aspect and the second aspect. When the polyfunctional group-containing compound is a compound having two or more hydroxyl groups in the molecular chain, various kinds of the mercapto group-containing compound can be used within the range in which the effects of the present invention are exerted. As the polyfunctional hydroxy compound, for example, various diols which are two-functional hydroxy group-containing compounds having two hydroxyl groups can be used, and various polyols having three or more groups can be used. In the above, from the viewpoint of forming a plurality of crosslinks between the polyfunctional permeation-containing compound and the polyfunctional crosslinkable compound (for example, a polyfunctional isocyanate or a polyfunctional barium compound), it is preferred to use A polyfunctional hydroxyl group-containing compound having three or more hydroxyl groups is used as the polyfunctional hydroxyl group-containing compound. As a multi-g-containing radical compound, from the viewpoint of improving the insulating property, it is preferred to contain a phenol-modified polyfluorene oxide, a polybutadiene polyol, a hydrogenated polybutadiene polyol, and a poly At least one of the carbonate polyols. Further, as the polyfunctional hydroxyl group-containing compound, those having an aliphatic structure are preferred. Thereby, the water resistance is improved and the elasticity is made low, so that the warpage can be reduced and the insulation reliability can be improved. From the above viewpoints, as the polyfunctional hydroxyl group-containing compound, preferred are the hydrogenated polybutadiene polyols and polycarbonate polyols in the above-exemplified specific examples, especially from the viewpoint of reducing warpage. A polycarbonate polyol can be preferably used. In the resin composition of the present invention, it is preferred that the content of the t 'polyfunctional transradical compound is from 5 parts by mass to 60 parts by mass relative to 100 parts by mass of the polyimine. The base compound is 5 parts by mass to 158118.doc •23·201237101. The above can form sufficient cross-linking between the polyfunctional crosslinkable compounds, and thus it becomes possible to reduce the warpage at the time of hardening. In addition, by making the polyfunctional base-based compound 60 parts by mass or less, the excess radical in the resin composition is reduced. Therefore, the insulation reliability after curing of the resin composition can be improved. Further, it is preferable that the content of the polyfunctional ketone-containing compound is 5 parts by mass to 3 parts by mass based on 100 parts by mass of the polyimine. As the polyfunctional hydroxyl group-containing compound, it is preferred to use a number average molecular weight of 500 to 3,000. Here, the number average molecular weight means the number average molecular weight of the molecular weight in terms of styrene measured by gel permeation chromatography. If the number average molecular weight of the polyfunctional hydroxyl group-containing compound is 5 Å or more, the resin composition becomes low in elasticity, so warpage can be reduced. In addition, when the number average molecular weight of the polyfunctional ketone-containing compound is 3 Å or less, the viscosity of the resin composition can be reduced, so that the embedding property in the wiring portion or the via portion of the wiring board is improved. Further, the number average molecular weight of the polyfunctional hydroxyl group-containing compound is preferably from 500 to 2,000 from the viewpoint of the low elasticity and viscosity of the resin composition. (C) Polyfunctional crosslinkable compound As the polyfunctional crosslinkable compound, a common polyfunctional crosslinkable compound can be used in the resin composition of the first aspect and the second aspect. When the polyfunctional crosslinkable compound has two or more crosslinkable functional groups, various polyfunctional crosslinkable compounds can be used within the range of the effects of the present invention. Here, the term "crosslinkable functional group" means a functional group which can form a crosslink bond between a hydroxyl group or a thiol group of a polymer compound and a hydroxyl group of a polyfunctional hydroxyl group-containing compound. Examples of the crosslinkable functional group include an isocyanate group, 158118.doc

S -24 - 201237101 ° 恶 ° Sitting on the Lin Keji, etc., but not limited to these. Further, as the polyfunctional crosslinkable compound, a bifunctional crosslinkable compound having two crosslinkable functional groups can be used. A crosslinkable compound having three or more crosslinkable functional groups can also be used. The polyfunctional crosslinkable compound ′ is, for example, a polyfunctional isocyanuric acid compound having two or more isocyanato groups or a polyfunctional oxazoline compound having two or more oxazoline groups. As the polyfunctional crosslinkable compound, a polyfunctional isocyanate compound containing two or more isocyanate groups is preferably used. According to this configuration, a three-dimensional network can be formed between the isocyanate group of the polyfunctional isocyanate and the mesogenic group of the polyfunctional hydroxyl group-containing compound via an amino phthalate bond, and is contained in the polymer compound. The interaction between the imino group and the guanamine group, or the hydroxyl group and the ketone group and the thiol group and the NH group contained in the amino phthalate structure are hydrogen bonds. Thereby, the low repulsive property of the resin composition can be improved, and moderate fluidity is exhibited in the resin composition due to the combination of the plasticity of the polymer compound and the elasticity of the resin composition. As a result, for example, the two physical properties (fluidity and viscosity) which are necessary for the case where the resin composition is used as the interlayer insulating film of the multilayer flexible printed wiring board can be realized at the same time, and thus can be used as interlayer insulation. In the case of having a polyfunctional isocyanate compound, if it has two or more isocyanate groups, various isocyanate compounds can be used in the range which has the effect of this invention. In the case where the resin composition material of the present invention is used as an interlayer insulating film such as a multilayer flexible wiring board, the resin composition is required to flow into the wiring portion or the through hole portion of the wiring board, and the other resin is required. The composition does not flow out from the end of the wiring board and is somewhat retained. The reason is that, in the pressing step under the pressure of high pressure 158118.doc -25 - 201237101, if the inflow into the through hole is attempted sufficiently, the resin composition usually flows out from the end portion of the wiring board, so that wiring exists. The thickness of the insulating layer at the end of the board i is thinned, resulting in a decrease in insulation. Therefore, for example, when a polyfunctional isocyanate is used as the polyfunctional crosslinkable compound in the above resin composition, the amine group formed by the isocyanate group of the polyfunctional isocyanate and the hydroxyl group of the polyfunctional hydroxyl group-containing compound The acid ester bond bonds the polyfunctional hydroxy compound to the polyfunctional isocyanate compound and produces a hydrogen bond interaction between the urethane structure and the polymer compound. Thereby, the fluidity necessary for the resin composition to flow into the opposite wiring portion and the insulation of the end portion of the wiring portion can be simultaneously achieved by the combination of the plasticity of the polymer compound and the elasticity of the resin composition. The thickness of the film prevents the resin composition from flowing out to a moderate viscosity necessary to prevent it. As a result, the resin composition is prevented from flowing out from the end portion of the wiring board, and the resin composition does not flow out from the end portion of the wiring board to some extent, so that very good embedding property can be achieved. Further, as the polyfunctional crosslinkable compound, a blocked isocyanate group-containing block isocyanate obtained by reacting a polyfunctional isocyanate containing two or more isocyanate groups with a blocking agent may be used. In this case, it is preferred that the polyfunctional crosslinkable compound is polymerized by reaction with a hydroxyl group of a polyfunctional hydroxyl group-containing compound, heat resistance due to crosslinking formation, and chemical resistance. It is a one containing two or more blocked isocyanate groups. Further, from the viewpoint of forming a crosslinkage bond between the polyfunctional hydroxyl group-containing compound and the isocyanate compound, it is preferred to use a polyfunctional isocyanate or a blocked isocyanate containing three or more isocyanates as the polyfunctional hydroxy group 158118.doc -26 - 201237101 Base compound. Further, as the polyfunctional crosslinkable compound, a polyfunctional compound having two or more oxazolyl groups is also preferably used. According to this configuration, the oxazoline group of the polyfunctional oxazoline compound reacts with the hydroxyl group of the polyfunctional hydroxyl group-containing compound to form a guanamine bond. Further, when the polymer compound has a hydroxyl group or a slow group, it is polyfunctional. The chewing sulphate compound reacts with a thiol group or a thiol group to form a crosslinked structure (3-dimensional cross-linking) comprising a guanamine bond and/or a guanamine vinegar. Thereby, a three-dimensional crosslinked three-dimensional network comprising a guanamine bond and/or a guanamine ester is formed between the polymer compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound, so that The interaction between the hydrogen bond and the hydrogen bond between the polymer structure and the chemical bond, and the flexibility of the polyfunctional group-containing compound can be effectively reflected to the polymer compound, thereby achieving sufficient warpage reduction and excellent heat resistance. . When the polyoxazoline compound is a compound having two or more oxazoline groups, various oxazoline compounds can be used within the range in which the effects of the present invention are exerted. In the resin composition of the present invention, the content of the polyfunctional crosslinkable compound is preferably 5 parts by mass and 60 parts by mass based on 100 parts by mass of the polymer compound. When the content of the polyfunctional crosslinkable compound is 5 parts by mass or more, sufficient crosslinking can be formed with the polyfunctional hydroxyl group-containing compound, and this can reduce the warpage at the time of curing. In addition, when the content of the polyfunctional crosslinkable compound is 60 parts by mass or less, the flow of the polymer compound during heating and pressurization is improved, and the south hole penetration property can be improved. Furthermore, the content of the polyfunctional crosslinkable material 2 is preferably 5 parts by mass to 3 parts by mass based on 1 part by mass of the polymer compound. 158118.doc •27·201237101 In the resin composition of the present invention, preferred is a molar ratio of a hydroxyl group contained in the polyfunctional hydroxyl group-containing compound and a crosslinkable functional group contained in the polyfunctional crosslinkable compound. It is a hydroxyl group/crosslinkable functional group = 0.5 to 1. In this way, the hydroxy group contained in the hydroxy group-containing compound becomes excessive with respect to the crosslinkable functional group of the polyfunctional crosslinkable compound, and thus the polyfunctional 3 hydroxy compound is appropriately formed. Crosslinking bonds between functional crosslinkable compounds. Therefore, it is possible to suppress the shrinkage of the polyimide which is hardened by the resin composition, and it is possible to achieve sufficient reduction in warpage and excellent heat resistance at the time of curing. (D) Photosensitizer The resin composition of the present invention contains a photosensitizer, whereby it can be used as a photosensitive dendrimer composition. As the photosensitizer, a common photosensitizer can be used in the second aspect and the second aspect of the tree. The photosensitizer is not particularly limited as long as it has a property of changing its structure due to light irradiation and causing a change in solubility with respect to a solvent, and various chemicals can be used as a photosensitizer, and for example, it can be suitably used. A (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds. Further, in the resin composition of the present invention, a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is preferably contained from the viewpoint of improving resolution and insulating properties. A compound of (meth)acrylic acid having three or more double bonds. Further, in the resin composition of the present invention, the (meth) acrylate compound having three or more double bonds is preferably a compound of the following formula (1 〇) from the viewpoint of insulation resistance value or reduction of warpage. Expressed as a compound. The compound represented by the following formula (1〇) is not embedded in the skeleton of the polymer compound to form 158118.doc •28·201237101 Crosslinker as the second component 'thus prevents the shrinkage of the polymer compound during hardening' When the compound represented by the formula (10) does not have a functional group which lowers the electrical insulating property such as a hydroxyl group, it is presumed that a straight crosslinked body can be formed, and the glass transition point (Tg) or the elastic modulus of the cured film becomes high. 'Insulation resistance value is increased. General formula (10)

(in the formula (10), 'r2. represents a hydrogen atom or a methyl group, and the plurality of sands independently represent a carbon number of 2 to a carbon number of 5, and may be the same or different. f is 1 to 1 An integer of 0. In the present invention, the yoghurt compound having two or more photopolymerizable unsaturated double bonds is preferably used as a resin residue having a photopolymerizable unsaturated double bond. a (meth)propionic acid vinegar compound having two double bonds and a (meth)acrylic acid vinegar compound having three or more double bonds. A (meth)acrylic acid vinegar compound having three or more double bonds Since a rigid crosslinked body is formed between the polyfunctional permeation-containing compound, it is presumed that the elastic modulus and the glass transition point (Tg) of the cured film are increased, and the insulation reliability is improved. (E) Photopolymerization initiator is used herein. The resin composition of the invention is preferably used in combination with a photopolymerization initiator in the case of using the above-mentioned photosensitizer 158118.doc -29-201237101. As a photopolymerization initiator, in the first aspect and the second A common photopolymerization initiator can be used as the photopolymerization initiator in the aspect of the resin composition. In the case of a compound which initiates polymerization by activation with various active light, ultraviolet light, etc., various β-forms can be used. As the photopolymerization initiator, for example, an oxime ester or the like can be suitably used. In the composition, a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds and a photopolymerization initiator are preferably used, and this can be suitably used as a photosensitive resin composition. (F) Flame Retardant In the resin composition of the present invention, a flame retardant is preferably contained. As the flame retardant, a common flame retardant can be used in the resin composition of the first aspect and the second aspect. The type of the flame retardant is not particularly limited, and examples thereof include a halogen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, and an inorganic flame retardant. Further, as the phosphorus compound, a compound containing a phosphorus atom in the structure is used. The phosphorus compound is, for example, a phosphate compound or a phosphazene compound. These flame retardants may be used alone or in combination of two or more. The resin composition of the present invention preferably contains a phosphorus compound, whereby the flame retardancy of the resin composition can be improved. In the resin composition, the phosphorus compound preferably contains a phosphate compound and/or a phosphazene compound, whereby the flame retardancy of the resin composition can be particularly improved. 158118.doc 30-201237101 Resin of the present invention In the composition, a cured product (cured film) can be obtained by heating or drying at a predetermined temperature. The cured product can be dried, for example, by applying the resin composition of the present invention to a substrate. Further, the photosensitive resin composition containing a photosensitizer can also be used as a photosensitive film. The resin film and the photosensitive film can be used as an interlayer insulating film or a wiring protective film of a flexible printed circuit board, for example. Suitable for use. The cured product of the present invention can be obtained by heating the above resin composition at 10 ° C to 130 ° C for 5 minutes to 60 minutes, and then heating at 16 (rc~2 Torr (rc for 15 minutes to 60 minutes). The resin film of the present invention comprises a substrate and a resin composition provided on the substrate. In this case, a copper foil, a carrier film, or the like can be used as the substrate. Further, in the resin film of the present invention, Preferably, a carrier film, a resin composition provided on the carrier film, and a cover film provided on the resin composition are provided, whereby the surface of the resin film can be protected. The copper resin is used as the substrate, and the resin composition is provided on the copper plate. As described above, the resin composition is dried on the steel foil to form an interlayer insulating film such as a multilayer flexible wiring board. The wiring board of the present invention comprises: a substrate having a wiring and a resin composition which is disposed to cover the wiring, and the resin composition is provided by covering the wiring as described above. The composition 'can be used as a wiring pattern of the wiring board The resin composition of the present invention contains a low molecular weight polyfunctional hydroxyl group-containing compound which is well compatible with the polymer compound and a polyfunctional crosslinkable compound 158118.doc -31 - 201237101, Therefore, the viscosity of the resin composition can be reduced to improve the fluidity, thereby embedding in the through hole or wiring pattern provided on the insulating substrate of the wiring board in the manufacturing process of the flexible printed wiring board. Since it can be used as an interlayer insulating film for a multilayer flexible wiring board or a wiring protective film, the outline of the manufacturing process of the wiring board of the present invention will be described with reference to Fig. 1. Fig. 1A As shown, a double-sided flexible substrate 10 is used in the manufacture of a multilayer flexible wiring board, and the double-sided flexible substrate 10 includes an insulating substrate 11 and is provided on the two main surfaces of the insulating substrate layer 11. Copper foils 12a and 12b. First, after laminating a dry film on the copper foils 12a and 12b, a part of the copper foils 12a and 12b is removed by exposure, development, and etching of the copper foils 12a and 12b. A through hole 13 is formed in the insulating substrate 11. Copper plating 14 is formed on the surface of the through hole 13 to electrically connect the copper foils 12a and 12b of the two faces (refer to FIG. 1B). Next, as shown in FIG. 1C, the flexible portion is formed by etching. The copper foil 12b in the region of 6 is removed. Next, the resin composition of the present invention is filled in the through hole 13 to perform an insulation treatment. Here, the polyfunctional isocyanate compound is used in the resin composition of the present invention as described above. When the polyfunctional crosslinkable compound has a hydroxyl group and/or a carboxyl group as a polymer compound, the resin composition exhibits moderate fluidity and viscosity. Thus, even in the case where a minute via 13 is provided At the same time, as shown in FIG. 1D, the laminated body 15 is laminated on the copper foils 12a and 12b, respectively, and the laminated body 5 includes the copper foil 5a and the present. The protective layer 15b obtained by applying the resin composition of the invention to the copper foil 15a. Here, 158118.doc • 32-201237101 In the case where polyimine is used as the polymer compound in the resin composition of the present invention, it becomes unnecessary to imidize after coating. Thereby, it is possible to carry out the layering using rapid pressing without the need for laminating and then hardening treatment. Next, as shown in FIG. 1E, after the copper foil i5a and the protective layer 15b are removed by etching or the like, copper plating 14 is performed to re-form the copper foil as the external conductive layer and the copper foil 12a as the inner conductive layer. Electrical connection. Next, the copper foil 15a is patterned by a subtractive method or the like to form a wiring pattern. Finally, as shown in Fig. 1F, the resin composition of the present invention is applied onto the copper foil subjected to the wiring pattern processing to form the protective film crucible 7. Here, as described above, a polyfunctional isocyanate compound is used as the polyfunctional crosslinkable compound in the resin composition of the present invention, and as a polymer compound, in the case of having a hydroxyl group and/or a carboxyl group, in the resin composition Shows moderate fluidity and stickiness. Therefore, even when a fine wiring pattern is formed, the resin composition can be filled between the wiring patterns to perform insulation protection. Further, the resin film of the present invention preferably has an interlayer insulation resistance of 1 〇 9 卩 or more in an insulation reliability test at a temperature of 85 〇 c, a humidity of 85 〇 / 〇, and 1000 hours, and a viscosity of 120 kPa to 220 C of 550 pa. .s ~100000 pa .s, and an elastic region having an elongation of less than 20% and a plastic region having an elongation of 5% or more, and the film thickness of the interlayer insulating layer is 4 〇μηι or less. When the resin film and the resin film formed on the copper foil are laminated on the wiring board, the through hole portion can be satisfactorily embedded, and the resin plate can be suitably used without flowing the resin at the end portion. When it is used as an interlayer insulating film, resin is required to flow into the wiring portion or the via portion of the wiring board, and on the other hand, the resin composition is required to be held to some extent without flowing out from the end portion of the wiring board. The reason is that in the pressing step under high pressure, in the pressing step, if the inflow to the through hole is attempted sufficiently, the resin composition usually flows out from the end portion of the wiring board, and wiring exists. The thickness of the insulating layer at the end of the board is reduced, resulting in a decrease in insulation. In the case of the above constitution, by controlling the viscosity of the resin film 12 (rc 〜 22 〇 (>c and the elastic region and the plastic region of the resin film, it is possible to simultaneously achieve the inflow of each other by the prior art) In the through hole and in the prevention of the resin composition flowing out from the end portion of the wiring board, very good embedding property can be achieved. That is, 'as a resin film 120. (: viscosity of ~22〇t, if it is laminated When the viscosity of between 120 ° C and 220 ° C used is 5,000 Pa·s or more, the resin composition can be prevented from flowing out from the end portion of the wiring board and good embedding property can be obtained if the viscosity is 100,000 pa · S In the elastic region in which the elongation of the resin film is less than 20%, the resin composition can be prevented from flowing out from the end portion of the wiring board, and the laminate is formed by a general-purpose laminated device, for example, a vacuum press. Good embedding property can be achieved by a plastic region in which the elongation of the resin film is 50% or more. Further, by making the thickness of the interlayer insulating layer 4 μm or less, an extremely good low repulsive property is exhibited, so that it is small. Portable electronic machine The interlayer insulating resistance in the insulation reliability test at a temperature of 85 ° C, a humidity of 85%, and a time of 1000 hours is ι 〇 9 Ω or more, even if the film thickness of the interlayer insulating layer is 40 μm or less. In the following, the embodiment of the present invention will be described in detail. In the following first to fourth embodiments, the resin composition of the second aspect is mainly used. In the following first to fourth embodiments, the polymer compound to be used may be appropriately selected.

158118.doc -34- S 201237101 and used as the resin composition of the first aspect. (First Embodiment) As a material used in the production of a flexible printed circuit board, a resin conjugate of a polyimine precursor comprising a partial oxime imidization of one of polyamic acid has been proposed. In the resin composition, by using a polyamidimide precursor obtained by imidating a part of poly-aracine, the warpage caused by the shrinkage of the polyimine can be reduced, and the film can be cooled at a low temperature. The ruthenium imidization is carried out to suppress the reaction of the polyimide precursor with the wiring material by the ruthenium imidization, and the development treatment by the alkaline aqueous solution is facilitated. However, due to the high functionality and weight reduction of the flexible printed circuit board in recent years, it is not always possible to sufficiently reduce the warpage in the case of using the resin containing the polyimide precursor, and also regarding heat resistance. Expectations are improved. The inventors of the present invention have focused on the use of a polyimine having a polyamic acid structure and a polyimine structure as a structural unit as the (A) polymer compound. Furthermore, the present inventors have found that an isocyanate compound (block) containing (A) as a polymer compound, (B) a polyfunctional hydroxyl group-containing compound, and (c) as a polyfunctional crosslinkable compound The isocyanate compound), and the molar ratio of the hydroxyl group contained in the poly-S-containing hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate compound is within a predetermined range, thereby obtaining a reduction in the interesting property at the time of hardening, and It is excellent in heat resistance, and can be suitably used as a surface protective film for a semiconductor element, an interlayer insulating film, a protective layer for a printed wiring board, or a material such as a rim film interlayer insulating film. In the resin composition, the polyfunctional permeation-containing compound is not embedded in the month 4 of the polyimine and is present as the second component in the polyfunctional P group 158118.doc • 35- 201237101

Since the compound forms a three-dimensional crosslink with the blocked isocyanate compound, the shrinkage of the polyimine molecular chain at the time of hardening can be suppressed, warpage can be suppressed, and the melt viscosity of the resin composition before hardening can be lowered to form a through hole. Increased burial. Further, since the polyimine structure has a polyphthalic acid structure (the polyamic acid structure has a heat crosslinkable functional group) as a structural unit, a polyfluorene-containing compound and a blocked isocyanate compound are formed via a polyfluorene. A 3-dimensional network of imines. By this, the warpage at the time of hardening can be reduced. Further, polyimine has good compatibility with other components, and has a three-dimensional structure or a network structure interpenetrating [Inter Penetrati〇n Netw〇rk (ipNW polyfluorene imide structure as a structural unit, thus exhibiting High heat resistance (for example, hot solder heat resistance). Further, by including a blocked isocyanate compound, the carboxyl group is deactivated at a low temperature, and it can be cured at a low temperature, thereby preventing the polyimine at the time of hardening. The first embodiment of the present invention will be described in detail with reference to the first embodiment of the present invention. The resin composition according to the first embodiment of the present invention contains (a) a polyimine and (B) a polyfunctional hydroxyl group-containing compound. And (c_1) an isocyanate compound (block isocyanate compound) having a polyamidene structure and a polyamic acid structure as a structural unit, and a hydroxyl group and a blocked isocyanate compound contained in the polyfunctional hydroxyl group-containing compound The molar ratio of the isocyanate group to the hydroxyl group / isocyanate group = 0.5 to 1. In the resin composition, the hydroxyl group and the block contained in the polyfunctional hydroxyl group-containing compound The molar ratio of the isocyanate group contained in the cyanate ester to the hydroxyl group/isocyanate group is 0.5 to 1 ', and the amount of the isocyanate group is excessive with respect to the hydroxyl group. It is presumed that the composition can be expressed by the mechanism shown below.出耐158118.doc

S -36- 201237101 Heat. The isocyanate group reacts with a hydroxyl group to form a urethane structure, but since the amount of the isocyanate group is excessive with respect to the hydroxyl group, the isocyanate group remains. The remaining isocyanate group reacts with a carboxyl group of a polyglycolic acid structure contained in the polyimine which remains after the imidization reaction to form a guanamine structure or a urea structure. That is, chemical crosslinking between the polyimine and the block isocyanate compound and chemical crosslinking between the polyfunctional hydroxyl group-containing compound and the blocked isocyanate compound are formed by thermal hardening. As described above, a plurality of types of cross-linking by reaction between isocyanates and the like form a three-dimensional network, thereby exhibiting further heat resistance. Next, the details of each composition constituting the resin composition will be described. (a) Polyimine The polyimine used in the resin composition of the present embodiment can be obtained, for example, by reacting tetrarexic acid-Sf with a diamine. The four tetrahydrous dianhydrides used are not limited to the use of previously known tetracarboxylic dianhydrides. As the tetracarboxylic acid di-field, an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride can be used. Further, the diamine to be used is not limited, and a previously known diamine can be used. Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'. biphenyltetracarboxylic dianhydride, and 2,3,3·, 4 ι·biphenyl. Tetraphthalic acid dianhydride, 2,2,3,3'-biphenyltetradecanoic acid dianhydride, 3,3,4,4,_benzophenone tetracarboxylic acid monoanhydride, 2,2',3,3 '-benzophenone tetradecanoic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, Manufacture of bis(3'4-dicarboxyphenyl)ethane dianhydride, hydrazine, bis(2,3-dicarboxyphenyl)ethane-anhydride, bis(3,4-di-repentylphenyl) Dimensional liver, bis(2,3_bis-sulfophenyl) decane-anhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,3,_oxo-dual stupid 158I18.doc • 37· 201237101 Citrate dianhydride, 4,4,-oxydiphthalic dianhydride, 2,2-bis(4-(4-aminophenyl)oxy)propane, 1,3·dihydrogen -1,3-di-oxyl_5-isobenzopyrene-acid-1,4-phenylenedicarboxylate, 4-(2,5·di- oxytetrahydrofuran_3_基广丨'^私四Hydrogenated naphthalene-1,2-dicarboxylic anhydride, 1,2,5,6-naphthalene tetraphthalic acid dianhydride, 2,3,6,7-carotene phthalic acid dianhydride, 2,3,5,6-pyridyl Tetracarboxylic acid dianhydride, 3,4,9,10-dicain tetraphenyl phthalic anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2_bis (4 -(3,4-dicarboxyloxy)phenyl)hexafluoropropane dianhydride, 2 2•bis(4_(3,4·dicarboxybenzyloxy)phenyl)hexafluoropropane dianhydride, 2 2,_bis(tri-Imethyl)-4,4.-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride. Examples of the aliphatic tetracarboxylic dianhydride include a ring. Butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic acid monoanhydride, 5-(2,5-one side oxy group Tetrahydro-3-0fusyl)·3 -methyl_3_cyclohexan 1,2-diphthalic acid dianhydride, bicyclo[2,2,2]octyl-7-ene-2,3, 5,6_tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. The above tetracarboxylic dianhydride may be used singly or in combination of two or more. From the viewpoint of the heat resistance of the imine or the polymerization rate, among the above tetracarboxylic dianhydrides, 3,3·, 4,4,-biphenyltetraphthalic acid dianhydride, 4,4-oxo-phthalic acid may be mentioned. Formic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dioxane, double (3,4-two rebellion Phenyl) dianhydride is particularly preferred. Specific examples of the diamine include 3,3,-diaminodibenzophenone, 4,4·-diaminobenzophenone, and 3,3. '-Diaminodiphenyl ether, 4,4,-diaminodiisopropyl ether, 1,3-bis(3-aminophenoxy)benzene, anthracene, 4-bis(4-aminophenoxy) Not bis(3-(3-amine basic oxy)phenyl), bis(4-(4-aminophenoxy)phenyl)ether, 1,3-bis(3-(3-amino) Phenoxy)phenoxy)benzene, 14•bis (4(4_158118.doc •38· 201237101 aminophenoxy)phenoxy)benzene, bis(3-(3-(3-aminophenoxy) Phenoxy)phenyl)ether, bis(4-(4-(4-aminophenoxy)phenoxy)phenyl)ether, 1,3-bis(3-(3-(3-) Aminophenoxy)phenyloxy)phenoxy)benzene, 1,4-bis(4-(4-(4-aminophenoxy)phenoxy)phenoxy)benzene, 4,4' - bis(3-aminophenoxy)biphenyl, 4,4.-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(3-aminophenoxy)benzene Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]_1,1, 1,3,3,3-hexafluoropropyl , 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, para-benzene Diamine, bis(3-aminophenyl) sulfide, bis(4-aminophenyl) sulfide, bis(3-aminophenyl) sulfoxide, bis(4-aminophenyl) sulfoxide , bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]butane, α:,ω - bis(2-aminoethyl)polydimethyloxane, bis(3-aminopropyl)polydimethyl oxazepine, (^...bis(4-aminobutyl) poly Dimethyl methoxy oxane, α, ω-bis(4-aminophenyl) polydidecyl fluorene oxide, bis(3-aminopropyl) polydiphenyl fluorene, etc., but not Limited to these. Preferred is 4,4'-bis(3-aminophenoxy)biphenyl, iota, 3_bis(3_(3-aminophenoxy)phenoxy)benzene, 1,3-bis( 3-aminophenoxy)benzene, polyoxyalkylene diamine. Further, as a diamine, bis(2.aminoethyl)polydimethyloxane, α,ω-bis(3-aminopropyl)polydidecyloxyne, bis-amine Butyl) polydimethyloxane, α,ω-bis(4-aminophenyl)polydimethyloxane, α,ω-bis(3-aminopropyl)polydiphenylfluorene Oxyalkanes and the like are also preferred. Among the above diamines, from the viewpoint of reducing the warpage of the cured product of the resin composition, it is preferable to use the oxyethylene diamine or the polyoxypropene 158118.doc •39-201237101 bisdiamine, Other polyoxyalkylene diamines and the like which contain an alkylene group having a different number of carbon chains. Examples of the polyoxyalkylene diamines include JEFFAMINE ED-600 ' ED-900 ' ED-2003 ' EDR-148, HK-511 and other polyoxyethylene ethylamine or JEFFAMINE D-23 manufactured by Huntsman Corporation of the United States. 0, D-400, D-2000, D-4000, polyetheramine 0-230, D-400, D-2000 and other polyoxyalkylene diamine or JEFFAMINE XTJ-542, XTJ533, XTJ536 manufactured by BASF, Germany Such as having a polytetradecyl group extending ethyl group and the like. Among them, EDR-148, D_230, D-400, HK-511 and the like having a relatively low molecular weight can be a polymer having a relatively high glass transition temperature, and therefore can be preferably used in applications requiring heat resistance and chemical resistance. use. On the other hand, D-2000 having a relatively high molecular weight is excellent in flexibility and the like. Further, from the viewpoint of the balance between heat resistance, chemical resistance, flexibility, and solvent solubility, the weight average molecular weight of the polyoxyalkylene diamine is preferably from 400 to 3,000, and particularly preferably from 400 to 2,000. Preferably, 〇-400, 〇-2000, ED-600, ED-900, and XTJ-542 can be used. The polyimine used in the resin composition of the present embodiment has a polyimine structure and a polyamic acid structure as structural units. Thus, together with the polyamidiamine moiety having good compatibility with other components, and the polyamic acid moiety having a thermally crosslinkable functional group, thereby curing at low temperature by reaction with the blocked isocyanate When the carboxyl group remaining at the time is deactivated, the block isocyanate and the polyfunctional hydroxyl group-containing compound can suppress warpage. Further, the polyimine used in the resin composition of the present embodiment preferably contains By polyether structure of polyimine. The reason is 158118.doc •40· 201237101. By virtue of the polyether structure in the skeleton, the glass transition temperature and the elastic modulus of the hardened material after thermal hardening can be suppressed, thereby further reducing the warpage. Further, after thermosetting, a chemical crosslink is formed between a polyimine having a polyether structure and a compound having a heat crosslinkable functional group, and the polyaminan having a polyether structure has a polyalkylene oxide chain. Therefore, a three-dimensional network can be formed due to the local interaction between the polymer chains, and heat resistance is exhibited. Further, as the polyimine, a polyimine containing a polyimine moiety having a structure of the following formula (2) is preferably used. It is used to increase the solvent solubility of polyimine. General formula (2)

(In the formula (2), acetamidine and Z2 represent a tetravalent organic group. 丫丨, Y2, Y3, Y4 and Ys represent an alkylene group having a carbon number of 1 to a carbon number of 5, and may have a side chain. b, c and d represent an integer of 1 to 50.) Further, as the polyimine, it is also preferred to use a polyimine containing a polyimine moiety having a structure of the following formula (11) . The solvent solubility of the polyimine is improved by including a polyimine portion having a structure of the following formula (11). As the polyimine, a polyimine containing a polyimine moiety having a structure of the above formula (2) or the following formula (11) is preferably used. I58118.doc -41 · 201237101 [Chem. 18] General formula (11)

(In the formula (11), 'Z5AZ6 represents a tetravalent organic group. γ6, γ7, %, in the above formula (2), Y, γ2, γ ν 铋Α 2 Υ3, Υ4, 丫5 series carbon number Examples of the alkylene group having 1 to a sufficient number of 5 are τ &, ethyl, propyl, isopropyl, butyl, and isobutyl. The bases b, c and d represent 1 to The wisdom of 50 is preferably 3 to 40, more preferably 5 to 3 〇. In the above formula (11), B and the heart are phenyl, biphenyl, and phenyl. The organic group 'for example, may be listed as "the present ether group, benzophenone group, diphenyl sulfone group, and a group. Among them, a biphenyl group, a diphenyl junyl group, a diphenyl group, a diphenyl sulfone is preferred. Further, in the above formula (1)), Y6'Y7, Y8, m, K and Y丨3 represent a fluorenyl group. Examples of ruthenium 6, Y7 include, for example, a The base, the ethyl group, the propyl group, the exo-propyl group, the #" Λ * butyl group, the isobutyl group and the like have a carbon number of 1 to a carbon number of 5. Also, as γ, ν

Examples of γ8, γ9, YlQ, Υιι, and U Y丨3 include hydrazine, 7萁rylethyl, propyl, butyl, and phenyl. Among them, preferred is methyl, ? It is a total of two groups, ethyl propyl group and butyl group, more preferably methyl 'ethyl group, propyl group. g represents an integer of 3 to 1 ,, preferably 5 to 7 〇, more preferably 158118.doc

S • 42· 201237101 is 10~50. Further, among the monoamines of the polyimine, it is preferred that the content of the diamine having the structure of the following formula (10) is 15 mol% or more and 85 mol = or less. It is intended to improve the solvent solubility and low elastic modulus of polyimine. General formula (12) Y4-

H2N—Yt-ίο—Y2-U〇—y3\/q. ο (In the formula (12), 'Yl, Υ2, Υ3, Υ4, and Υ5 represent an alkylene group having a carbon number of 1 to a carbon number of 5, Further, in the above formula (12), Y2, Y3, and ytterbium are preferable from the viewpoint of adhesion to the substrate, in addition to the side chain. b, c&d. 4 and 丫5 have two or more kinds of alkylene groups. Further, among all the diamines in the polyimine, it is preferred that the content of the diamine having the structure of the following formula (13) is 15 mol% or more and 95 mol% or less. It is intended to improve the solvent solubility and low elastic modulus of polyimine. General formula (13)

Yl2 I. -Si—Y7 - ΜΗ: Yl3 Υιο Η2Ν—YrSi—〇4Si—〇丫9 LY11 158118.doc ·43· 201237101 (in formula (13) 'γ6, γ7, γ8, γ9, Υι〇, Υιι丫12 and 丫|3 means that the fire i base β g is not an integer of 3 to 100.) Further, as the polyamidimide, the imidization ratio is self-forming and the cross-linking function is formed. From the viewpoint of crosslinking of the isocyanate compound of the polyfunctional crosslinkable compound, it is preferably 25% or more and less than 100%, more preferably 25°/. Above 98%. If the polyamidimide has a ruthenium imidation ratio of 98. /. In the following, the carboxyl group in the polyimine precursor which is crosslinked with the compound having a thermally crosslinkable functional group remains sufficiently, so that it exhibits chemical resistance and heat resistance after curing. Further, if the polyamidimide has a hydrazine imidation ratio of 250/. When the above is cured, the carboxyl residue remaining in the test solution is reduced, and the chemical resistance and heat resistance can be exhibited. Further, in the above embodiment, the resin composition of the second aspect using the polyimine having a polyimine structure and a polyaminic acid structure is described, but it may also be In the range of the effects of the present invention, a polyimide composition having substantially no polyamic acid structure is used, and it is used as the resin composition of the first aspect. In this case, since the imidization ratio of the polyimine is 100%, there is no need for the imidization reaction, and the deterioration of the wiring layer is suppressed to exhibit good insulation reliability and heat resistance. Next, a description will be given of a method for producing a polyimine. For the method for producing a polyimine of the present embodiment, all methods for producing a polyimide having a known method can be applied. Among them, a method of reacting in an organic solvent is preferred. Examples of the solvent to be used in such a reaction include hydrazine, hydrazine dimethylformamide, N,N-dimethylacetamide, and N-methyl-2.嘻 咬 ketone, γ-butyrolactone, hydrazine, 2-dimethoxyethane, tetrahydrofuran, hydrazine, 3- dimethyl • 44· 158118.doc

S 201237101 Burning, 1,4-二0 规 i i, dimethyl ke s λ λ — Τ sulf sulfoxide, Ben, toluene, xylene, tricresene, phenol, cresol, benzoic acid 8 曰, the present butyl formate and the like. These may be used singly or in combination of two or more. Further, the concentration of the reaction raw material in the reaction is usually 2% by mass to _%, preferably 3 % by mass to 70% by mass. The molar ratio of the diterpene tetradecanoate to the diamine in the reaction range is in the range of 〇·8~Μ. In the case of this range, the molecular weight can be increased, and the elongation and the like are also excellent. Preferably, 〇.9~]. Bu is better than the weight of om polyimine. The average molecular weight is (5) is 5 or more. (10) y. Here, the so-called weight average molecular weight refers to the average molecular weight in a known amount. The poly(ethylene) is the weight average molecular weight measured by gel permeation chromatography. The weight average molecular weight is more preferably 1 Torr or more and 6 Å or less, and most preferably 20,000 or more and 50,000 ounces. When the weight average molecular weight is 5,000 or more and lessooo or less, the warpage of the protective film obtained by using the resin composition is improved, and the low repulsiveness and heat resistance are excellent. Further, it is possible to apply a film having a desired thickness at the time of printing without bleeding, and it is excellent in mechanical properties such as elongation of the obtained protective film. The brewing imine can be obtained by the method described below. First, a polycondensation reaction is carried out by subjecting a reaction raw material to a polycondensation reaction at room temperature. Next, 'the polyimine is preferably heated to 100 ° C to 400 ° C to carry out oxime imidization' or chemical imidization using a ruthenium imide such as acetic anhydride, thereby obtaining inclusion Polyimine having a polyimine structure having a repeating unit structure corresponding to polylysine. In the case of performing imidization by heating, in order to remove the by-produced water, 158118.doc •45-201237101 is preferably an azeotropic agent (preferably toluene or xylene) using Dean_Stark The type dehydration device performs dehydration under reflux. Further, it is preferred that the formation of the polyamidene containing the polyacrylic acid structure is carried out together with the thermal imidization reaction by the reaction, and the structure comprising the polyimine structure and the polyamic acid structure is obtained. Polyimine. That is, it is preferred to "suspend or dissolve the diamine component and the acid dianhydride component in an organic solvent" at 80. (: ~22 (the reaction of TC is heated, whereby the formation of polyimine and the dehydration of the ruthenium iodide are carried out together to obtain a polyimine. Further, the polymer backbone of the polyimine The terminal can also be blocked by a terminal blocking agent containing a monoamine derivative or a carboxylic acid derivative. The terminal of the polymer backbone of the polyimine is blocked, and thus the storage stability derived from the terminal functional group is excellent. Examples of the blocking agent containing a monoamine derivative include aniline, o-toluidine, m-toluidine, p-anisidine, 2,3-dimethylaniline, 2,6-dimethylaniline, and 3,4-di. Toluidine, 3,5-dimethylaniline, o-chloroaniline, m-aniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, o-Aminophenol, p-aminophenol, m-aminophenol, o-aminoanisole, m-aminoanisole, p-aminoanisole, o-aminophenethyl ether, m-aminophenylether, p-amine Phenylethyl ether, o-aminobenzaldehyde, p-aminobenzaldehyde, m-aminophenyl aldehyde, o-aminobenzonitrile, p-aminobenzonitrile, m-amino group Benzotrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenyl phenyl mystery, 4-aminophenyl Phenyl mystery, 2-aminobenzidine, 3-amino 2 awkward • 46- 158118.doc

S 201237101 Ketone 4-Amine, a brew, 1, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4-aminophenyl phenyl sulfide, 2-amino Phenylphenyl sulfone, 3-aminophenyl phenyl sulfone, 4-amino phenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 5-amino group- 1-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino- An aromatic monoamine such as 1-naphthol, 8-amino-2-naphthol, anthraquinone-based anthracene, 2-aminoguanidine or 9-aminoindole. Among them, an aniline derivative can be preferably used. These may be used singly or in combination of two or more. As the blocking agent containing a carboxylic acid derivative, a carboxylic anhydride derivative is mainly mentioned. Examples of the carboxylic anhydride derivative include phthalic anhydride, 2,3-benzoquinone dicarboxylic anhydride, 3,4-diphenyl'fluorenone dicarboxylic anhydride, and 2,3-dicarbylphenyl. Ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl phthalic anhydride, 3,4·diphthalic anhydride, 2,3-dicarboxyphenyl sulfone anhydride, 3 , 4_ dicarboxyphenyl strepyl hard anhydride, 2,3-dicarboxyphenyl phenyl thioether anhydride, 3,4- retinophenyl phenyl phthalic anhydride, 1,2-naphthalene dicarboxylic acid wild, 2,3-naphthalene dihydrogenate liver, 1,8-naphthalene monocarboxylic acid, 1,2-decanoic acid if, 2,3-decanoic acid liver, 1,9-nonanedicarboxylic anhydride, etc. Dicarboxylic anhydride. Among these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used. These may be used alone or in combination of two or more. The polyimine obtained by the above method can be used as it is without using a solvent, or it can be used in the resin composition of the present embodiment by further preparing a necessary solvent, an additive or the like. Further, in the above embodiment, a polyimine structure having an aliphatic diamine component and a polyglycolate 158118.doc • 47·201237101 as a structural unit are used as the (A) polymer compound. The resin composition of the second aspect of the polyimine is described, and the polyimine which is substantially free of the polyamic acid structure may be used as the above-mentioned effect. I used a mixed resin composition. (Β) Polyfunctional hydroxyl group-containing compound The polyfunctional group-containing compound used in the resin composition of the present embodiment means a monomer having two or more hydroxyl groups per molecule chain. In the case of a hydrocarbon group containing an aliphatic, an aromatic or an alicyclic group in the skeleton, the self-inhibition of the structure represented by the following formula (14) is preferable in terms of improving the insulating property. In view of warpage, it is preferred to contain an aliphatic compound. The reason for this is that by having an aliphatic skeleton, hygroscopicity can be suppressed without impairing the effect of suppressing warpage, and high insulation properties can be exhibited even when absorbing moisture. Further, in the case of containing a long-chain aliphatic group, the effect of suppressing warpage becomes high and is preferable. General formula (14) H〇4fxyYffz^fx 〇Η (In the formula (14), X-type aromatic, γ-based carbon number is 丨~ carbon number is (7) aliphatic 'Z-based (four) base , § base, carbon (tetra), amino formate, argyl functional group 'h = 0 to 2 integer, Bu (a) integer, divination ~ face integer.) And 'especially for electronic materials, please Among them, it is preferred that the halogen is not contained in gas or gas. 158118.doc

S.48-201237101 Specific examples of the polyfunctional hydroxyl group-containing compound include polybutadiene diol such as PTMG1 000 (manufactured by Mitsubishi Chemical Corporation) and polybutadiene diol such as G-1000 (manufactured by Sakamoto Soda Co., Ltd.). a polycarbonate diol such as hydrogenated polybutadiene diol such as -1000 (manufactured by Japan Soda Co., Ltd.), DURANOL T565 1, DURANOL T5652, DURANOL T4671 (manufactured by Asahi Kasei Chemicals Co., Ltd.), and PLACCEL CD (manufactured by Daicel Chemical Industries, Ltd.). Polycaprolactone diol such as PLACCEL 200 (manufactured by Daicel Chemical Industries, Ltd.), bisphenols such as bisphenol A (manufactured by Daicel Chemical Industries, Ltd.), hydrogenated bisphenols such as Rikabinol HB (manufactured by Nippon Chemical Co., Ltd.). Among them, polybutadiene diol, hydrogenated polybutadiene diol, and polycarbonate diol are preferred from the viewpoint of improving the insulating property, and polycarbonate is preferred from the viewpoint of reducing warpage. Glycol. Further, as the polyfunctional hydroxyl group-containing compound, it is preferably liquid at room temperature from the viewpoint of reducing warpage and solubility in an organic solvent. The molecular weight is preferably from 500 to 3,000, and particularly preferably from 500 to 2,000. The polyfunctional hydroxyl group-containing compound is preferably contained in an amount of from 3 parts by mass to 70 parts by mass per 100 parts by mass of the resin composition, in view of reduction in warpage, solder heat resistance, and chemical resistance. More preferably, it contains 5 parts by mass to 60 parts by mass. In the present embodiment, the polyfunctional hydroxyl group-containing compound having two hydroxyl groups is described as the (B) polyfunctional hydroxyl group-containing compound, but it may be used in the range of the effect of the present invention. More than one hydroxyl group polyol, and the like. 158118.doc -49- 201237101 (cl) Block Isocyanate Compound The blocked isocyanate compound used in the resin composition of the present embodiment is an isocyanate and a blocker having two or more isocyanate groups in the molecule. The compound obtained by the reaction. Examples of the isocyanate compound having two or more isocyanate groups in the molecule include hydrazine, 6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4-toluene diisocyanate. 2,6-nonyl diisocyanate vinegar, benzodiazepine diisocyanate, 4,4·_dicyclohexyl methane diisocyanate, 4,4·-enylated diisocyanate, different Fro-diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, phenyl phenylene, 4_2 Isocyanic acid, phenyl-2,6-diisocyanate, 1,3,6-hexamethylene triisocyanate, or hexamethylene diisocyanate. Examples of the blocking agent include alcohols, phenols, ε-caprolactam, jiang, active methylene, thiols, amines, quinones, amines, imidazoles, ureas. , amine carbamates, imines, or sulfites. Specific examples of the blocked isocyanate compound include Duranate SBN-70D, ΤΡΑ-Β80Ε, ΤΡΑ_Β80Χ, 17Β-60ΡΧ, MF-B60X, Ε402-Β80Τ, ME20-B80S, MF-K60X manufactured by Asahi Kasei Chemical Co., Ltd. Hexamethylene diisocyanate (hereinafter also referred to as "HDI") such as Κ6000 is a blocked isocyanate. Moreover, as a product of Mitsui Chemical Polyurethane Co., Ltd., the product name Takenate Β-882Ν, the trade name of the toluene diisocyanuric acid block isocyanate, Takenate β·830, and 4 4, _ diphenylmethane diisocyanate are mentioned. The trade name of block isocyanate is Takenate B-815N, which is Takeate B-846N as i,3·bis(isocyanatemethyl)cyclohexane block isocyanic acid 158118.doc •50- 201237101 ester. Further, a product manufactured by Japan Polyurethane Industry Co., Ltd. under the trade name of CORONET®-2503, 2515, 25〇7, 2513, or MILLIONATE MS-50, or Baxenden, which is an isophorone diisocyanate-block isocyanate, may be mentioned. No. 795〇, 7951, 799〇, etc. These block isocyanate compounds may be used singly or in combination of two or more. Further, in the present embodiment, the blocked isocyanate compound is described as the (c) polyfunctional crosslinkable compound, and the above polyfunctional isocyanate compound having two or more isocyanate groups may be used instead of the funeral Cyanate compound. Further, in place of the polyfunctional isocyanate compound, a polyfunctional compound can be used in the range in which the effects of the present invention are exerted. Further, the resin composition may contain an organic solvent in addition to the polyimine, the polyfunctional hydroxyl group-containing compound, and the latent isocyanate compound. The reason for this is that n is dissolved in an organic solvent and can be preferably used as a varnish. Examples of such an organic solvent include N,N_: methylacetamide, hydrazine, hydrazine-diethylacetamide, N,N-dimethylformamide, and N,N-diethylformamide. , Ν· A m (4) and other amine solvent, γ · butyl vinegar, γ · pentane (tetra) and other internal vinegar refrigerant monomethyl sulfoxide, diethyl hydrazine, hexamethyl sulfoxide and other sulfur-containing solvents ' A bismuth, benzene and other hydrazine solvents, diethylene glycol diterpene (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethanol dimethyl ether, monocentric, Tetrahydrofuran, butyl benzoate, ethyl benzoate, formazan benzoate and other preparations. χ, these organic solvents may be used singly or in multiples. 158118.doc • 51- 201237101 In terms of properties, it is preferred to use butyl benzoate and benzoic acid. In particular, the use of γ-butyrolactone, triethylene glycol dioxime ether, and the composition of the flame retardant of the flame retardant from the high boiling point and the low water absorption may further include the type of the flame retardant flame retardant. There is no special: limited, including (4) compounds, phosphorus compounds and inorganic flame retardants. These flame retardants may be used alone or in combination of two or more. The amount of the flame retardant to be added is not particularly limited and may be appropriately changed depending on the type of the inhibitor to be used. For example, it can be used in the range of 5 mass% to 5 mass% based on the content of the polyimine. Examples of the element-containing compound include an organic compound containing gas and a compound containing bromine. Specifically, pentabromodiphenyl ether and octabromodiphenyl can be cited.

Shout, ten play diphenyl scales, four 淳婶 threats, since I and so on. ~ "Twelve appearances and four deserts A" as phosphorus-containing compounds, can be cited as rhyme, phosphine, phosphine oxide, vinegar, and squaric acid from the purpose of (4) compounds, especially from the compatibility with polyamidiamine compositions In view of the above, it is preferred to use (iv) a nitrile, a phosphine oxide, or a squaric acid vinegar. As a specific example of the filler-containing compound, a phosphazene derivative FPl〇〇, FPn〇, traitor 3 manufactured by Fushimi Pharmaceutical Co., Ltd. may be mentioned. Fp4〇〇, etc. Examples of the inorganic flame retardant include a compound and a metal hydroxide. Examples of the ruthenium compound include aluminum oxide and pentoxide as metal hydroxides, and examples thereof include aluminum hydroxide. Magnesium hydroxide, etc. Further, by recording the compound with the above-mentioned dentate-containing compound (IV), it can be decomposed by the thermal decomposition of I58118.doc

S •52· 201237101 Produces a dentate enthalpy in the temperature zone. The cerium oxide captures halogen from the flame retardant, so the flame retardancy can be multiplied. The inorganic flame retardant is not dissolved in the right solution and is dissolved in an organic solvent, so that the particle size of the powder is preferably 疋1 〇〇 μηι or less. The reason for τ is that if the particle size is below 100 μηι, the grain is easily mixed into the poly-branched man. ^ ΒΗ ^ amine, and in a, and the transparency of the tree after the hardening is damaged. In order to improve the flame retardancy of the group, the particle size of the powder is preferably 50 μΓη or less, and particularly preferably 1 〇 or less. Further, as a flame retardant, it is also possible to use a nitrogen compound. The nitrogen-containing compound may be used as a flame retardant, and the above-mentioned element-containing compound, the bowl-containing compound, the inorganic flame retardant, and the nitrogen-containing compound may be used in combination of two or more kinds as a flame retardant. The amount of the nitrogen-containing compound to be added is not particularly limited, and may be changed depending on the type of the flame retardant to be used. As a nitrogen-containing compound. The amount can be measured, for example, in the same manner as the above-mentioned flame retardant based on the content of the polyimine. Use within the range of ~50% by mass. Examples of the nitriding-containing material include melamine cyanuric acid vinegar manufactured by Nissan Chemical Co., Ltd., and the company. When the coating film is formed, the viscosity and the enthalpy change can be adjusted according to the coating method. It may also be added by adding a filler or a rheology imparting agent as needed. Further, an additive such as a known antifoaming agent or a leveling agent or a pigment may be added. In addition, when a coating film is formed, a urethane-based catalyst may be added and used as an amine phthalate-based catalyst, and ϋ-CAT SA manufactured by San-Apro Co., Ltd. may be cited. 1〇, 603, 506, U-CAT (registered trademark) 1102, an organic hydrazine compound manufactured by Matsumot〇 Fine Chemical Co., Ltd., 鍅K-KAT manufactured by Nanben Chemical Co., Ltd., and the like. 158118.doc •53· 201237101 The resin composition may further contain a compound having a heat crosslinkable functional group. Examples of the compound having a thermally crosslinkable functional group include a triazine system, a benzoxazine compound, and an epoxy compound. As the triazine-based compound, melamine and melamine cyanurate are preferred. Examples of the melamines include melamine derivatives, condensates of compounds having a structure similar to melamine, and melamine. Specific examples of the melamines include, for example, methylolated melamine, melamine monoamine, decylamine cyanamide, and formazan: decyl melamine, cyano melamine, aryl decylamine, honey white Amine, melem, melon, and the like. Examples of the melamine cyanurate include a molar reactant such as cyanuric acid and melamine. Further, the number of amine groups or hydroxyl groups in the melamine cyanurate may be substituted by other substituents. The benzoxazine compound may be one containing only a monomer, or may be polymerized in several molecules to form an oligomer state β χ ' or a benzoxazine compound having a different structure may be used at the same time. Among them, bisphenol benzoxazine can be preferably used. Further, the resin composition can be used as a negative photosensitive resin composition by further adding an acrylic monomer and a photoradical generating agent. Further, it can be used as a positive photosensitive resin composition by adding a photoacid generator. The cured product can be obtained by heating the above resin composition. The addition state is not particularly limited, and it is preferred to carry out heating for 5 minutes to 6 minutes in each of the temperature zones of 2 stages, more preferably 1 〇〇e > c 〜 13 〇 (>c After heating for 5 minutes to 6 minutes, heat it for 15 kn. to ~60 minutes under 16 〇艽 to 2 Torr. Make it hard in 2 temperature zones as described above. 158118.doc

S-54-201237101, controlling the reaction between the compounds contained in the resin composition, can form a three-dimensional network. Further, by this, the heat resistance or chemical resistance of the cured product can be improved. More specifically, it is as follows. First, a polyfunctional hydroxyl group-containing compound is mainly reacted with a blocked isocyanate compound in a low temperature region (e.g., 10 ° C to 130 ° C) to form a urethane structure. Thereby, a chemical crosslinking between the polyfunctional hydroxyl group-containing compound and the blocked isocyanate compound is formed (hereinafter referred to as "step (I)"). Thereafter, a ruthenium imidization reaction of polyimine is mainly produced in a high temperature region (for example, 16 (TC to 200 ° C). Further, a polyfluorene in the polyimine remaining without unimlination is produced. The reaction of a carboxylic acid of an amino acid with an isocyanate group forms a guanamine structure or a urea structure, etc., thereby forming a chemical crosslink between the polyglycolic acid and the isocyanate 11 (hereinafter referred to as "step (11)" By the three-dimensional network formed by the cross-linking I and the cross-linking II, a cured product excellent in heat resistance can be obtained. Further, the isocyanate group remaining after the formation of the cross-linking II can be used. The remaining isocyanate groups are reacted with each other, whereby the active species are eliminated, and the insulating properties of the cured product can be improved. In the above step (II), depending on the thickness of the formed resin composition film, The oven or the hot plate is set to a temperature of 150 ° C to 220 ° C and heated in an inert atmosphere such as air or nitrogen for 5 minutes to 1 minute to remove the solvent. The heating temperature can be treated. The time is fixed as a whole, and the temperature can be gradually increased. The resin composition film can be used by It is formed by printing on a surface of a flexible printed circuit board or a semiconductor wafer by a known screen printing or precision dispensing method. The resin composition can exhibit excellent heat resistance by thermal curing, and thus can be used as a semiconductor element. Surface-hardened film, interlayer insulating film, and adhesive sheet, 158118.doc -55- 201237101 Protective insulating film for printed wiring boards, surface protective film for printed circuit boards, etc., suitable for various electronic parts. For example, as flexible A printed circuit board is coated with a resin composition on one part of the circuit board using Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (the thickness of the insulating layer is 25 μm, and the conductor layer is copper foil F2-WS〇8 μιη). To make it harden. The uncoated portion is plated with nickel-gold, which can be used as an external terminal. The surface protective film formed as described above exerts good insulating properties. Further, the thermal curing of the resin composition of the present embodiment is carried out under relatively low temperature conditions (e.g., 160 ° C to 200 ° C), so that oxidation of copper does not occur. The reason why such low-temperature hardening can be carried out is that the carboxylic acid reacts with the blocked isocyanate compound (accurately, the isocyanate compound which has been removed by heating), so that it becomes unnecessary to completely imidize and become unnecessary. 〇 It is heated at high temperatures. Further, the resin composition of the present embodiment can be used as a resin film by being applied to a substrate and dried. In addition, a double-sided copper foil plate of Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (the thickness of the insulating layer is 25 μηι, and the conductor layer is copper foil F2_WS (18 μηι)) is used to form a double-sided component mounting circuit board. The resin composition is applied and cured in addition to the component mounting portion of the circuit board, and the resin composition is used as a surface protective film, and excellent insulating properties can be exhibited. Here, the film thickness of the surface protective film is preferably from 1 μm to 50 μm. This is because the film thickness is 1 μm or more, and the operation becomes easy. When the thickness is 5 μm or less, it is easy to bend and it is easy to assemble. Furthermore, the resin composition of the present embodiment can also be provided by containing (D) photosensitive. 56-158118.doc

S 201237101 was used as a photosensitive resin composition. Further, a photosensitive film can also be obtained by applying a photosensitive resin composition to a substrate. Furthermore, the resin composition of the present embodiment can be suitably used as an interlayer insulating film such as a multilayer flexible wiring board by drying the resin composition on the copper foil. In addition, the resin composition of the present embodiment can be suitably used as a protective film for a wiring pattern of a wiring board by providing a resin composition so as to cover the wiring pattern formed on the substrate. (Second Embodiment) In the manufacturing process of the flexible printed circuit board, a coating layer excellent in electrical insulation reliability, bending resistance, heat resistance, and flame retardancy is required. In order to realize such a coating layer, a resin composition containing a polyaminic acid using an aliphatic diamine as a diamine component has been proposed. In the resin composition, the aliphatic diamine is contained in the poly-brenic acid. Therefore, there is a case where the developability is lowered for the following reasons: the molecular weight of the varnish which is obtained by dissolving the resin composition in the solvent is largely lowered. Further, when the pattern is formed by the lithography method, the residual film ratio is lowered, the pattern shape is deformed, and the like. The inventors of the present invention have focused on the use of a polyimine having a polydiamine structure and a polyglycolic acid structure as a structural unit as the (A) polymer compound. Furthermore, the present inventors have found that by containing (A) as a polymer compound, a polyimine having a polydiimide structure containing an aliphatic diamine component and a polyaminic acid structure as a structural unit, (B) a bifunctional hydroxyl group-containing compound as a polyfunctional hydroxyl group-containing compound, (c) a blocked isocyanate compound as a poly-B crosslinkable compound, and a photosensitizer, 158118.doc • 57-201237101, developability and warpage are good, A photosensitive composition having excellent insulating properties. In the photosensitive resin composition, a hydroxyl group of a bifunctional hydroxyl group-containing compound reacts with an isocyanate group of a blocked isocyanate compound to form an aminocarboxylic acid S structure, and a bifunctional hydroxyl group-containing compound is not embedded in a polyimine skeleton. The ground is present as a second component in the photosensitive resin composition. Thereby, the shrinkage of the polyimine skeleton at the time of hardening can be prevented, and the warpage can be reduced. Further, since the polydiimide component of the polyimine has an aliphatic diamine component, the molecular weight reduction due to the depolymerization of the polyglycolic acid structure can be suppressed. With this, the molecular weight is stabilized, so that the reduction in the residual film ratio or the deformation of the pattern shape when the pattern is formed by the lithography method can be suppressed, and the deterioration of the developability can be suppressed. Hereinafter, a second embodiment of the present invention will be specifically described. The photosensitive resin composition of the second embodiment of the present invention contains (a) a polyimine, (b) a bifunctional group-containing compound, (c-1) isocyanate compound (block isocyanate compound), and a photosensitizer. The molar ratio of the isocyanate group contained in the trans-group and the blocked isocyanate compound contained in the bifunctional hydroxyl group-containing compound is 0.5/1. In the resin composition, the molar ratio of the hydroxyl group contained in the bifunctional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate compound is hydroxy/isocyanate group = 0.5 to 1, so that excess isocyanate group and polyfluorene are present. A carboxylic acid reaction of a polyfluorene-amine structure contained in an imine. By this, a three-dimensional network is formed, and excellent insulation reliability can be achieved. Hereinafter, each component will be described in detail. (a) Polyimine 158118.doc 58-201237101 First, the polyimine in the photosensitive resin composition of the present embodiment will be described. In the photosensitive resin composition of the present embodiment, the polyketamine can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride to be used is not limited, and a previously known tetracarboxylic dianhydride can be used. As the tetracarboxylic dianhydride, an aromatic tetracarboxylic acid or an aliphatic tetracarboxylic dianhydride can be used. Further, the diamine to be used is not limited, and a previously known diamine can be used. In the photosensitive resin composition of the present embodiment, it is preferred to have a polyanilin structure represented by the following formula (3) from the viewpoint of self-developability and molecular weight stability. And the polyamic acid structures represented by the following general formula (4) are each a repeating structural unit.通 ] & β β ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' --- ΗΟη|Ύ〇Η Ο Ο

(In equations (3) and (4), Rl, r2, r4, R p p n ^ x 5 〜, R8, R10,

Rii, Ri3*!^4 independently represent a hydrogen atom or -r, and the number of extinctions is 1 to a carbon number of 20

The organic base of mussels may be the same or different. R Κ δ, Han 9, R12 and R15 158118.doc • 59- 201237101 An organic group having a carbon number of 1 to a carbon number of 4, and m, η, and p independently represent an integer of 0 or more and i00 or less. Rie said that the organic price of 4

Xv | - represents an organic group having a carbon number of 1 to a carbon number of 90. Further, the term "imine" is preferably an amide component which comprises a polyamine represented by the following formula (15) and which constitutes a polyimine structure represented by the above formula (3). [Chem. 23] Domain HfNH2 *^11 R|4 3

General formula (15) H2N~R R2 Rs Re (in the formula (15), R丨, R2, &, &, &, &, Ri, R" ' and

Rl4 independently represents a hydrogen atom or an organic group having a carbon number of 1 to a carbon number of 20, and may be the same or different. ^ It is assumed that the carbon number is an organic group having a carbon number of 20, and m, n, and p are each independently an integer of 30 30 or more, and satisfy t $ (m+n+p)g. As a method for synthesizing the polyimine, a tetrakis-di-gf and an aliphatic diamine represented by the above formula (15) are polymerized and cyclized to obtain a poly-imine. A method of polymerizing a diamine represented by the following formula (16). In the formula (16), r" represents an organic group having a carbon number of 〗 〖~ a carbon number of 9 。.) as a tetracarboxylic acid Two needles can be cited as _3,3,,4,4,_tetradecanoic acid dianhydride (hereinafter referred to as "BPDA"), two scorpion __3,3,,4,4,_tetracarboxylic acid (referred to as "BTDA" for short), two needles of oxydiphthalic acid (hereinafter referred to as "DpA"), diphenylphosphonium-3,3',4,4·-tetracarboxylic dianhydride, ethylene glycol Double (stupidized tridecanoic acid monoester anhydride) (hereinafter referred to as "tmeg"), p-phenylene bis (powdered tridecanoic acid monoester anhydride), dual bismale (trimellitic acid monoester acid =) Between, styling, bis(trimellitic acid monoester anhydride), phenyl bis(trimellitic acid monoester anhydride), pentanediol bis(trimellitic acid monoester anhydride) (hereinafter referred to as "5-BTAj", bismuth diol bis (powdered triacetic acid monoacetate), pyromellitic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 4,4, (2 , 2· hexafluoroisopropylidene) bisphthalic acid dianhydride, m-triphenyl_3,3,4,4,4-tetracarboxylic dianhydride, 1,2, 4,5_cyclohexanetetracarboxylic dianhydride, bicyclo[2,2,2]octyl-7-ene-2'3,5,6-tetracarboxylic dianhydride, cyclobutane·1,2,3,4 _tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6:3,5-dianhydride, 4-(2,5-di-tertiary oxytetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-indole, :^ Dicarboxylic acid anhydride, etc. The above-mentioned tetracarboxylic dianhydride may be used singly or in combination of two or more kinds. Further, from the viewpoint of developability of polyanilin, BpDA, ODPA, BTDA, TMeg are more preferable. (4) Old. The structure represented by 5_bta and decanediol bis (p-trimethylene carboxylic acid as the above formula (〗 〖5) is not a single amine, and if it has the above formula (15), it is exemplified. Diamine-based 3,6-dioxy 158118.doc * 61 - 201237101 octyl polyoxyl ethylamine compound, JEFFAMINE EDR-148, EDR-176, etc. manufactured by Huntsman Co., Ltd. Amine compound, JEFFAMINE D-230, D-400, D-2000, D-4000, polyether amine D-230, D-400, D-2000, etc. a compound, a compound having a different alkyloxy group, etc., such as HK-511, ED-600, ED-900, ED-2003, XTJ-542, etc. By using these compounds having an alkyloxy group, a polyfluorene can be obtained. The warpage of the Fpc after calcination of the imine is reduced. In the diamine represented by the above formula (15), 'm, η, and p are each independently an integer of 〇 or more and 3 Å or less. From the viewpoint of insulation reliability, it is preferable that l$(m+n+p)$30' is more preferably 3S(m+n+p)$l〇. For example, l$(m+n+P)S30 has a short skeleton of an alkyloxy group, and it is presumed that the elastic modulus of the polyimine is increased and the insulation reliability is improved. Further, in the case where the usual oxyalkylene group skeleton is short, there is a tendency to exhibit warpage. However, in the present embodiment, it is presumed that the bifunctional hydroxyl group-containing compound and the blocked isocyanate are used in combination. When the warpage is maintained in a good state, the insulation reliability is further improved. The polyimine of the present embodiment has a polyimine structure and a polystyryl structure, and each of them is a repeating structural unit, and a diamine represented by the above formula (15) is introduced into the polyimine structure. The molecular weight of the polyimide and varnish is stable. If the diamine of the above formula (15) is introduced into the poly-amino acid structure, the aliphatic diamine has a higher basicity, and in comparison with the previous poly-proline, the poly-aracine is promoted. Depolymerization, & sub-quantity reduction becomes significant. It can be introduced into the polyimine structure; ρ is stabilized by the testability of the aliphatic triamine to 158118.doc -62- 201237101. Examples of the diamine represented by the above formula (16) include bismuth(4-aminophenyloxy)hydrocarbon, 1,4-bis(4-aminophenoxy)alkane, anthracene, 5 _Bis(4-aminophenyloxy)alkane, 1,4-diaminobenzene, hydrazine, 3-diaminobenzene, 2,4-diaminomethyl, 4,4'-diaminodiphenyl Methane, 4,4,-diaminodiphenyl ether, 3,4,-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethylmonoaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,7-monoamino-dimercaptobenzophenone _5,5_dioxide, 4,4·-diamino-indolenone, 3,:V-monoaminobenzophenone, 4,4'-bis(4-aminophenyl)sulfide Ether, 4,4'-diaminobenzimidamide, iota, 3-bis(4-aminophenoxy)_2,2-dimethylpropane, 1,2-bis|; 2-(4 -Aminophenoxy)ethoxy]Ethylene, 99_bis(4-aminophenyl) drug, 5-amino-1-(4-aminoindenyl)_ι, 3,3-trimethyl Dihydroanthracene, 1,4-bis(4-aminophenoxy) stupid, 1,3-bis(4-aminophenoxy) stupid, 1,3-bis(3-aminophenyl fluorenyl) Benzene (hereinafter referred to as APB), 4, 4'-double 4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2.bis(4-aminophenoxy)propylamine (hereinafter referred to as BAPP) ), trimethylene-bis(4-aminobenzoate) (hereinafter abbreviated as TMAB), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminobenzene 4-Aminobenzoic acid vinegar, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2- Bis[4-(4-amine basic oxy) phenyl] hexafluoropropanone, 1-amino-3-aminoindolyl-3,5,5-tridecylcyclohexane, 3,3' ··Dicarboxy-4,4·-diaminodiphenylnonane, 3,5-diaminobenzoic acid, 3,3′·.dihydroxy-4,f-diaminobiphenyl, 1, 3-bis(4-aminophenoxybenzene) and the like. Among them, APB, BAPP, and TMAB are preferred from the viewpoints of low Tg and developability of polyimine. These diamine moieties 158118.doc • 63· 201237101 can also be used as the diamine used in the polyimine. Further, in the present embodiment, it is preferred that the polyimine has a structure represented by the following formula (6) as a repeating unit. General formula (6)

C

(In the formula (4), R1, R2, R4, R5, R7, R8, R10, Rn and R1A R!4 each independently represent a hydrogen atom or an organic group having a carbon number of 丨 and a carbon number of 2〇. It can be the same or different. ^, ^, ^, 尺^ and 尺^ represent an organic group having a carbon number of 4 and a valence of 20, and m, n, and p each independently represent an integer of 30 or more 〇. The tetravalent organic group is represented, and the r-gate represents an organic group having a carbon number of 1 to a carbon number of 90. A, B, and c represent mol% of each unit, and satisfy 〇.1〇$ (A+B). /(A+B+C)^ 〇.) From the viewpoint of the structure of the above formula (6), from the viewpoints of self-developability, interest, and insulation reliability, it is preferable that 〇.1〇S(a+ b) / (a + b + c) ^ to, more preferably (M5S (A + B) / (A + B + C) $ ο", further more than 1 gui: 〇. 2WA + B) / ( A+B+C) The structure (A+B) containing the above-mentioned diamine represented by the above formula can be reduced by 〇1〇 or more with respect to the whole. X' by inhibiting the elastic modulus and the glass transition by making the conformation (A+B) containing the diamine represented by the above formula (15) to 〇85 or less with respect to the whole, ''Ό Λ Λ The decrease of the point (Tg) keeps the insulation reliable, and the structure of the polyamidimide (A+B) is relatively old with respect to the whole. In the case of 85 or less, the solubility is improved in the alkaline developing solution with respect to 15811S.doc • 64 · 201237101, and the developability is improved. The end of the main chain of the polyimine is not particularly limited as long as it does not affect the performance. The terminal end of the acid dianhydride or the monoamine used in the production of the polyimine may be blocked by another acid anhydride, an amine compound or the like. The average molecular weight of the weight of the chitoimide is preferably 1 Å or more. Here, the weight average molecular weight means a molecular weight measured by gel permeation chromatography using a known weight average molecular weight of polystyrene as a standard. From the viewpoint of the weight average molecular weight 'from the strength of the polybenzazole amount, it is preferably 1,000 or more. Further, from the viewpoint of the viscosity and moldability of the polyimine-containing resin composition, the following is preferable. More preferably, the weight average molecular weight is 5,000 or more and 500,000 or less, more preferably 10,000 or more and 300,000 or less, and most preferably 20,000 or more and 5 or less. The polyimine having a polyimine structure and a poly-proline structure as a repeating unit, respectively, can be produced by reacting an acid dianhydride with a diamine in a non-equal molar amount and synthesizing the first stage. The step of the quinone imine moiety (step 1), followed by the second stage of the step of synthesizing the polyaminic acid moiety (step 2). The following steps are explained. (Step 1) The procedure for synthesizing the polyimine portion of the first stage will be described. The step of synthesizing the polyimine portion in the first stage is not particularly limited, and a known method can be applied. More specifically, it can be obtained by using ~々>2:. First, the diamine is dissolved and/or dispersed in a polymerization solvent, and an acid dianhydride powder is added thereto at 158118.doc -65 - 201237101. Then, a solvent azeotroped with water is added, and the by-product water is azeotropically removed using a mechanical stirrer, and heating is carried out for 5 hours to 96 hours, preferably 0.5 hours to 30 hours. In this case, the monomer concentration is 5% by mass or more and 95 Å/Å or less, preferably 1% by mass or more and 90% by mass or less. In the case of synthesizing the polyimine portion, it is possible to add It is known that an imidization catalyst is used to obtain a polyimine moiety, and a polyimine moiety can also be obtained by a catalyst-free medium. The ruthenium-based catalyst is not particularly limited, and examples thereof include an acid anhydride such as acetic anhydride. a lactone compound such as γ-valerolactone, γ-butyrolactone, 7-telic acid, azlactone, coumarin, or γ-lactone, such as pyridine, 啥琳, Ν-曱A tertiary amine such as a morpholine or a triethylamine, etc., may be used alone or in combination of two or more kinds thereof, in particular, from the viewpoint of the height of the reactivity and the influence on the subsequent reaction. Particularly preferred is a mixture of γ-valerolactone and guanidinium and a non-catalyst. The amount of the ruthenium imidization catalyst added is preferably 1 part by mass. 50 parts by mass or less, more preferably 30 parts by mass or less. As the reaction solvent used in the synthesis of the polyimine moiety, for example, dimethyl An ether compound having a carbon number of 2 or more and 9 or less, such as diethyl ether, mercaptoethyl ether, tetrahydrofuran, dioxane, ethylene glycol dioxime ether, diethylene glycol dimethyl hydrazine or triethylene glycol dimethyl sulfonate a ketone compound having a carbon number of 2 or more and 6 or less such as acetone or methyl ethyl ketone; a carbon number of 5 such as n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane or decalin; a saturated hydrocarbon compound having less than 1 以上 above; such as benzene, toluene, xylene, mesitylene, and chlorinated aromatic compounds having a carbon number of 6 or more and 10 or less; such as B 158118.doc • 66· 201237101 Western An ester compound having a carbon number of 3 or more and 12 or less such as methyl hydrazine, ethyl acetate or γ-butyrolactone oxime benzoate; carbon number such as gas-like, di-halogen methane, ι, 2-di-ethane It is a functional element containing less than 1 ; above; for example, acetonitrile ' Ν, Ν 甲基 甲基 醯 Ν Ν Ν Ν Ν 曱 曱 曱 曱 曱 曱 曱 曱 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基a nitrogen-containing compound of 2 or more and 10 or less; a sulfur-containing compound such as a dimercapto sulfoxide. These may be sputum or two or more. A particularly preferred solvent is an ether compound having 2 or more and 9 or less carbon atoms, an ester compound having 3 or more and 12 or less carbon atoms, an aromatic hydrocarbon compound having 6 or more and 10 or less carbon atoms, and a carbon number of 2 or more. The following nitrogen-containing compounds may be arbitrarily selected in consideration of industrial productivity, effects on subsequent reactions, etc. In the synthesis of the polyamidene moiety, it is preferred that the reaction temperature be 15 ° C or more. When the reaction temperature is 15 〇c or more, the reaction starts and is 250. (: The following is not activated by the catalyst. It is preferably 20 C or more and 220. More preferably, it is 2 〇 ° C or more and 200 ° C or less. The reaction needs to be different depending on the purpose or reaction conditions, and is usually within 96 hours, and particularly preferably in the range of 3 Torr to 3 Torr. Implementation. (Step 2) Next, the step of synthesizing the polyamic acid moiety of the second stage will be described. The synthesis of the second stage polyamine moiety can be carried out by using the polyimine fraction obtained in the step 1 as a starting material and polymerizing by chasing an amine and/or an acid anhydride. The superposition temperature at the time of synthesis of the second-stage polyaminic acid moiety is preferably 〇°C or more and 250° C. or less, more preferably 158118.doc •67-201237101 is 0 C or more and 100 c or less, particularly preferably 〇 It is above 80〇c. The time required for the reaction in the synthesis of the poly-aracine is different depending on the purpose or the reaction conditions, and is usually within 96 hours, and particularly preferably in the range of from 3 minutes to 3 hours. As the reaction solvent, the same reaction solvent as used in the synthesis of the polyimine portion in the step 1 can be used. In this case, the synthesis of the polyaminic acid moiety can be carried out directly using the reaction solution of the step 1. Further, a solvent different from the reaction solvent used in the synthesis of the synthetic polyimine moiety can also be used. Examples of such a solvent include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dioxime ether, diethylene glycol dimethyl hydrazine, and diethylene glycol dioxime ether. Such an ether compound having a carbon number of 2 or more and 9 or less; a ketone compound having a carbon number of 2 or more and 6 or less such as propylene or butanone; such as n-pentane, cyclopentane, n-hexane, cyclohexane, methyl a saturated hydrocarbon compound having a carbon number of 5 or more and 1 Torr or less such as cyclohexane or decalin; a carbon number such as benzene, toluene, diphenyl, mesitylene, or tetralin is 6 or more and less than An aromatic hydrocarbon compound; an ester compound having a carbon number of 3 or more and 12 or less such as methyl acetate, ethyl acetate, γ-butene, methyl benzoate; for example, gas-like, mono-methane, 1,2- a halogen-containing compound having a carbon number of 1 or more and 10 or less such as acetonitrile, N,N-dimethylformamide, hydrazine, hydrazine dimethyl ethanoamine, hydrazine-methyl-2- A nitrogen-containing compound having a carbon number of 2 or more and 1 Torr or less such as pyrrolidone; a sulfur-containing compound such as dimethyl hydrazine. These solvents may be used alone or in combination of two or more. The solvent which is particularly preferable is an ether compound having a carbon number of 2 or more and 9 or less, an ester compound having a carbon number of 158118.doc -68 · 201237101 3 or more and 12 or less, and a carbon number of 6 or more. A compound or a nitrogen-containing compound having 2 or more and 10 or less carbon atoms. These can be arbitrarily selected for industrial productivity, influence on subsequent reactions, and the like.醯 After the production, the polyimine can be used in the reaction solvent, and can be recovered and purified by the following method. Further, the recovery of the polyimine after the production can be carried out by subtracting the solvent from the reaction solution. The method for purifying the polyamidiamine includes a method of removing the acid dianhydride and the diamine which are insoluble in the reaction solution by pressure reduction, pressure filtration or the like. Further, a purification method in which a reaction solution is added to a poor solvent to cause precipitation, that is, so-called reprecipitation, can be carried out. Further, in the case of a polyimine which is required to have a purity, it is also possible to use a purification method using extraction of supercritical carbon dioxide. In the photosensitive resin composition of the present embodiment, the bifunctional hydroxyl group-containing compound and the blocked isocyanate are contained to improve the insulation reliability and to suppress warpage. It is presumed that the crosslinked body is formed by the reaction of the hydroxyl group contained in the bifunctional hydroxyl group-containing compound with the isocyanate group contained in the blocked isocyanate, and thus the insulation reliability is improved. Further, since the bifunctional hydroxyl group-containing compound is present as a second component without being embedded in the skeleton of the polyimide, it is possible to prevent shrinkage of the polyimide phase skeleton during curing and to suppress warpage. Further, by including a blocked isocyanate, the carboxyl group can be deactivated at a low temperature and can be cured at a low temperature. Therefore, shrinkage of the polyimine skeleton at the time of curing can be prevented, and distortion can be suppressed. Further, in the above embodiment, an example in which poly(imine) is used as the (Korean) 158118.doc • 69· 201237101 knives is described, but a polylactoic acid-free structure may also be used. As a (A) polymer compound, polyugly imine, a polyamine which does not contain a polyimine structure, and a polyamine quinone which has a polyphthalic acid structure and a polyimine structure. Further, in the resin composition of the present embodiment, from the viewpoint of heat resistance, the hydroxyl group contained in the bifunctional hydroxyl group-containing compound and the mole of the isocyanate group contained in the blocked isocyanate are preferably a hydroxyl group/isocyanate group. =0.5~1. (b) The bifunctional hydroxyl group-containing compound is a bifunctional hydroxyl group-containing compound, and the same as the polyfunctional hydroxyl group-containing compound used in the resin composition of the first embodiment can be used within the range of the effects of the present invention. . (c-1) Block Isocyanate Compound The block isocyanate compound can be the same as the blocked isocyanate compound used in the resin composition of the above-mentioned Example. In the same manner as the resin composition of the first embodiment, other polyfunctional isocyanate compounds or polyfunctional isocyanate compounds can be used in the range of the effects of the present invention. (D) Photosensitive Agent The photosensitive resin composition of the present embodiment contains a (fluorenyl) acrylate compound having at least two photopolymerizable unsaturated double bonds as a photosensitizer, and further contains (E) a photopolymerization initiator. . The photosensitizer in the photosensitive resin composition of the present embodiment is a compound which has a property of being changeable in structure due to light irradiation and having a change in solubility with respect to a solvent. In the present embodiment, 70. 158118.doc

The photosensitive resin composition of the form of S 201237101 contains a (fluorenyl) acrylate compound having two or more photopolymerizable unsaturated double bonds and a photopolymerization initiator, and therefore has two or more photopolymerizable Since the (meth) acrylate compound of the double bond is saturated to form a crosslinked body, developability and insulation reliability are improved. Examples of the (fluorenyl) acrylate compound having two or more photopolymerizable unsaturated double bonds include dihydroarylene alcohol diacrylate and ethylene oxide (EO) modified bisphenol A dimethyl group. Acrylate, EO modified hydrogenated bisphenol A dipropylene oxime, 1,6-hexanediol (mercapto) acrylic acid vinegar, iota, 4-cyclohexanediol bis(indenyl) acrylate, polypropylene glycol (fluorenyl) acrylate, polyethylene glycol bis(indenyl) acrylate, 2-bis(p-hydroxyphenyl)propane bis(indenyl)acrylic acid, tris(2-propenyloxyethyl) Tricyanate, ε-caprolactone modified bis(propylene oxyethyl) isomeric cyanurate, glycerol tris(methyl) propyl hydrazine 1 曰, dipyridyl propyl acrylate Tris(meth)acrylate, polyoxyl-propyltrim-ylpropanepropane tri(meth)acrylate, polyoxyethylidene trishydroxypropylpropane tris(meth)acrylate, dipentaerythritol five (曱) Acrylate, trimethyl propylene triglycidyl ether (meth) acrylate, bisphenol hydrazine diglycidyl ether bis(indenyl) acrylate, β hydroxypropyl _|3, _ (Propylene oxy-oxypropyl phthalate, phenoxy polyethylene glycol (decyl) acrylate, hydrazine basic ethoxypoly(vinyl) acrylate, pentaerythritol tris(fluorenyl) propyl Orthoester, pentaerythritol tetrakis(meth)acrylate, pentaerythritol tris/tetrakis(fluorenyl) acrylate, etc. "In view of self-developing or warpage after calcination, yttrium-modified bisphenol a is preferred. Dimethacrylate, hydrazine-modified hydrogenated bisphenol A diacrylate, pentaerythritol tri/tetra(meth) acrylate. 158118.doc •71- 201237101 Also, from the viewpoint of self-developability and insulation reliability, Preferred is a combination of a compound having two double bonds and a compound having three or more double bonds. A compound having three or more double bonds forms a straight crosslinked body, and thus the elastic modulus or glass transition point of the cured film is estimated ( Tg) becomes high, and insulation reliability is advanced. Generally, when a compound having three or more double bonds is contained, there is a tendency for warpage to occur due to an increase in cross-linking points. However, in the present embodiment, a warp-containing group is included. Compound does not Since the compound having a double bond forms a crosslinked structure and exists as a second component in the photosensitive resin composition, the surface curvature can be reduced. As a compound having three or more double bonds, pentaerythritol tri/tetraacrylate can be mentioned. (trade name: ARONIX (registered trademark) M-306, manufactured by Toagosei Co., Ltd.), trimethylolpropane PO modified triacrylate (trade name: ARONIX M-3 10, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate vinegar (trade name: A-TMMT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), E-modified glycerol tris(mercapto) acrylate (trade name: A-GLY-9E (EO modified 9 mol), Shin-Nakamura Chemical Manufactured by Industrial Co., Ltd., di-trimethylolpropane tetraacrylate (trade name: ARONIX M_4〇8, manufactured by Toagosei Co., Ltd.), dipentaerythritol 5 and hexaacrylate (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd. )Wait. The amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is from the viewpoint of 'self-developability' when the amount of the polyimine is set to 1 part by mass. It is preferable that it is 5 parts by mass or more and 60 parts by mass or less, and more preferably 10 parts by mass or more and 40 parts by mass or less. -72· 158118.doc

S 201237101 In the case where the resin composition of the present embodiment is not used as a photosensitive resin, it is not always necessary to use (D) a photosensitizer. (E) Photopolymerization initiator as a photopolymerization initiator' can be exemplified by benzoin dimethyl condensate such as 2,2-dimethoxy-oxime, 2-diphenylethane-1-one Ketones, styrenes, dipropyl ketals, stupid diphenyl ketals, benzoin ethers, benzoin ethyl ether. Sesone, 2,4-dimethyl alpha serotonin, 2,4-diethyl. Seidone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-isopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone, 2- Gas thioxanthone, 4-air thioxanthone, 1 · gas _ 4-propoxy thioketidine, benzophenone, 4,4, bis (didecylamino) benzophenone [米其An aromatic ketone compound such as lysine, 4,4'-bis(diethylamino)benzophenone or 2,2-dimethoxy-2-phenylacetophenone, octomer dimer, etc. Acridine compound such as a dimer of a dimer, a phenyl acridine, α,α-dimethoxy oxime-morpholinyl-methylthienylacetophenone, 2,4,6-tridecyl An oxime ester compound such as benzamidine bisphosphonium phosphine oxide or fluorenyl-aryl _α-amino acid, p-didecylaminobenzoic acid, p-didecylaminobenzoic acid, p-diethylamino group Benzoic acid, p-diisopropylaminobenzoic acid, p-benzoate, μhydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenylpropanone, ^[4-(2-Hydroxyethoxy)-benzyl]-2-yl-2-yl-1-propan-1-one, 2-yl-l-{4-[(2- Basicity of α-hydroxyl burning such as hydroxy-2-indolyl-propionyl)-benzyl]phenyl}_2-methyl-propane·buxone Ketones '2-methyl-1 -(4-mercaptoπ-sepeno)_2-indole-l-propylpropan-1-one, 2-(dimethylamino)_2-[(4-methyl) α-Aminoalkylphenones such as phenyl)methyl]-1-[4-(4-indole-morpholino)phenyl]-1-butanone, 2,4,6-trimercaptobenzene Mercapto-diphenyl-phosphine oxide, bis(2,4,6-trimethylphenyl fluorenyl)·Bist 158118.doc -73- 201237101 fluorenylphosphine oxides such as phosphine oxides, 1, 2 -octanedione 1-[4-(phenylthio)_2_(〇·benzophenone)], ethyl ketone 1-[9-ethyl_6_(2-methylbenzylidene)·9Η_咔An oxime ester such as oxazol-3-yl]-1-(anthracene-ethene). Among these, from the viewpoint of sensitivity, 'excellent vinegars are preferred. In the case where the amount of the polyamidimide is 1 part by mass, the amount of the photopolymerization initiator is preferably 0.01 parts by mass or more and 40 parts by mass or less from the viewpoint of sensitivity and resolution. More preferably, it is 0 5 parts by mass or more and 35 parts by mass or less. (F) Phosphorus compound It is preferred that the photosensitive resin composition contains a phosphorus compound. The phosphorus compound is not limited as long as it contains a phosphorus atom-containing compound in the structure. The phosphorus compound of the present invention may be a phosphate compound having a phosphate structure or a phosphazene compound having a phosphazene structure. Examples of the phosphate compound include a phosphate ester having an aliphatic hydrocarbon group as a substituent such as tridecyl phosphate, triethyl sulphate, tributyl phosphate, triisobutyl phosphate, or tris(2-ethylhexyl) phosphate. a phosphate such as tris(butoxyethyl)acetate or the like, which is substituted with an aliphatic organic group containing an oxygen atom, triphenyl phthalate, triphenyl phenyl phosphate, tris(xylylene) phosphate, and isophthalic acid. A phosphate compound or the like having an aromatic organic group as a substituent such as phenol bis(diphenyl phosphate). In the above, from the viewpoint of the self-developability, tris(butoxyethyl) phosphate and triisobutyl phosphate are preferable. Examples of the phosphazene compound include the following formula (17). The structure represented by the formula (18) and the like. 158118.doc -74- 201237101 [Chem. 26] General formula (17)

^2| 0 —Point=Ν· Λ R22 V General formula (18)

G R23 ΟP=N- I0 I R24 ............

W is not limited as R21 R22 R23 and r24 in the nitrile compound of the above formula (10), and is an organic group having a carbon number of i or more plus or less. When the carbon number is 1 or more, it is present. It is preferable to exhibit a tendency to be flame-retardant. When the carbon number is 20 or less, it tends to be compatible with polyimine, and it is preferable from the viewpoint of exhibiting flame retardancy. The functional group of the aromatic compound. Examples of such a functional group include a phenyl group, a 2.f-phenyl group, a 3-methylphenyl group, a fluorenylphenyl group, a 2: phenyl group, and a 3-amino group. a base having a phenyl group such as a phenyl group, a phenyl group, a cyanophenyl group, a cyanophenyl group, a cyanophenyl group, a 4-cyanophenyl group, or the like, and a naphthyl group such as a 1-naphthyl group or a 2-naphthyl group. The functional group is derived from 15S118.doc •75· 201237101. The functional group of the nitrogen-containing heterocyclic compound such as tetrazole or the like, and the like. These compounds may be used alone or in combination of two or more. For use in combination, it is preferred to have a compound of a phenyl group, a 3-methylphenyl group, a 4, a phenyl group, and a cyanophenyl group. Said In the phosphazene compound, if it is 3 or more and 25 or less, it is limited to. When it is 3 or more, it exhibits flame retardancy, and if it is the following, it has high solubility in an organic solvent. In the phosphazene compound represented by the above formula (18), w is preferably 3 or more and 10,000 or less, and is not limited to 3 or more, and is preferably 3 or more. When the flame retardancy is 〇〇〇 or less, the solubility in an organic solvent is high. Among them, in particular, from the viewpoint of ease of availability, it is preferably 3 or more. The phosphazene compound is not limited to an organic group having a carbon number of 3 or more and 30 or less. Among them, as G, it is preferred that -N=P(〇C6H5)3 '-N=P( 〇C6H5)2(〇C6H4OH) '-N=P(OC6H5)(〇C6H4〇H)2 ^ -N=P(0C6H40H)3, -N=P(〇)(〇c6H5), -N=p( o) (〇c6H4〇H). As j ', it is preferable that Οί^Η5)4, _p(〇C6H5)3(〇C6H4〇H), -P(OC6H5)2(〇C6H4OH)2, -P (〇C6H5)(OC6H4OH)3, -p(oc6H4〇H)4, -P(〇)(〇c6H5)2^-P(0)(0C6H40H)2 > -P(0)(0C 6H5) (0C6H40H) and so on. As the phosphorus compound, a phosphorus compound can be used, and two or more kinds of phosphorus compounds can be used in combination. The amount of the compound to be added in the photosensitive resin composition is from the viewpoint of the self-developability or the like when the amount of the polyimine is 100 parts by mass.

S -76- 201237101 is preferably 5 parts by mass or less. From the viewpoint of the flame retardancy of the hardened body, it is more preferably 45 parts by mass or less. Moreover, when it is 5 mass parts or more, an effect is exhibited. (G) Other compounds In the photosensitive resin composition, other compounds may be contained in a range which does not adversely affect the performance. Specific examples thereof include a thermosetting resin used to improve the toughness, solvent resistance, and heat resistance (thermal stability) of the film after firing, and a compound reactive with polyimine. Further, a heterocyclic compound for improving the adhesion and a pigment or dye for coloring the film may be mentioned. Examples of the thermosetting resin include an epoxy resin, a cyanic acid (tetra) grease, an unsaturated polyacetal resin, and benzo. Oxazine resin, benzoxene, resin, melamine resin, maleimide compound, and the like. Examples of the compound which has an antibiotic activity with a polyruthenium group include a compound which can react with a carboxyl group, an amine group or a terminal group in the polymer to form a three-dimensional crosslinked structure. Among them, the more advanced a 丄 圭 圭 圭 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 。 。 。 。 。 。 。 。 For example, there is a compound obtained by subjecting an amine group such as an amine compound such as an amine to a salt structure by using an acid such as a sulfonic acid, and protecting it by a sulfonic acid compound, and purging it with a chlorinated compound. Thereby, it is possible to produce a hot base generator which does not exhibit alkalinity at room temperature and which can be deprotected by heating to produce a base. The heterocyclic compound is not limited to a compound containing a heterocyclic ring. Here, the hetero atom 7 hetero atom in the present embodiment may be exemplified by oxygen, sulfur, nitrogen, and phosphorus. As a specific example, for example, Tian* Mickey, sitting, 2-ten-alkyl M. • ΊΊ 158118.doc 201237101. An imidazole such as 2-ethyl-4-methylimidazole or 2-phenylimidazole, such as N-alkyl substituted imidazole such as 1,2-dimethyl-salt, 丨-benzyl-2-indole An aromatic group-containing imidazole such as imidazole, 1-benzyl-2-stackylimidazole, etc., decyl cyanoethyl 2 - hydrazinyl oxime, cyanoethyl-2-ethyl-4-hydrazinyl oxime, An imidazole compound such as an imidazole such as a cyano group, such as a cyano group, a 1-cyanoethyl imidazole or a 1-cyanoethyl-2-phenylimidazole, etc. Triazole compounds such as benzotriazole, 1-(1,2,-dicarboxyethylbenzotriazole), 1 (2 ethylhexylaminodecyl benzotriazole), 2-methyl-5 An oxazole compound such as phenyl benzoxazole. As a pigment or a dye, a phthalocyanine type compound is mentioned. The amount of the other compound to be added is not limited to 1 part by mass or more and 30 parts by mass or less. When it is 1 part by mass or more, the coloring property of the film may be sufficiently increased, and if it is 3 parts by mass or less, there is no adverse effect on photosensitivity or the like. The photosensitive resin composition may optionally contain an organic solvent. If the organic solvent is such that the polyimine is uniformly dissolved and/or dispersed, the organic solvent may be, for example, dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran or the like. An ether compound having a carbon number of 2 or more and 9 or less such as an alkylene oxide, an ethylene glycol dimethyl ether, a diethanol monomethyl sulphate or a diethylene glycol dimethyl sulphide; a carbon number such as acetone or methyl ketone is 2 or more and 6 or less a ketone compound such as n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane or decahydronaphthalene; a saturated hydrocarbon compound having a carbon number of 5 or more and 1 Torr or less; such as benzene, toluene, An aromatic hydrocarbon compound having a carbon number of 6 or more and 10 or less such as toluene, mesitylene or tetralin; such as methyl acetate, ethyl acetate, 158118.doc

S -78· 201237101 An ester compound having a carbon anisotropy such as butyrolactone or methyl benzoate of von 3 or higher; for example, carbon number such as gas imitation, dichlorodecane, and 1 2_ _隹' _ hexane a halogen-containing compound of 1 or more and 10 or less; such as carbon such as acetonitrile, N,N-dimethyldecylamine, N,N-dimethylacetamide, N-methyl 9-methyl-2-pyrrolidone A nitrogen-containing compound having a number of 2 or more and 10 or less; for example, a sulfur-containing compound 0 of 2 ▲ 〒 亚 ia, which is preferably a mixture of 1 or 2, or more. The solvent which is particularly preferable is a compound having a carbon number of 2 or more and 9 or less, a brewing compound having a carbon number of 3 or more and 9 or less, an aromatic hydrocarbon compound having a carbon number of 6 or more and 1 or less, and a carbon number of 2 or more and 10 or less. A nitrogen-containing compound, or a work type thereof, or a mixture of two or more thereof. χ, from the viewpoint of the solubility of polyimine, preferred is triethylene glycol n Ν _ methyl · 2 _ π 洛 鲷 鲷, γ-butane vinegar, N, N-dimethyl amide , N,N-dimethyletheneamine. The degree of the polyimide of the resin composition containing the polyimine and the organic solvent is not particularly limited as long as the concentration of the resin molded body can be formed. From the viewpoint of the film thickness of the resin molded body to be produced, the concentration of the polyimine is preferably 1% by mass to ±, and the concentration of the polyanilin is higher than the uniform thickness of the film thickness of the resin molded body. The best is 9 〇 mass% or less. From the viewpoint of the film thickness of the obtained resin molded body, it is more preferably 2% by mass or more and 80% by mass or less. (H) Photosensitive film The photosensitive resin composition of the present embodiment can be suitably used for the formation of a photosensitive film. The photosensitive film of this embodiment can be obtained by applying a photosensitive resin composition to a substrate. Further, in the photosensitive 臈158118.doc 79: 201237101 of the present embodiment, it is preferable to include a carrier film, the photosensitive resin composition provided on the carrier film, and the photosensitive resin composition. Cover the film. The concentration of the polyimine in the photosensitive resin composition is preferably 1 mass from the viewpoint of producing a photosensitive film. /. The above-mentioned 90% by mass or less is considered to be preferably 1% by mass or more from the viewpoint of the film thickness of the photosensitive film from the viewpoint of the film thickness of the polyimide film, and the viscosity of the photosensitive resin composition and the uniformity of the film thickness. It is considered that 'it is preferably 9% by mass or less. From the viewpoint of the film thickness of the obtained photosensitive film, it is more preferably 2% by mass or more and 80% by mass or less. Next, a method of producing a photosensitive film will be described. First, a photosensitive resin composition is applied onto a substrate. The substrate is not limited as long as it is a substrate that does not damage when the photosensitive film is formed. Examples of such a substrate include a ruthenium wafer, glass, ceramics, heat resistant resin, carrier film, and the like. As the carrier film, a polyethylene terephthalate film or a metal film can be cited. From the viewpoint of good handling, a heat-resistant resin and a carrier film are preferable, and a polyethylene terephthalate film is particularly preferable from the viewpoint of the releasability after pressure-bonding of the substrate. The coating method may, for example, be bar coating, roll coating, die coating, knife coating, dip coating, blade coating, spray coating, shower coating, spin coating, slit coating, brush coating or the like. After the coating, a heat treatment called prebaking may be performed by a hot plate or the like as needed. In the case of producing a photosensitive film containing a photosensitive resin composition, a solution of the photosensitive resin composition is applied onto an arbitrary substrate (carrier film) by any method. Next, the photosensitive resin composition is dried and dried, and then formed into a laminated film comprising a carrier film and a photosensitive film. 158118.doc οη • 80 -

S 201237101 Further, at least one layer of an anti-fouling or protective cover film may be provided on the photosensitive film to form a laminated film. In the laminated film of the present embodiment, the cover film is not limited as long as it is a film that protects the photosensitive film such as low-density polyethylene. (I) Flexible printed wiring board The photosensitive film of this embodiment can be suitably used for a flexible printed wiring board. The flexible printed wiring board of the present embodiment includes the above-mentioned photosensitive film provided with a substrate made of a wiring and covering the wiring on the substrate. The flexible wiring board can be obtained by pressure-bonding a photosensitive film to a substrate having a wiring, performing alkali development, and then satin burning. Examples of the substrate having a wiring in the flexible printed wiring board include a hard substrate such as a glass epoxy substrate or a glass maleimide substrate, or a flexible substrate such as a copper-clad laminate. . Among them, a flexible substrate is preferred from the viewpoint of bendability. The method of forming the flexible printed wiring board is not limited as long as it forms a photosensitive film on the substrate so as to cover the wiring. As such a formation method, hot pressing, hot lamination, hot vacuum pressing, hot vacuum lamination, or the like is performed in a state where the wiring side of the substrate having the wiring is in contact with the photosensitive film of the embodiment. Method, etc. Among them, from the viewpoint of embedding the photosensitive film between wirings, 'preferably, hot vacuum pressing and hot vacuum lamination. The heating temperature at the time of laminating a photosensitive film on a green substrate is not limited. The temperature at which the film can be adhered to the substrate is not limited. From the viewpoint of the connection on the substrate or the viewpoint of photodegradation or side reaction, it is preferable that it is 3 (rc or more, or less. More preferably, it is a thief or more, i50.: 158118.doc • 81 - 201237101 or less The whole surface treatment of the substrate having the wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and aqueous sodium persulfate treatment. The photosensitive film can be dissolved by light irradiation by alkali development after light irradiation. Outside the part, the negative green lithography method can be performed. In this case, the light source can be cited as a high M mercury lamp, an ultra high pressure mercury lamp, a low pressure mercury lamp, a metal self lamp, a gas lamp, a fluorescent lamp. , 嫣 灯 ' 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛 氛Examples of such a solution include an aqueous solution of sodium carbonate, a carbonated product, an aqueous solution of hydroxyxanthine, an aqueous solution of hydrazine hydroxide, an aqueous solution of tetramethyl hydride hydroxide, etc. From the viewpoint of self-developability, carbon is preferred. The sodium aqueous solution and the aqueous sodium hydroxide solution. Examples of the development method include spray development, impregnation development, and dip-type development. / Next, the printed wiring board on which the photosensitive film is bonded is calcined to form a printed wiring board. The m-sintering is preferably carried out at a temperature of 3 〇〇 c or more and 4 (10) 艽 or less from the viewpoint of removal of a solvent or a side reaction or decomposition. More preferably, it is 1 〇〇 ° C or more, 3 〇(rc below. The reaction environment for calcination can be carried out in an air environment or in an inert gas atmosphere. In the manufacture of printed wiring boards, the time required for the calcination varies depending on the reaction conditions, usually within 24 hours. It is particularly suitable to be carried out in the range of from hr to 8 hours. The polyimine and the photosensitive resin composition of the present embodiment have good warpage after curing and good developability after 158118.doc -82·201237101 In the field of electronics, the protective layer formed of a printed wiring board or a circuit board used in forming an operation panel or the like of various electronic devices is formed in the field of electronics. The insulating layer of the laminated substrate is used for the protection or insulation of the slab wafer, the semiconductor wafer, the semiconductor device, the semiconductor mounting substrate, the heat radiating plate, the lead pin 'semiconductor itself, etc. used in the semiconductor device. In the use of forming a film on an electronic component to be used, as described above, a protective film for protecting a wiring formed on a stone wafer, a copper foil laminate, a printed wiring board, or the like is referred to as a cover layer. The form of the polyimide and the photosensitive resin composition can be suitably used for a substrate for a flexible printed wiring circuit (FPC), a substrate for tape and tape automatic bonding (TAB), an electrical insulating film for various electronic devices, and A substrate for a liquid crystal display, a substrate for an organic electroluminescence (EL) display, a substrate for an electronic paper, a substrate for a solar cell, and particularly a cover layer for a flexible printed wiring circuit. (Third Embodiment) As a material used in the production process of the flexible printed circuit board, a resin composition comprising the following polyimine: The polyamine structure of the diamine component having a polyoxyalkylene moiety and a polyimine structure. In these resin compositions, the oxoxane name is only present in the polyamic acid structure. Therefore, there is a problem that the polyamidene structure shrinks and warps when hardened, and the molecular weight of the poly-proline or the like is lowered (4), and the development time of the dry resin film becomes unsatisfactory. Also, as a material, the parts that can be used as a flexible brush substrate can be cracked - 158118.doc -83- 201237101

The high-acceleration test (HAST) has been carried out, and a material having high insulation reliability against HAST and suppressing warpage in order to improve connection reliability has been demanded. The inventors of the present invention have focused on the use of a polyimine having a polyfluorene structure having a decane moiety and a polyamine structure as a structural unit as the (A) polymer compound. Further, it has been found to be specific as a photosensitizer by containing (A) a polyimine structure having a polyfluorene structure having a polyoxyalkylene moiety and a polyphthalic acid structure as a polymer compound, and (D) as a photosensitizer. The (meth) acrylate compound of the structure and the photosensitive resin composition of (E) photopolymerization initiator can realize the photosensitive resin composition which has the outstanding HAST resistance. In the photosensitive resin composition, since the polypyridinium structure contains the agglomerated portion, the decrease in the molecular weight of the polyamic acid structure can be suppressed, so that the deterioration of developability can be suppressed. Further, since the polyimine portion of the molecular chain is imparted with moderate flexibility, the warpage of the resin film during curing can be reduced. Further, since the bifunctional hydroxyl group-containing compound and the blocked isocyanate compound are contained, shrinkage and segregation of the polyimine having a polyoxo-oxygen moiety can be suppressed, the distortion at the time of curing can be reduced, and the heat-reducing property can be improved, and the base can be suppressed. The adhesion of the material is reduced. Hereinafter, the third embodiment of the present invention will be specifically described. The photosensitive resin composition of the third embodiment of the present invention contains: (&) polyimine having a polyimine structure and a polyaminic acid structure as a structural unit, and (D) having two or more photopolymerizable groups A (meth)acrylic acid vinegar compound having an unsaturated double bond and (E) a photopolymerization initiator. Hereinafter, each constituent element will be described. 158118.doc •84· 201237101 (a) Polyimine The polyimine of the present invention has a polyimine structure represented by the following formula and a polyfluorene represented by the following formula (8) The amino acid structure serves as a block copolymer of repeating structural units, respectively. The polyimine of this embodiment can be synthesized by using acid dianhydride and diamine. General formula (7)

0 0 (In the formulas (7) and (8), 'Z3 and Z4 are derived from the following formula (9). The tetravalent organic group of the carboxylic acid dianhydride may be the same or different. The carbon number is 1 to an organic group having a carbon number of 30, and r19 represents an organic group having a valence of 1 to a carbon number of 30, and e is an integer of 1 or more and 20 or less.) (9) 158118.doc •85. 201237101

The polyamidene structure thus contains a oxyfluoride moiety in the polyimine structure. Thereby, the polyimine portion of the molecular chain is imparted with moderate flexibility, so that the warpage of the film after calcination can be reduced. Further, since the polyimine contains the polyamic acid structure represented by the above formula (8), an aromatic ring is introduced into the molecular chain. II. This suppresses the decrease in the molecular weight of the polyaminic acid structure, so that the storage stability of the photosensitive resin composition and the development time stability of the dry film are improved. Further, the polyaminic acid structure and the polyimine structure of the polyimine contain a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the above formula (9), thereby imparting a moderate degree of rigidity to the molecular bond. The heat resistance is improved and the insulation reliability (resistance) is increased. Examples of the acid dianhydride used in the present embodiment include tetrazoic acid dianhydride (hereinafter abbreviated as "PMDA"), oxydiphthalic dianhydride (hereinafter abbreviated as "ODPA"), and biphenyl tetraindole. Acidic anhydride (hereinafter referred to as "BPDA"). Regarding oxydiphthalic dianhydride and biphenyltetracarboxylic dianhydride, although structural isomers are present, the structure thereof is not particularly limited. Further, § hai and other acid dianhydrides may be used singly or in combination of plural kinds. Examples of the aromatic diamine used in the present embodiment include anthracene, 3-bis(3-aminophenoxy)phenyl, 1,4-bis(3-aminophenoxy)benzene, and a heart. Bis-amine basic oxy) stupid. From the viewpoint of warpage, a flexible ruthenium, 3-bis(3-aminophenoxy)benzene, is preferred. 158118.doc -86 - 201237101 Further, the polyoxymethylene diamine used in the present embodiment is not particularly limited as long as it has a structure represented by the following formula (19). General formula (19) H2N-Rtr--Si4〇Si-+TMRir-NH2 R,s V Rt./ In the above formula (7) and the above formula (19), the e system satisfies i An integer of $e^2〇. When e is 20 or less, alkali solubility and HAST resistance 4 become good. The e in the above formula (15) is preferably 1 or more and 15 or less, more preferably y or more and i 2 or less from the viewpoint of the properties of the produced polyimine and the flame retardancy. In the above formula (7) and the above formula (19), Ri8 is not limited as long as it has a divalent organic group having a carbon number of i or more and 30 or less, and is a divalent organic group having a carbon number of 丨 or more and 3 Å or less ( RM, from the viewpoint of flame retardancy, is preferably a divalent organic group derived from an aliphatic saturated hydrocarbon having a carbon number of (7) or less represented by CH2, C2H4, C3h6, C4li8 or the like. In the above formula (19), the organic group having a carbon number of at most 3 Å or less may be the same or different. The organic group (Rl9) having a carbon number of 30 or more may be an aliphatic saturated tobacco group. An aliphatic unsaturated hydrocarbon group, an organic group containing a cyclic structure, and a combination thereof. Examples of the aliphatic saturated hydrocarbon group include a methyl group, an ethyl group, and a propyl group. 158118.doc •87·201237101 a second-stage hydrocarbon group such as a butyl group, a pentyl group or a hexyl group, a first-stage hydrocarbon group such as a 'isobutyl group or an isopentyl group; a third-stage hydrocarbon group such as a third butyl group; and the like. Examples of the above aliphatic unsaturated hydrocarbon group include a vinyl group. a hydrocarbon group containing a double bond such as a propyl group, a hydrocarbon group having a triple bond such as an ethynyl group, or the like. Examples of the functional group including a cyclic structure include a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group or a cyclooctyl group; and a polycyclic functional group such as a decyl group or a ruthenium group; I 士 夕 环 环 S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S An aromatic hydrocarbon group having a phenanthrene ring structure, etc. The organic group (Ri9) having a carbon number of mno or less may be a dentate atom, a hetero atom or a metal atom. Examples of the element include a fluorine atom and a chlorine atom. Further, examples of the hetero atom include oxygen, sulfur, gas, and a dish. Examples of the metal atom include ruthenium and titanium. The organic group (R19) having an anisotropy of 1 or more and 30 or less contains a hetero atom and/or a metal. In the case of an atom, ' Ris may be directly bonded to a bonded hetero atom and/or a metal atom, or may be bonded via a hetero atom and/or a metal atom. As the above formula (7) and the above formula (19) When considering the flame retardancy, it is preferable that the carbon number is not the following. From the viewpoint of the solvent solubility of the polyimine, the carbon number is particularly preferably 1 or less. As the compound represented by the above formula (19), RI8 represents a compound in which a propyl group and a ruler 19 are not methyl groups. Listed by PAM-E (n = 2) > KF-801〇(n= ι〇), X-22-161 A(n= 20) ' 1 it Kang V a system &; BYl6_87l (n-2), and Sichuan (n_i〇). \5Sm.doc

S-88-201237101 Further, a compound in which Ri8 represents a propyl group and Ro represents a phenyl group is X-22-166〇B_3 (n~20) manufactured by Shin-Etsu Chemical Co., Ltd. If the end of the main chain of the polyimine is a structure that does not affect the performance, there is no particular limitation. I may be the end of the main chain of the acid dianhydride or the amine used in the production of the polyimine. The end of the main chain is blocked by other acid anhydrides, amine compounds and the like. The weight average molecular weight of the polyimine is preferably 1 Å or more and 1 Torr or less. Here, the weight average molecular weight means a molecular weight measured by gel permeation chromatography using a known weight average molecular weight of polystyrene as a standard. The weight average molecular weight is preferably 1,000 or more from the viewpoint of the strength of the polyimide film. Further, from the viewpoint of the viscosity and moldability of the resin composition containing polyimine, it is preferably 1 or less. The weight average molecular weight is more preferably 5,000 or more and 500,000 or less, particularly preferably 10,000 or more and 300,000 or less, and most preferably 25,000 or more and 50,000 or less. The production method shown in the second embodiment can be used as a method for producing a polyanilin having a polyimine structure and a polyaminic acid structure as repeating units. Further, in the above embodiment, the second aspect of the polyimine which has a polyimine structure having a fluorene alkane moiety and a polyphthalic acid structure as a structural unit as the (A) polymer compound is used. Although the resin composition is used in the range of the effect of the present invention, it can be used as the resin composition of the first aspect, by using a polyimine which does not substantially contain a polyaminic acid structure. . 158118.doc -89 - 201237101 (b) Bifunctional hydroxyl group-containing compound The photosensitive resin composition of the present embodiment preferably contains a bifunctional hydroxyl group-containing compound and a blocked isocyanate compound. The bifunctional ketone-containing compound does not have a direct bond with the polyimine, and thus is not embedded in the skeleton and exists as a second component. Thereby, shrinkage of the polyamidene skeleton at the time of hardening can be prevented, and warpage can be suppressed. Further, by including a compound of the blocked isocyanate S, the carboxyl group of the polyimine is deactivated at a low temperature, and the resin can be cured at a low temperature. Therefore, shrinkage of the polyimine skeleton at the time of curing can be prevented, and ruthenium can be suppressed. In the photosensitive resin composition of the present embodiment, the hydroxyl group contained in the bifunctional hydroxyl group-containing compound and the isocyanate group contained in the block isocyanide Sa are considered from the viewpoint of heat resistance. The ear is preferably a thiol/isocyanate group = 0.5 to 1. The bifunctional hydroxyl group-containing compound can be the same as the bifunctional hydroxyl group-containing compound used in the resin composition of the above-described first embodiment. Further, as the bifunctional hydroxyl group-containing compound, a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups may be used insofar as it exhibits the effects of the present invention. In the present embodiment, the bifunctional hydroxyl group-containing compound is preferably in terms of the reduction in the taste, the solder heat resistance, and the chemical resistance of the resin composition. It contains i part by mass to 7 parts by mass of 'more preferably 1 part by mass to 60 parts by mass. (c-1) Block Isocyanate Compound The blocked isocyanate compound can be the same as the blocked isocyanate compound used in the resin composition of the above-mentioned 158118.doc 201237101. In the present embodiment, as the (c) polyfunctional crosslinkable compound, an example in which a blocked isocyanate compound is used is described. However, it is also possible to use two or more isocyanates in the range which has the effect of the present invention. A polyfunctional isocyanate compound or a polyfunctional crosslinkable compound having two or more crosslinkable functional groups or a polyfunctional oxazoline compound. (d) (fluorenyl) acrylate compound As the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, dihydroindenyl alcohol diacrylate and ethylene oxide can be cited. EO) modified bisphenol a dimercapto acrylate, E 〇 modified hydrogenated bisphenol a diacrylic acid vinegar, 1,6-hexanediol (mercapto) acrylate, i, 4_cyclohexanediol II (Meth) acrylate, polyethylene glycol bis(indenyl) acrylate, polypropylene glycol bis(indenyl) acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylic acid vinegar, three (2) - propylene methoxyethyl) isomeric cyanurate, ε_caprolactone modified bis(propylene oxyethyl) isocyanate, glycerol tris(meth) acrylate vinegar , trimethylolpropane tri(meth)acrylate, polyoxyethylidene tris-propylpropanepropane tris(decyl)acrylate, polyoxyl-propyltrihydroxymethylpropane tris(meth)acrylate , dipentaerythritol penta(indenyl) acrylate, trimethyl propyl triglycidyl ether (mercapto) acrylate, bisphenol quinone diglycidyl squamous (methyl) Ethyl ester, β-hydroxypropyl-β'-(propylene decyloxy)-propyl phthalate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethyl Glycol (meth) acrylate, pentaerythritol tris(mercapto) acrylic acid, pentaerythritol tetrakis(meth) acrylate, pentaerythritol tri/tetrakis (fluorenyl) acrylate, and the like. 158118.doc 201237101 The photosensitive resin composition of the present embodiment contains a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds. From the viewpoint of self-resolution or _HAST property, (4) is a (meth) acrylate compound having three or more double bonds. Examples of the (mercapto)acrylic acid lysing compound having three or more double bonds include pentaerythritol tri/tetraacrylic acid (manufactured by Toagosei Co., Ltd., ar〇nix M-306), and pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). , Α-ΤΜΜΤ), E0 modified glycerol tris(methyl) acrylate vinegar (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-GLY-9E (E〇 modified 9 m〇1)), ternary trishydroxyl Methyl propane tetraacrylate (manufactured by Toagosei Co., Ltd., AR〇NIx M_ 408), dipentaerythritol penta and hexaacrylate (manufactured by Toagosei Co., Ltd., ARONIX M-403), and the like. Further, 'in the present embodiment', as a (meth) acrylate compound having three or more double bonds, from the viewpoint of insulation resistance (resistance or warpage), a more preferable formula (1〇) The compound is represented by the fact that the compound represented by the following formula (10) is not embedded in the skeleton of the polyimine to form a crosslinked body as the second component, thereby preventing aggregation at the time of hardening. The shrinkage of the imine skeleton can suppress warpage. In addition, since it does not have a functional group which reduces electrical insulation, such as a hydroxyl group, it is estimated that the rigid crosslinked body is formed in the polyimine matrix of this embodiment. The Tg or the modulus of elasticity of the cured film becomes high, and the HAST resistance is improved. [Chem. 30] Formula (10)

I58118.doc -92- S 201237101 ο ΪΗ20-( —6~CH2 Η30~°Η2^—CH20-(e-C%-( iH20*{i-〇^—9~c =CH2

base. The plurality of Es may be independently the same or different. F (in the formula (10), the ruler 2〇 represents a hydrogen atom or a group represents a slave number of 2 to a carbon number of 5, and is an integer of 1 to 10.) In the above formula (10), as a carbon number Examples of the exfoliation group having 2 to a carbon number of 6 include an exoethyl group, a propyl group, an exo-propyl group, a butyl group, an isobutylene group, a neopentyl group, and the like. More preferably, from the viewpoint of self-resolution, E is an alkylene group having 2 carbon atoms or 3 carbon atoms. Further, in the above formula (ι), from the viewpoint of flame retardancy, it is particularly preferable that f is 1 or more and 5 or less. Examples of the compound represented by the above formula (1〇) include ARONIx M-350 (E: exoethyl, f: 1), m_36〇 (e•extended ethyl, f: 2) manufactured by Toagosei Co., Ltd. M-310 (E: propyl, f: 1), M_321 (E: propyl, f: 2), SR5 〇 2 (E: Ethyl, f: 3), SR9035 (E) manufactured by SARTOMER : Elongate ethyl, f: 5), etc. These may be used alone or in combination. Further, in the photosensitive resin composition of the present embodiment, from the viewpoint of distortion or resolution after satin burning, it is preferred to use a (meth) acrylate compound having two double bonds in combination with 3 More than one double bond (mercapto) acrylic vinegar compound. As a (fluorenyl) acrylate compound having two double bonds, it can be classified into a fat 158118.doc-93-201237101 aliphatic di(methyl)(tetra) acid s| and an aromatic group having a bis(tetra) structure) 8 purpose. As an aliphatic di(meth)acrylic acid, it can be listed as ethylene glycol di(indenyl)acrylic acid, polypropylene glycol di(indenyl)propionic acid vinegar, polybutylene glycol di(methyl). Acrylate, polyethylene-polypropylene glycol, bismuth citrate and the like. Specifically, from the viewpoint of suppression of the taste, the preferred soil is nonaethylene glycol diacrylic acid (manufactured by Shin-Nakamura Chemical Co., Ltd., 9G), heptapropanediol dimethylpropane (tetra) (Naka Nakamura Chemical Industry Co., Ltd. In addition, as the aromatic di(meth)acrylic acid vinegar, a compound represented by the following formula (20) can be mentioned. [Chem. 31] Formula (20) h2c=c-c4e-o 2 I II ' r25o

(In the formula (20), Ur26 represents a hydrogen atom or a methyl group. The plurality of E independently represent an alkylene group having a carbon number of 2 to a carbon number of 6 (may be the same or different). In the above, examples of the alkylene group (E)' having a carbon number of 2 to a carbon number of 6 include an exoethyl group, a propyl group, an exo-propyl group, a butyl group, an isobutyl group, and a pentyl group. New amyl and so on. In the above formula (20), 1 and k are respectively! The above integer is less than 1〇, and 2Sl+k$20. When 1 and k are each 1 Å or less, the flame retardancy and the resistance to hasi are improved. Further, from the viewpoint of warpage and resolution, it is more preferable that 1 and k in the formula 158118.doc S. 201237101 (20) are 3 or more and 6 or less, respectively, and 1 + kS 12 . Specific examples of the above formula (20) include ARONIX M-208 (R25, R26: hydrogen atom, e: exoethyl, 1, k, and 2) manufactured by Toagosei Co., Ltd., and Shin-Nakamura Chemical Industry Co., Ltd. Manufactured bpe_5〇〇(R25, R26: methyl, E: extended ethyl, l+k=l〇), BPE-900 (R25, R26: methyl, E: extended ethyl, l+k=17) , A-BPE-500 (R25, R26: hydrogen atom 'E: ethyl, l+k=l〇), A-B1206PE (the following general formula (21), R25: hydrogen atom, R26: methyl group, E1: Ethyl, E2: propyl, ll+kl=6, 12+k2=12) and the like. General formula (21)

The amount of the (fluorenyl) acryl vinegar compound having two or more photopolymerizable unsaturated double bonds is considered to be self-resolution in the case where the amount of the polyimine is set to 丨〇〇 by mass. It is preferable that it is 5 parts by mass or more and 6 parts by mass or less, and more preferably 1 part by mass or more and 4 parts by mass or less. In the case where the resin composition of the present embodiment is not used as a photosensitive resin, it is not always necessary to contain a (meth) acrylate compound as the (D) photosensitizer. (E) Photopolymerization initiator The photopolymerization initiator can be the same as the photopolymerization initiator described in the second embodiment. 158118.doc -95· 201237101 (F) Scale compound As the phosphorus compound, the same as the phosphorus compound shown in the above second embodiment can be used. In addition, as a phosphazene compound represented by the above-mentioned general formula (17), Rabhle (registered trademark) Fp_3〇〇, Fp_390, (of Fushi Pharmaceutical Co., Ltd., abbreviated as Fp_3〇〇 (R2i=R22=) 4 cyanophenyl), abbreviated as FP-390 (R21=R22=3-mercaptophenyl)). (G) Other compounds Further, in the photosensitive resin composition of the present embodiment, other compounds may be contained in a range which does not adversely affect the performance. The other compound is the same as the other compound described in the second embodiment. (H) Photosensitive film. The photosensitive resin composition of the present embodiment can be combined with the photosensitive resin of the second embodiment. The object is similarly used in the formation of a photosensitive film. (I) Flexible printed wiring board The photosensitive resin composition of the present invention can be suitably used in a flexible printed wiring board in the same manner as the photosensitive resin composition of the second embodiment. (Fourth Embodiment) As a material used in the production of a flexible printed circuit board, a resin composition containing an aqueous solution of an aqueous solution which is soluble in an aqueous solution and a solvent-soluble polyimide is proposed. All of the guanidine acid is imidized and contains a hydroxyl group and/or a carboxyl group. In the resin composition, it can be used as a laser-free processing in the manufacture of a flexible printed wiring board, by using an aqueous test. 96 - 158118.doc

S 201237101 Interlayer insulation for channel processing with solution or solvent. However, the solvent or the aqueous solution used in the manufacturing steps of the flexible printed wiring board is poor in tolerance, which causes an improvement in requirements. In addition, when the insulating material in the form of a solvent-free film is laminated on a wiring board by a hot press method, it is used as an interlayer insulating film, and since it is a polymer compound, the resin has poor fluidity and is buried in the via hole. Poor sex and expect to improve. The inventors of the present invention have focused on the use of a solvent-soluble polyimine having a hydroxyl group and/or a carboxyl group and a decane moiety as the (A) polymer compound. Further, the inventors of the present invention have found that by containing a solvent-soluble polyimine as a polymer compound, (B) a bifunctional hydroxyl group-containing compound as a polyfunctional hydroxyl group-containing compound, and (c) as a polyfunctional crosslinkable compound The oxazoline compound can be processed by a solvent or an alkaline aqueous solution before the crosslinking reaction, and exhibits good through-hole embedding property, and has excellent resistance to a solvent and an alkaline aqueous solution after the crosslinking reaction. Receptive alkali soluble resin composition. Hereinafter, a fourth embodiment of the present invention will be specifically described. The resin composition of the fourth aspect of the present invention contains (a) a polyimine having a transradical group and/or a carboxyl group, (b) a bifunctional hydroxyl group-containing compound, and a (c-2) oxazoline compound, and is relative to the poly The content of the bifunctional hydroxyl group-containing compound and the oxazoline compound is from 2 parts by mass to 45 parts by mass per 100 parts by mass of the quinone. In the resin composition, since the polyimine has a hydroxyl group and/or a carboxyl group, and the content of the bifunctional group-containing compound and the oxazoline compound is within a specific range, the through-hole embedding property is excellent before crosslinking. It is soluble in an aqueous alkaline solution and becomes insoluble in an aqueous alkaline solution after 'crosslinking'. Further, since the polyimine has a hydroxyl group and/or a carboxyl group, it can react with the oxazoline compound to inhibit 158118.doc-97-201237101 warping, and the 2gflb hydroxylated material is not embedded in the skeleton of the polyimine. Since it exists as a 2nd component, it can prevent shrinkage of the poly-imine skeleton at the time of hardening, and can suppress a warpage. Further, by deactivating the carboxyl group at a low temperature by containing the oxazoline compound, the carboxyl group can be cured at a low temperature, so that shrinkage of the polyimine skeleton at the time of curing can be prevented, and warpage can be suppressed. In the resin composition, since the polyimine has a hydroxyl group and/or a carboxyl group, it becomes soluble in an alkaline aqueous solution before hardening, and becomes insoluble in an alkaline aqueous solution after hardening, and exhibits a high degree. Heat resistance (for example, higher solder heat resistance). Moreover, the warpage at the time of hardening can be suppressed by the said structure. Further, although the structure of the polyimine has a hydroxyl group and/or a carboxyl group, a bifunctional hydroxyl group-containing compound is present in the resin composition, whereby shrinkage of the polyimine skeleton at the time of curing can be prevented. That is, the bifunctional hydroxyl group-containing compound is not embedded in the skeleton, but is contained as the second component, whereby the warpage of the cured product obtained from the resin composition can be further reduced. Further, since the oxazoline compound is contained, it is possible to achieve insolubility in the aqueous solution and further increase in the heat resistance by the formation of the polymer and the formation of the parent by the reaction with the hydroxyl group. Further, the content of the difunctional hydroxy group-containing compound and the oxazoline compound is from 2 parts by mass to 45 parts by mass per 100 parts by mass of the polyimine, and the polyimine is excessive with respect to the other components. Due to this configuration, it is presumed that heat resistance can be exhibited by the mechanism as shown below. The oxazoline group reacts with a hydroxyl group to form a structure comprising a C=mercapto group or an nh group, but the oxazole and the carboxylic acid contained in the polyimine remaining after the oxime imidization reaction The reaction 'forms a guanamine structure or a urea structure containing a C=mercapto group or an NH group. also

158118.doc _98 S 201237101 ie, the chemical cross-linking between the polyimine and the oxazoline compound formed by thermal hardening, and the chemical interaction between the bifunctional ketone-containing compound and the oxalate compound Union. As described above, the cross-linking of a plurality of types forms a three-dimensional cross-linking, and the poly-imine which is excellent in heat resistance is excessive, whereby further thermal properties are exhibited. Next, the details of each composition constituting the resin composition will be described. (a) Polyimine The polyimine used in the resin composition of the present embodiment has a hydroxyl group and/or a carboxyl group as a structural unit. Thus, the polyimine structure moiety is hardened by reacting with the crosslinkable functional group of the polyfunctional crosslinkable compound, thereby exhibiting insolubility in the aqueous alkaline solution after hardening. Further, by decomposing the carboxyl group remaining at the time of low-temperature curing by reaction with an oxazoline compound and/or a blocked isocyanate compound, an oxazoline compound and/or a blocked isocyanate compound can be used. The bifunctional group contains a trans-based compound to suppress distortion. The polyimine used in the resin composition of the present embodiment has a hydroxyl group and/or a carboxyl group as a structural unit. The hydroxyl group and/or the carboxyl group can be introduced into the polyimide by using a diamine having a hydroxyl group and/or a carboxyl group. Examples of such a diamine include 2:5-diaminophenol, 3,5-diaminophenol, 4,4l-(3,3'-dihydroxy)diaminebiphenyl, 4,4. '-(2,2'-Dihydroxy)diaminobiphenyl, 2,2|-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3-hydroxy-4-aminobiphenyl ( 11 into 6), 4,4,-(3,3,-dicarboxy)diphenylamine, methylenebisaminobenzoic acid (MBAA), 2,5-diaminobenzoic acid (DABA), 3,3,-dicarboxy-4,4丨-diaminodiphenyl ether and the like. 158118.doc •99- 201237101 For the other constitution of polyimine, the same can be used in the above embodiment, and in the above embodiments, the use of a base and/or a slow base and a broken oxygen The solvent-soluble polyi-imine of the site is described as the resin composition of the second aspect of the polymer compound (4), but it is also possible to use substantially no polyamine in the range of the effect of the present invention. The polyethylenimine having an acid structure is used as the resin composition of the first aspect described above. As the method for producing the polyimine of the present embodiment, the same method as the method for producing the polyimine shown in the first embodiment described above can be used. (b) Bifunctional hydroxyl group-containing compound The bifunctional group-containing compound used in the resin composition of the present embodiment means a matrix containing two base groups with respect to the -molecular chain. In the case where a hydrocarbon group such as an aliphatic, aromatic or alicyclic group is contained in the skeleton, it is considered from the viewpoint of improving the insulating property in the case of crosslinking with the π-causal compound. It is preferred to have a structure represented by the following formula (14) in the skeleton, and it is considered to be a compound of the formula (14) which contains an aliphatic compound. The reason for this is that by having an aliphatic skeleton, the hygroscopicity can be suppressed without impairing the inhibitory effect of the distortion, and even if it absorbs moisture, it exhibits high insulation properties, and further contains long fat. (4) The effect of the base is improved and preferably 0 [Chemical 33] General formula (14)

H04fx^(YH side (X OH 158118.doc -100- 201237101 (in the formula (14), X-based aromatic, Y-based carbon number is 1 to an aliphatic group having a carbon number of 10, and the lanthanide is selected from an ether group. , ester group, carbonate group, urethane group, urea group functional group, h=0~2 integer, i=0~1 integer, j=l~1000 integer.) Again, in order to 1 cross-linking of a smectite compound, preferably a terminal compound. Further, particularly in the use of an electronic material, it is preferably a halogen such as fluorine or chlorine. As a specific example of a bifunctional hydroxy group-containing compound, Polybutadiene glycol such as PTMG1000 manufactured by Mitsubishi Chemical Corporation, polybutadiene diol such as G-1000 manufactured by Japan Soda Co., Ltd., hydrogenated polybutadiene diol such as GI-1000, and DURANOL T5651 manufactured by Asahi Kasei Chemicals Co., Ltd. DURANOL T5652 > DURANOL T407 1 and polycarbonate diols such as PLACCEL CD manufactured by Dasailu Chemical Industry Co., Ltd., polycaprolactone diols such as PLACCEL 200 manufactured by Daicel Chemical Industry Co., Ltd., bisphenols such as bisphenol A, new Hydrogenated bisphenols such as Rikabinol HB manufactured by Japan Chemical and Chemical Corporation, X-22-182 manufactured by Shin-Etsu Chemical Co., Ltd. 1, BY16-752, BY16-799 and other two-terminal phenol-modified polyoxane manufactured by Dow Corning, etc. In these, from the viewpoint of improving insulation, it is preferred to have two-terminal phenol-modified polyoxane, The polybutadiene diol, the hydrogenated polybutadiene diol, and the polycarbonate diol are preferably a two-terminal phenol-modified polyfluorene oxide or a polycarbonate diol from the viewpoint of reducing warpage. The difunctional hydroxyl group-containing compound is preferably liquid at room temperature, and preferably has a number average molecular weight of 500 to 3,000, from the viewpoint of a decrease in warpage and solubility in an organic solvent. The most preferable is the number of 158118.doc • 101 - 201237101. The average molecular weight is 500~2000. As a bifunctional trans-containing compound, it is considered to reduce the tormentation, solder heat resistance and chemical resistance. The amount of the resin composition is preferably from 3 parts by mass to 70 parts by mass, more preferably from 5 parts by mass to 60 parts by mass, based on 100 parts by mass of the resin composition. Further, in the present embodiment, as (B) Functional hydroxyl-containing compound's 2-functional inclusion of two hydroxyl groups Although the base compound has been described, a polyol containing two or more kinds of a base group may be used in the range in which the effects of the present invention are used. (c-2) ° The oxalate compound is in the resin composition of the present embodiment. The oxalin compound is a compound having two or more oxazoline groups in the molecule. As the oxazoline compound VII, it is preferably a polyimine (polymer compound) and/or a bifunctional hydroxyl group. When cross-linking is formed between the compounds, there are at least two C=0 bases and/or fluorenyl groups in the cross-linking. Specific examples of the oxazoline compound include: 丨 'Hongshuang ^^ dihydro _ 2 oxazolyl) benzene, K2 〇 1 〇 E, K 2 〇 2 〇 e, K 203 0E manufactured by Nippon Shokubai Co., Ltd. , 2,6-bis(4-isopropyl-2-y. oxazol-2-yl), bite, 2,6-bis(4-phenyl-2-oxazolin-2-yl)pyridine, 2,2ι_isopropylidenebis(4-phenyloxazoline), 2,2'-isopropylidenebis(4_t-butyl-2-oxazoline), and the like. These oxazoline compounds may be used singly or in combination of two or more. The cured product can be obtained by heating the above resin composition. The heating state is not particularly limited. In order to be soluble in an alkaline aqueous solution, it is preferred to carry out heating at 50 ° C to 140 ° C for 丨 minute to 6 〇 minutes. Another. Outside 158118.doc 201237101

Should become 'insoluble in alkaline aqueous solution.

It is fixed in the whole time, and is cross-linked by adding it in an inert environment such as air or nitrogen. The heating temperature can be treated and the temperature can be raised slowly. The resin composition film can be printed on a surface of a flexible printed circuit board or a semiconductor wafer by a known screen printing or precision dispensing method to form a β resin composition which can exhibit excellent heat resistance by thermal curing. Therefore, it can be used as a surface cured film of a semiconductor element, an interlayer insulating film, a bonded sheet, a protective insulating film for a printed wiring board, a surface protective film of a printed circuit board, an interlayer insulating film, and the like, and is suitable for use in various electronic parts. For example, the resin composition may be applied to a copper foil F2-WS (12 μm) and dried at 95 «»c for 12 minutes to prepare a resin-attached copper foil having an insulating layer thickness of 15. As a flexible printed circuit board, 'Espanex Μ (manufactured by Nippon Steel Chemical Co., Ltd.) (the thickness of the insulating layer is 25 μηι, and the conductor layer is copper foil F2-WS (18 Μ·1»)), by vacuum pressing The copper foil with resin is laminated on the circuit substrate for 1 minute, and a photosensitive etching resist layer is formed on the copper foil, and the etching resist and the resin composition are made of an alkaline aqueous solution. After dissolving, after forming the channel, the protective layer was peeled off and hardened at 18 ° C for 1 hour, whereby an interlayer insulating film was obtained. The interlayer insulating film formed as described above can exhibit good insulating properties. Further, the resin composition of the present embodiment is thermally cured at a relatively low temperature condition (for example, 160 ° C to 200 ° 〇 〇, because 158118.doc -103· 201237101 does not cause oxidation of steel. A double-sided copper foil plate made of ESpanex M (manufactured by Nippon Steel Chemical Co., Ltd., having a thickness of 25 μηη of insulating layer and a copper foil F2_ws〇8 μιη) is used as a double-sided component circuit board. The resin composition is applied onto the substrate, dried, and cured by an aqueous alkaline solution. The resin composition can also be used as a surface protective film to exhibit good insulating properties. The film thickness of the surface film is preferably from 1 pm to 50 μm. The reason for this is that the operation is facilitated by making the film thickness i μπι or more, and if it is 50 μm or less, the bending can be easily made and the assembly can be facilitated. In addition, the resin composition of the present embodiment can be used as a photosensitive resin composition by containing (D) a photosensitive agent. Further, a photosensitive film can be obtained by applying a photosensitive resin composition to a substrate. Further, the resin composition of the present embodiment may contain (F) a phosphorus compound and may be used from the viewpoint of improving flame retardancy. As the (F) phosphorus compound, a dish ester compound or a scalonitrile compound or the like can be used. Furthermore, the resin composition of the present invention can be suitably used as a layer-insulating film such as a multilayer flexible wiring board by drying a resin composition on a steel foil. In addition, the resin composition of the present embodiment can be suitably used as a protective film for a wiring pattern of a wiring board by providing a resin composition so as to cover a wiring pattern formed on a substrate. Further, the resin composition may contain an organic solvent in addition to the polyimine, the bifunctional hydroxyl group-containing compound, and the oxazoline compound. The reason for this is that it can be preferably used as a varnish by being dissolved in an organic solvent. 158118.doc •104- 201237101 2:: This organic solvent can be enumerated as: n, n• dimethyl acetamide, n, n_ decylamine, N, N-dimethylformamide, N, N Ethyl amide, t, , / Λ 〇 〇 〇 酿 酿 酿 酿 酿 酿 酿 γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ Ethyl sub-milling, hexamethylene sulfoxide and other sulfur-containing agents '曱19, benzene (four) solvent, diethylene glycol diethylene glycol·,) monoethylene glycol dimethyl ether (triethylene glycol dioxime ether) ), tetraethanol dimethoate, dioxane, tetrachlorine. husband. South, astringent vinegar, benzoic acid ethyl vinegar, benzomethazine, etc. Further, these organic solvents may be used singly or in combination of plural kinds. In particular, from the viewpoint of the high Buddha point and low water absorption, it is preferred to use γ butyl peptone, diethylene glycol dioxime ether, butyl benzoate or ethyl benzoate. [Examples] Hereinafter, examples for carrying out the effects of the present invention will be described. Further, the present invention is not limited by the following examples. The resin composition of the first embodiment of the present invention will be described with reference to the following Example 1 and Comparative Example 1. Further, in the following examples, Samples 1 to 32 are the resin compositions of the second aspect, and Samples 33 to 35 are the resin compositions of the first aspect. (Example 1) A sample 1 containing a cured film of a resin composition was prepared, and its characteristics were confirmed. In the present embodiment, as a resin composition, Asahi Kasei Chemical Co., Ltd., which is a polycarbonate diol, is added to a varnish of a polyimine (hereinafter referred to as polyimine) having a quinone imidization ratio of 88%. DURANOL SBN-70D (NCO content) manufactured by Asahi Kasei Chemicals Co., Ltd., manufactured as DURANOL T5651 (molecular weight 1000; or less, polyfunctional ketone-containing compound oxime), hexamethylene 158118.doc-105·201237101 diisocyanate-block isocyanate It is 10_2 wt%; hereinafter referred to as isocyanate compound A). The polyfunctional hydroxyl group-containing compound A was 5 parts by mass, and the isocyanate compound A was 5 parts by mass based on the mass fraction of the polyimine. In addition, the polyamidimide A was blended in an amount of 30% by mass based on the resin composition. In this case, the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound and the mole ratio hydroxyl group/isocyanate group of the isocyanate group contained in the isocyanate compound A are 0.9. Hereinafter, a method for synthesizing polyiminamide a, a method for producing a cured film, and a method for evaluating each characteristic will be described. [Polyimide A] The method for synthesizing polyimine A will be described. First, a nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation well were attached to a three-neck separable flask. JEFFAMINE XTJ-542 (manufactured by Huntsman, weight average molecular weight i〇〇〇) 4〇g, ι,3-bis(3-aminophenoxy)benzene (eight-8) was placed in an ice water bath at °C. ) 23.519 §, phthalic anhydride 2.027 g, γ-butyrolactone (GBL) 60 g, ethyl benzoate (BAEE) 60 g, toluene 20 g, Y-valerolactone 12 g, η pyridine 18 g , the floor is mixed evenly. Further, 3,3,4,4,-dibenzophenone tetradecanoic acid dianhydride (BTDA) 18.966 g, 3,3',4,4'-diphenyltetracarboxylic acid two needles were added in small amounts each time. (〇8〇) 19.616§» After stirring for 0.5 hours, the temperature was raised to 170 ° C and heated for 4 hours. In the reaction, the by-produced water was azeotroped with toluene, and a spherical condenser having a moisture separation well was used. Dehydration is carried out under reflux. After removing the by-produced water, the reflux was stopped, and the toluene was completely removed. After cooling the system to 60 ° C, add BTDA 5.293 g, • 106- 158118.doc

S 201237101 APB 4_780 g. After 5 hours, it was cooled to room temperature. Next, the resultant was subjected to pressure filtration by a filter of 5 μm to thereby obtain a polyimide varnish having a ruthenium iodide ratio of 88%. Further, the above imidization ratio can be determined by an IR method. Specifically, based on the peak of the benzene ring in the vicinity of 1480 cm·1, the ruthenium imidization ratio was determined based on the ratio of the absorbance to the peak of the quinone ring formed around 13 80 cm·1. The imidization rate of C at any temperature is set to A3 at an absorbance of 1480 cm1 at any temperature, and the absorbance at 1380 cm·1 is set to B3 ' according to C=((B3/A3-Bl/Al) /(B2/A2-Bl/Al))xl〇〇(%) is calculated. Here, 'synthesized at 50 ° C at 8 (the absorbance at 1480 cm·1 of the resin dried under TC is set to A1, and the absorbance at 1380 cm·1 is set to B1. Also 'will be in the atmosphere, 22〇.(: The absorbance at 1480 cm·1 of the resin subjected to heat treatment for 60 minutes is set to A2, and the absorbance of 1380 cnT1 is set to B2. Also for each peak, before and after the peak, to the valley of the peak Draw a suitable baseline by connecting the valleys, and define the height of each peak from the baseline (that is, the distance between each peak point and the line from the peak to the baseline to the intersection of the baseline) as the respective absorbance. The hydrazine imidization ratio C calculated in the above formula is 22 〇. (The value of the ruthenium imidization ratio at the time of heat treatment for 60 minutes is set to 1 〇〇%. [Production of cured film] by rod The above-mentioned resin composition was applied onto a substrate by a coater, and homogenized at room temperature for 5 minutes to 10 minutes, and heated in a hot air oven at 12 Torr for 60 minutes, followed by 180 ° C. After drying for 30 minutes, drying and hardening was performed to prepare sample 1. As a substrate, Toray Dupont was used. Manufacture of 158118.doc 201237101

Kapton (registered trademark) i〇〇EN. Further, the resin composition was applied to one surface of the substrate. The film thickness after drying and hardening was about 20 μm. [Evaluation of Warpage] The evaluation of warpage was evaluated by the ridge of the four corners of the sample. Specifically, the sample 1 was cut into 5 cm x 5 cm in an environment of a humidity of 50% at 23 ° C, and the geodesic angle was warped with respect to the ridge distance of the central portion. When the distortion is 1 mm or less, it is marked as 良好, and if it is 5 mm or less, it is marked as ◎, and when it is 15 mm or less, it is △, and when it is more than 15 mm, it is marked as X. . [Evaluation of Solder Resistance (Heat Resistance)] The solder resistance was evaluated by immersing the sample 1 cut at 3 cm x 3 cm in a solder bath at 260 ° C for 60 seconds based on the JPCA-BM02 specification. Visually inspect the appearance and confirm the presence or absence of changes in deformation, dissolution, etc., and the case where no change is found in more than 90% of the total area is recorded as 〇, and the case where 50% to 90% of the total area is found is not recorded as △, the case where the area where no change was found is less than 50% is referred to as X. [Evaluation of chemical resistance] The sample 1 was immersed in methyl ethyl ketone at room temperature for 1 minute, and the appearance of the coating film was visually inspected to confirm the presence or absence of changes such as deformation and dissolution. A situation in which no change is found in more than 90% of the total area is recorded as 〇, which is found in the overall area of 50. /. The case where ~90% of the changes were not found was recorded as △, and the case where the area where no change was found was less than 50% was recorded as χ. [Evaluation of Insulation Resistance at a Temperature of 85 ° C and a Moisture of 85%] As a substrate of a flexible printed circuit board, Espanex M (manufactured by Niigata 158118.doc -108 - 201237101 Iron Chemical Co., Ltd.) (insulation layer) was used. The thickness is 25 μm, and the conductor layer is copper foil F2-WS (18 μιη)). A comb-shaped wiring board having a line width/line pitch of 5〇μπι/5〇μηι is produced. On one part of the circuit board, the resin composition was applied and hardened so that the film thickness after hardening became 15 μm, and it was used as a sample! Hey. The conditions of the hardening were the same as those of the sample 1Α. Thereafter, the electric resistance was measured while being placed under conditions of dc 50 V, 85 ° C, and humidity of 85 °/❶ for 8 hours, and the case where the insulation resistance exceeded ΙΟ9 Ω was recorded as 〇, and the case where the 〇9 Ω was not reached was recorded. Why? [Evaluation of viscosity at 100 ° C to 220 ° C] The viscosity of 100 C to 220 C was measured using a measuring machine AR-G2 manufactured by TA Instruments, and 27 layers of resin film were used for lamination (the foregoing resin film was obtained from copper enamel). A sample obtained by removing the copper foil from the resin film of the substrate, in a rotor, a parallel plate having a diameter of 8 mm, strain: 〇·1%, frequency:! Hz, normal stress: 0.1 N (100 g) for evaluation. The case where the viscosity of i〇〇〇c~22〇eC is in the range of 5000 Pa»s to 100000 Pa.s is denoted by 〇, and the case where the area is less than 5000 Pa·s or more than 100000 Pa·s is denoted as X. . [Evaluation of elastic and plastic regions] Elastic and plastic regions are tensile tests on specimens with a width of 5 mm and a length of 100 mm at a distance of 50 mm and 100 mm/min between the chucks based on the jIS_C_2151 specification. The elongation rate until the point of the drop was set as the elastic region, and the elongation from the point of the drop to the point of the break was evaluated as a plastic region. The case where the elastic region is a plastic region having an elongation of less than 20% and an elongation of 5 〇〇/0 or more is referred to as 〇, and the elastic region is a plastic region having an elongation of 20% or more or an elongation of less than 50%. Is x. [Evaluation of interlayer insulation resistance] 158U8.doc 109- 201237101 The interlayer insulation resistance is made by using Espanex® (manufactured by Nippon Steel Chemical Co., Ltd.) (the thickness of the insulating layer is 25 μηι, and the conductor layer is copper foil F2_WS (18 μιη)). The base material of the flexible printed circuit board is laminated with a resin film made of a copper foil as a base material, and then placed under conditions of DC 50 V, 85 eC, and humidity of 853⁄4 for 1000 hours to measure electric resistance and insulation resistance between the resin films. For the case of 1 Λ 9 D or more, it is recorded as 〇 'The case where 109 Ω is not reached is denoted as X. [Evaluation of Through Hole Buriedness] The through hole embedding property was performed by cutting and polishing with a 4-layer wiring board produced by epoxy resin embedding. The case where the resin was buried in the through hole without gap was recorded as 〇, and the case where the gap was observed in the through hole was recorded as X. [Evaluation of Thermal Shock Test] The thermal shock test is based on the specifications of JPCA-HD01-2003, and the 4-layer wiring board produced is evaluated at -4 (TC, 120 ° C, 1000 cycles). In the case of less than 1%, it is recorded as 〇, and the case where more than 1% is used is referred to as X. [Evaluation of Resin Fluidity] Resin fluidity is measured by a vacuum press (180 〇C, 20 minutes, 4 MPa) The resin sheet with copper foil as the base material and the copper foil F2_ws (12 ^ claws) were laminated, and the resin bleed out at the end of the sample was visually evaluated. The case where the resin bleed out to be 1 mm or less was recorded as 〇 The case where the value exceeds 丨mm is denoted by X 0 The evaluation result of the sample 1 (sample 1A, sample 1B) is shown in the following Table i. It is understood from the following Table 1 that the resin composition of the sample 1 is used. Hardened matter • 110- 158118.doc

S 201237101 The warpage at the time of hardening is made public, and the brother's knife is suppressed and the solder resistance (that is, the heat resistance) is excellent, and the insulation property under the conditions of chemical properties or high temperature and high humidity is also excellent. Further, the cured product of the resin composition of Sample 1 was evaluated for good evaluation in any of the evaluation of the elastic region and the plastic region, the interlayer insulation resistance, the through hole embedding property, the thermal shock test, and the resin fluidity. Next, the cured resin film was prepared by using the resin composition blended under the conditions different from the sample 1, and the properties of the prepared samples 2 to 21 were confirmed. [Sample 2 to Sample 5] Samples 2 to 5 were produced in the same manner as the sample, using a resin composition containing polyiminoimine a, polyfunctional hydroxyl group-containing 16A, and g cyanate compound A. . The main difference between Samples 2 to 5 is the content of the polyfunctional hydroxyl-containing compound A and the isocyanate compound A. Specifically, the sample 2 was prepared by adding a resin composition containing 7.5 parts by mass of a polyfunctional hydroxyl group-containing compound A and 75 parts by mass of an isocyanate compound A to 100 parts by mass of the polyacrylonitrile A. In the third embodiment, a resin composition containing 10 parts by mass of a polyfunctional hydroxyl group-containing compound A and a hydrazine isocyanate compound A 10 oxime is added to a mass fraction of the polyimine. In the sample 4, a resin composition containing a polyfunctional phase-containing compound A 15 parts by mass and an isocyanate compound a 15 parts by mass added to 100 parts by mass of the polyimine A was used. A resin composition in which a polyfunctional hydroxyl group-containing compound A 1 〇 mass part and 15 parts by mass of guanidinium isocyanate compound A were added to 100 parts by mass of the polyimine was used. The preparation method, evaluation method, and the like of Samples 2 to 5 are the same as those of Sample 丨. [Sample 6 to Sample 9] 158118.doc 201237101 Samples 6 to 9 are obtained by using a poly-imine (hereinafter referred to as polyimine) having a sulfonium iodide ratio of 28%, which will be described later. It is produced by functionally containing a resin composition containing a hydroxy compound a and an isocyanate compound A. The main difference between Samples 6 to 9 is the content of the polyfunctional hydroxyl-containing compound A and the blocked isocyanate a. Specifically, the sample 6 is a resin composition in which 7.5 parts by mass of the polyfunctional hydroxyl group-containing compound A and 7.5 parts by mass of the isocyanate compound A are added to the mass part of the polyimide. maker. The sample 7 was produced by adding a resin composition containing 10 parts by mass of the base compound A and 1 part by mass of the isocyanate compound a to the mass part of the polyimine. The sample 8 was produced by adding a resin composition in which 30 parts by mass of the polyfunctional hydroxyl group-containing compound A and 30 parts by mass of the isocyanate compound A were added to the mass parts of the polyamidimide. The sample 9 was produced by adding a resin composition containing 60 parts by mass of the polybasic compound A and 60 parts by mass of the isocyanate compound A to 100 parts by mass of the polyimine B. The preparation method, evaluation method, and the like of Samples 6 to 9 are the same as Sample 1. [Polyimide B] The synthesis method of polyimine B is as follows. First, a nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation well were attached to a three-neck separable flask. JEFFAMINE XTJ_542 (manufactured by Huntsman Co., Ltd., weight average molecular weight 1 〇〇〇) 4〇g, γ-butyrolactone (GBL) 60 g, and ethyl benzoate (BAEE) 6〇g were placed in an ice water bath at 0°C. 2 g of toluene, 12 g of yttrium valerolactone, and 18 g of pyridine were stirred until uniform. Further, 3,3,4,4,-biphenyltetracarboxylic dianhydride (81 > 〇人) 11.76 〇§ was added in small amounts each time. Yu Yu 5 hours • 112- 158118.doc

S 201237101 After stirring, the temperature was raised to 170 ° C and heated for 4 hours. In the reaction, the by-produced water was azeotroped with toluene. The ball-type condenser tube having the moisture separation card was used for dehydration under reflux. After the removal of the by-produced water, the reflux was stopped, and the total benzene was removed. Cool the system to 60. (: After that, BPDA 35.6 g and APB 29·73 8 g were added. After 5 hours, it was cooled to room temperature. Secondly, the product was subjected to pressure filtration by a 5 μηη transition device, thereby obtaining a ruthenium imidization ratio. It is a 28% polyimine enamel varnish. [Sample 10 to Sample 15] Samples 10 to 15 are prepared by using a resin composition containing polyamid A and isocyanate compound A. Sample 10 The main difference between the sample and the sample 5 is that the polyfunctional hydroxyl group-containing compound B to F is used as the polyfunctional hydroxyl group-containing compound. DURANOL T5652 (molecular weight 2000) manufactured by Asahi Kasei Chemicals Co., Ltd. ^As a polyfunctional hydroxyl-containing compound c, DURANOL® 4671 (molecular weight 1000) manufactured by Asahi Kasei Chemicals Co., Ltd. as a polycarbonate diol is used as a polyfunctional ketone-containing compound. D' uses Gl〇〇〇 (molecular weight 1〇〇〇) manufactured by Japan's Soda Co., which is a polybutylene dilute diol. As a polyfunctional hydroxyl-containing compound E, it is manufactured by Japan Soda Co., Ltd. as hydrogenated polybutadiene diol. GI-1000 ( The amount of 1000p is used as the polyfunctional hydroxyl group-containing compound F, and PTMG1000 (molecular weight 1000) manufactured by Mitsubishi Chemical Corporation as polytetramethylene glycol is used. Sample 10 is used in an amount of 100 parts by mass relative to the polyimine. A resin composition containing a functional group of a hydroxyl group-containing compound Β 1 〇 by mass and 5 parts by mass of an isocyanate compound A. The sample oxime is used in an amount of 100 parts by mass relative to the polyamine I58118.doc -Π3- 201237101 imine A. Produced by adding a resin composition having a polyfunctional hydroxyl group-containing compound cl〇 mass-damaged or isocyanate compound A 1 〇 by mass. Sample 12 is used in a large amount relative to the mass fraction of polyethylenimine A } A resin composition containing a base compound D 30 parts by mass and an isocyanate compound A 3 parts by mass is used. Sample 13 is a polyfunctional hydroxyl group added to 100 parts by mass of the polyimine A. Produced by a resin composition of 3 parts by mass of the compound e and 30 parts by mass of the isocyanate compound A. The sample 14 was added with a polyfunctional content in comparison with the mass fraction of the polyimine. Produced by a resin composition of 30 parts by mass of the base compound F and 30 parts by mass of the isocyanate compound A. The sample 丨5 is used in which a polyfunctional hydroxyl group-containing compound is added to 100 parts by mass of the polyamid A. The resin composition of the mass part and the isocyanate compound A 7.5 parts by mass is produced. The preparation method or evaluation method of the sample 10 to the sample 15 is the same as that of the sample 1 [sample 16 and sample 17] Samples 16 and 17 were produced using a resin composition containing polyimine a and a polyfunctional group-containing compound A. The main difference between the sample 丨6 and the sample 丨7 is that any of the isocyanate compounds B and C is used as the isocyanate compound. As the isocyanate compound B, it is manufactured by Asahi Kasei Chemical Co., Ltd., which is a hexamethylene diisocyanate S

Duranate TPA-B80E (NCO content = 12.5 wt%). As the isocyanate vinegar compound C', part number 7951 (NCO content = 7.80 wt%) manufactured by Baxenden Co., Ltd. as isophorone diisocyanate block isocyanuric acid was used. Sample 16 was used in an amount of 158118.doc - 114 - relative to 100 parts by mass of the polyimine A.

S 201237101 A resin composition having 10 parts by mass of a polyfunctional hydroxyl group-containing compound A and 9 parts by mass of an isocyanate compound b. The sample 17 was prepared by adding a resin composition containing a polyfunctional hydroxyl group-containing compound A 1 part by mass and 14 parts by mass of an isocyanate compound C to 100 parts by mass of the polyimine A. The sample 16 and the sample 17 were produced or evaluated in the same manner as in the sample 1. [Sample 18 and Sample 19] Samples 18 and 19 were produced by using a resin composition containing polyiminoimine B, a polyfunctional hydroxyl group-containing compound A, and an isocyanate compound a. The main difference between the sample 18 and the sample 19 is the content of the polyfunctional hydroxyl-containing compound a and the isocyanate compound A, and the heating conditions at the time of curing. Specifically, the sample of the sample 1 8 is prepared by adding a resin composition containing 10 parts by mass of the polyfunctional hydroxyl group-containing compound A and 1 part by mass of the isocyanate compound to the polybenzamine b 1 by mass. By. In the sample 丨9, a resin composition in which a polyfunctional hydroxyl group-containing compound a 3 parts by mass or an isocyanate compound A 3 parts by mass is added to 100 parts by mass of the polyimine B is used. The heating conditions were carried out at 18 ° C for 6 minutes, and then at 180 ° C for 60 minutes (i.e., i8 ° C, 60 minutes χ 2). The sample 18, the method of producing the sample 19, the evaluation method, and the like except for the heating conditions were the same as those of the sample 1. [Sample 20 and Sample 21] The sample 20 and the sample 21 were produced in the same manner as the sample 1 by using a resin composition containing a polyimine a, a s-S «b-containing base compound a, and an isocyanate compound a. . The main difference between Sample 20 and Sample 21 is the polyfunctional hydroxyl group 158118.doc -115- 201237101 The content of the chemical A and the isocyanate compound A. Specifically, the sample 2 is used in an amount of 3 parts by mass of the polyfunctional 3 hydroxy compound A and 3 parts by mass of the isocyanate compound A with respect to 100 parts by mass of the polyimine A. And making. In the sample 21, a resin composition obtained by adding a polyfunctional hydroxyl group-containing compound A 7 parts by mass and an isocyanide sulfonium sulfonate A 70 parts by mass to 100 parts by mass of the polyacrylonitrile A was used. By. The sample 2〇, the method of producing the sample 21, the evaluation method, and the like are the same as those of the sample file. The evaluation results of Samples 2 to 21 are shown in Table 1 below. As is apparent from the following Table 1, the warpage at the time of curing of the cured product using the resin composition of the present embodiment is sufficiently suppressed, and the solder resistance (i.e., heat resistance) is excellent. It is also excellent in insulation under the conditions of resistance to aging or high temperature and humidity. Further, from the evaluation results of Samples 10 to 15 and the like, it is understood that polybutadiene diol, hydrogenated polybutylene dilute diol, and polycarbonate diol are preferably used from the viewpoint of improving insulation properties. As a polyfunctional perfluoro-based compound. In addition, it is preferable that at least 3 parts by mass to 7 parts by mass of the polyimine, more preferably 5, is contained with respect to 100 parts by mass of the resin composition. The mass parts are ~7 〇 parts by mass, and more preferably 5 parts by mass to -6 parts by mass. Further, from the evaluation results of the sample 18, the sample 19, and the like, it is understood that from the viewpoint of improving heat resistance or chemical resistance, it is preferred to use a heat treatment and a high temperature region in combination of a low temperature region ((10) to 13 generations) ( 160~min) heat treatment. However, the conditions of the heat treatment are not limited to this. Secondly, use it with the sample! ~ A cured film was prepared by mixing the resin composition under different conditions of sample 21, and the prepared sample Μ~sample 158118.doc was confirmed.

S -116· 201237101 Features. [Sample 22 to Sample 25] s Pattern 22 to Sample 25 were produced in the same manner as the sample using a resin composition containing a polyaniline c-F, a polyfunctional perfluoro-based compound A, and an isocyanate compound A. . The main difference between Samples 22 and 25 is the ruthenium imidization ratio of polyimine. Specifically, in the sample 22 to the sample 25, 15 parts by mass of the polyfunctional hydroxyl group-containing compound a and 15 parts by mass of the isocyanate compound A are added to the mass parts of the polyimine. Producer of the composition. The preparation method or evaluation method of Samples 22 to 25 is the same as Sample 1. [Polyimide C] A method for synthesizing the brewed imine C. First, a nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation well were attached to a three-neck separable flask. At room temperature 25 ° C, charged with triethylene glycol dimethyl hydrazine 15 g, γ-butyrolactone 35 g, toluene 2 〇 · 〇 g, 4, 4 · oxy diphthalic dianhydride (MANAC The company manufactures, abbreviated as 〇DpA)1〇86 g(35 〇〇mmol) * Granted to uniformity" thereafter 'heated to 80 °C and added polyoxydiamine (manufactured by Shin-Etsu Chemical Co., Ltd., abbreviated as KF -8010) 11.30 g (13.78 mm〇l)' After further stirring for 0.5 hour, the temperature was raised to 170 ° C, and heating was carried out for 4 hours. In the reaction, the by-produced water is azeotroped with toluene, and dehydrated under reflux using a spherical condenser having a water-separating taste. After removing the by-produced water, the "stop reflux" was carried out to remove all the toluene. After the system was cooled to 1 〇〇〇c, '14 g of maleic anhydride was added and stirred for 5 hours. After standing at room temperature and 25 ° C for 12 hours, 13_bis(3_aminophenoxy 158118.doc •117- 201237101) benzene (manufactured by Mitsui Chemicals, Inc., abbreviated as APB-N) 6_00 g was added. (20.52 mmol). The mixture was stirred at room temperature for 25 hours at 25 °C. Next, the resultant was subjected to pressure filtration through a filter of 5 μm to obtain a polyamidene C varnish having a sulfonium iodide ratio of 40%. [Polyimide D] The synthesis method of polyimine D is explained. First, a nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation well were attached to a three-neck separable flask. 15 g of triethylene glycol dimethyl ether, 35 g of γ-butyrolactone, 20.0 g of toluene, and 10.86 g of ODPA (35.00 mmol) were charged at room temperature at 25 ° C, and stirred until homogeneous. Thereafter, the temperature was raised to 80 ° C and KF-8010 11.30 g (13.78 mmol) was added. After further stirring for 2 hours, the first gossip 8-N 2.17 g (7.42 mmol) was charged and stirred for 0.5 hour, after which The temperature was raised to 170 ° C and heated for 4 hours. In the reaction, the by-produced water was azeotroped with toluene, and dehydrated under reflux using a spherical condenser having a water separation well. After removing the by-produced water, the reflux was stopped, and all the toluene was removed. After the system was cooled to 100 ° C, 0.14 g of maleic anhydride was added and stirred for 5 hours. After standing at room temperature at 25 ° C for 12 hours, a second APB-N 3.83 g (13.10 mmol) was added. Stir at room temperature 25 ° C for 5 hours. Next, the product was subjected to pressure filtration by a filter of 5 μm to obtain a ruthenium amination ratio of 60 ° /. Polyimide d varnish. [Polyimine oxime] A method for synthesizing polyamidoxime is described. The first time the synthesis method of the polyimine oxime was 4.03 g (13.78 mmol), and the second APB-N was 1.97 g (6.73 mm〇i). The combination of the amine oxime 158118.doc -118· 201237101 was carried out in the same manner to obtain a brewing imidization ratio of 80 ° /. Polyimide e varnish. [Polyimine F] The synthesis method of polyimine F is explained. The first APB-N method for the synthesis of polyimine d was 4.86 g (16.62 mmol), and the second APB-N was 1·〇3 g (3.52 mmol), in addition to The synthesis method of polyimine d was carried out in the same manner to obtain a polyamidene F varnish having a quinone imidization ratio of 90%. [Sample 26] The sample 26 was produced in the same manner as in Sample 1 using a resin composition containing polyiminoimine c, polyfunctional hydroxyl-containing compound A, and isocyanate compound A. The main difference between sample 26 and sample 22 is the addition of flame retardant components. Specifically, in the sample 26, 15 parts by mass of the polyfunctional hydroxyl group-containing compound A, 15 parts by mass of the isocyanate compound A, and phosphorus produced by Fushimi Pharmaceutical Co., Ltd. were added to the mass part of the polyimine. Produced by a resin composition of 23 parts by mass of a nitrile derivative FP-300 (flame retardant A). The production method, evaluation method, and the like of the sample 26 were the same as those of the sample 1. [Sample 27] Sample 27 was produced by using the same resin composition as Sample 26. The main difference between the sample 27 and the sample 26 is that the substrate used in [Production of the cured film] is specific, and in the case of the sample 27, the copper foil 1 manufactured by Furukawa Circuit Foil Co., Ltd. is used. ? 2 _ § 12 μιη film thickness as a substrate, formed on the matte surface of the copper foil with a cured film. The film thickness after drying and hardening is about 30 μηι. The other production method or evaluation method of the sample 27 is the same as that of the sample 1 of 158118.doc-119·201237101. [Sample 28] Sample 28 was produced in the same manner as in Sample 1 using a resin composition containing polyiminoimine c, polyfunctional hydroxyl-containing compound A, and isocyanate compound A. The main difference between sample 28 and sample 22 is the addition of flame retardant components and the addition of catalyst. In the sample 28, 18 parts by mass of the polyfunctional permeation-containing compound A, 18 parts by mass of the isocyanate compound A, and phosphorus produced by Fushimi Pharmaceutical Co., Ltd. were added to the mass of the polyamidiamine c 1 〇〇. Nitrile derivative FP-300 (flame retardant a) 27 parts by mass, melamine urethane MC-20NJ pulverized product manufactured by 堺Chemical Industries Co., Ltd. (flame retardant B; average particle size i. i μηι, maximum particle size control It is produced by using a resin composition of 3 to 10 parts by mass of a resin composition of u_CAT SA (registered trademark) 1〇2 (catalyst A) manufactured by San-Apro Co., Ltd. in an amount of 0.18 parts by mass. Furukawa using Furukawa for the preparation method or evaluation method of sample 28

12 μιη film thickness of copper foil F2-WS manufactured by Circuit Foil Co., Ltd. As a substrate, a cured film was formed on the matte side of the matte, and heated at 12 Torr for 10 minutes and at 200 Å. (: The film was dried and hardened for 15 minutes, and the film thickness after hardening was about 30 μm, except that it was the same as the sample 1. [Sample 29] The sample 2 was the same resin combination as the s pattern 28 The main difference between the sample 29 and the sample 28 is only the type of the catalyst. Specifically, U-CAT (registered trademark) 11〇2 (catalyst B) manufactured by San-Apro Co., Ltd. is used. 18.18 parts by mass. The other preparation method or evaluation method of the sample 29 is the same as that of the sample 28. The evaluation results of the sample 22 to the sample 29 are shown in the following Table 2. It is described that 120·158118. Doc

In the case of Table 2, it is understood that the warpage at the time of hardening of the cured product of the resin composition of Samples 22 to 29 is sufficiently suppressed, and the solder resistance (i.e., heat resistance) is excellent. Further, it was excellent in chemical resistance or high-temperature and high-humidity conditions, and the same effects as those of the resin compositions of Sample 丨 to Sample 2 shown in Table 1 below were obtained. Next, Samples 30 to 32 were prepared using the resin films prepared in Samples 27 to 29, and the properties were confirmed. [Sample 30] Sample 30 was produced by using the resin film obtained in Sample 27. The main difference between the sample 3 and the sample 27 is that the resin film is laminated on the wiring board. Specifically, Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (the thickness of the insulating layer is 25 μm, and the conductor layer is copper foil F2_wS (18 pm)) is used as the substrate of the flexible printed wiring board, and is 4 mm. After the copper plating was performed by using a through hole having a diameter of 0.1 mm, the resin film was laminated on the wiring board subjected to the round processing by a vacuum press (180 ° C, 20 minutes, 4 MPa). After the pattern processing, the laser path is processed in the center between the through holes, and copper plating is performed to form a * layer wiring board in which daisy chain is connected with 25 channels. [Sample 31 and Sample 32] Sample 28 was used for Sample 3, and Sample 29 was used for Sample 32. A wiring board was produced by the same method as Sample 30, and Sample 3 was prepared. The same method was used for evaluation. Next, a resin film prepared by using the resin composition blended under the conditions different from the sample of the sample 32 was used to confirm the properties of the sample 33 to the sample "158118.doc -121 - 201237101. 33] Sample 33 is used in Asahi Kasei Chemicals in which a polyfunctional hydroxyl group-containing compound A and a hexamethylene diisocyanate isocyanate are added to a varnish having a ruthenium iodide ratio of 1 〇〇 °. Duranate TPA_ 100 (NCO content 23.1 wt%, hereinafter referred to as isocyanate compound c) manufactured by the company. Polyfunctional hydroxyl group-containing compound is 1 part by mass, isocyanate, relative to 100 parts by mass of polyimine. The amount of the compound C is 4,4 parts by mass. Further, the polyamidimide G is blended in an amount of 30% by mass based on the resin composition. In this case, the polyfunctional content-containing compound is contained. The molar ratio of the isocyanate group contained in the isocyanate group D to the isocyanate group is 0.9. Using the resin composition, a wiring board is produced by the same method as the sample 3, by Sample 30 is the same method Evaluation [Polyimide G] The synthesis method of polyimine G. First, a nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation well were attached to a three-neck separable flask. Under the temperature of 25 ° C, charged with triethylene glycol dimethyl ether 15 §, γ-butyrolactone 35 g, methyl 2 〇〇 g, 4, 4, oxy phthalic acid dianhydride (manufactured by MANAC) , abbreviated as 〇DpA)1〇% g(35 〇〇颜〇1) and stirred until uniform. After that, the temperature is raised to 80. (: Add polyphosphonium diamine (manufactured by Shin-Etsu Chemical Co., Ltd., abbreviated as KF-) 8010)11.3〇g(i3.78 mm〇1) 'When the mixture is stirred for 0.5 hours, the temperature is raised to 17 (TC and heated for 4 hours. In the reaction +, the by-produced water is azeotroped with toluene, and has The water is /7 away from the ball type condenser tube and is dehydrated under reflux. Remove the by-product 158118.doc

S -122· 201237101 After water, the reflux was stopped and all of the toluene was removed. After the system was cooled to 100 ° C, 0.14 g of maleic anhydride was added and stirred for 0.5 hours. After standing at room temperature and 25 ° C for 12 hours, 1,3-bis(3-aminophenoxy)benzene (manufactured by Mitsui Chemicals, Inc., abbreviated as APB-N) 6.00 g (20.52 mmol), Γ-butyrolactone 35 g, toluene 20.0 g. After stirring for 0.5 hour, the temperature was raised to 170 ° C and heating was carried out for 4 hours. In the reaction, the by-produced water is azeotroped with toluene, and dehydrated under reflux using a spherical condenser having a water separation well. After removing the by-produced water, the reflux was stopped, and the toluene was completely removed. Next, the resultant was subjected to pressure filtration through a 5 μηι filter to obtain a polyamidene G varnish having a ruthenium iodide ratio of 1%. [Sample 34] The sample 34 was obtained by adding DURANOL T5650E (molar weight 500) and isocyanate compound D manufactured by Asahi Kasei Chemicals Co., Ltd., which is a diol of polycarbonate. The δ, T5650E was 5 parts by mass, and the isocyanate compound D was 4.4 mass injures to the mass of the polyamidiamine. Further, the polyamidimidine was blended so as to be 3% by mass based on the resin composition. In this case, the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound and the mole ratio of the isocyanate group contained in the isocyanate compound D are hydroxyl group 7 isocyanate group = 0.9. Using this resin composition, a wiring board was produced by the same method as the sample 30, and evaluated by the same method as the sample π. [Sample 35] '• Model 35 is used in the varnish of polybendimimine G. Polycarbonate a, hexamethylene 158118, which has an average hydroxyl number of 3,6, as a polycarbonate 70 alcohol. Doc -123· 201237101 The base diisocyanate (hereinafter referred to as isocyanate compound E). With respect to 100 parts by mass of the polyimine G, [polycarbonate polyol a was 62 parts by mass, and hexamethylene diisocyanate was 2 parts by mass. In addition, the polyamidimide G was blended so as to be 30% by mass based on the resin composition. In this case, the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound and the molar ratio of the isocyanate group contained in the ester compound E are hydroxy/isogenic acid base = 0.9. Using this resin composition, a wiring board was produced by the same method as the sample 3', and evaluation was performed by the same method as the sample 30. The evaluation results of the ancient sample 30 to the sample 3 5 are shown in Table 3 below. [Polycarbonate Polyol A] A method for synthesizing polycarbonate polyol A will be described. Add ethylene carbonate to a 2 liter flask filled with a Dixon packing 10 mm diameter and 300 mm length and a thermometer and agitator: Ec 87 i 6

.S (9.9 mol), trihydrocarbyl propane: TMP 530.8 g (3.96 mol), i 6_ hexanediol. HDL 351.6 g (2_98 mol), 1,5-pentanediol: pdl 31〇g (2.98 mol), heating and stirring under a reduced pressure of 20 t〇rr, and controlling the internal temperature to 120 ° C to 130 ° C. One side of the distillation tower was distilled from the top of the distillation column to form an EC and ethylene glycol, and the reaction was carried out for 18 hours. Next, the steaming tower was taken out and the degree of pressure reduction was 4 Torr to recover unreacted EC and diol. After the completion of the distillation of the unreacted material, the internal temperature was changed to 19 (TC, and the diol was distilled off while maintaining the temperature to carry out a self-condensation reaction. After the reaction for 5 hours, GPC (gel) was used. Permeation chromatography) analysis gave a colorless transparent viscous liquid having a number average molecular weight of 1014 (in terms of polystyrene). The yield was 1200 g. The liquid had the following physical properties. The composition (% by mole) was 158118.doc • 124- 201237101 HDL: PDL: TMP = 30.0: 21.7: 45.4, the unit containing other ether linkages has 0.4% 'OH valence (mgKOH/g) = 198.8, and the average number of base groups = 36. [Multifunctional hydroxyl-containing compounds Evaluation of Molecular Weight] The molecular weight of the polyfunctional hydroxyl-containing compound can be measured by gel permeation chromatography (manufactured by Tosoh Co., Ltd.), and evaluated by the number average molecular weight of the molecular weight in terms of styrene. The resin film of the resin composition of the sample 30 to the sample 35 was excellent in interlayer insulation resistance, via embedding property, solder resistance (that is, heat resistance), and thermal shock resistance, and was obtained as shown in the following table. Sample 丨~sample 21 The same effect as the fat composition. When using a polyimine having a ruthenium iodide ratio of 100% (samples 33 to 35) and using a polyfunctional hydroxy compound having three or more functional groups, (Sample 35), when a bifunctional isocyanate compound was used (Sample 35), and when an isocyanate compound other than blocked isocyanate (Sample 33 to Sample 35), good results were obtained. Example 1) As a comparative example, a cured film was prepared by using a resin composition blended under the conditions different from those of the above Example 1, and the properties of the produced sample were confirmed. In this comparative example, a comparison sample was prepared. [Comparative Sample 1 to Comparative Sample 3] Comparative s1 to Comparative Sample 3 were prepared using a resin composition containing polyimine i. Comparative Sample 1 to Comparative Sample The main difference between the three components is the component other than the polyamidiamine A. Specifically, the comparative sample i is a resin composition containing no hydroxy compound A and an isocyanate compound a, which does not contain a plurality of 158118.doc.125-201237101. And production. Compare sample 2 It is produced by using a resin composition in which 5 parts by mass of the polyfunctional hydroxyl group-containing compound A is added to 100 parts by mass of the polyimine a. The comparative sample 3 is used in an amount of 〇〇 by mass relative to the polyimine. It is prepared by adding a resin composition containing 5 parts by mass of the isocyanate compound A. The preparation method or evaluation method of the comparison s pattern 1 to the comparison sample 3 is the same as that of the first embodiment. 0 [Comparative Sample 4 and Comparative Sample 5] Sample 4 and Comparative Sample 5 were produced using a resin composition containing polyimine im a, polyfunctional perfluoro-containing compound A, and isocyanate compound a. The main difference between the comparative samples 4 and 5 is the content of the isocyanate compound a relative to the polyfunctional trans-group-containing compound A (that is, the hydroxyl group contained in the polyfunctional permeation-containing compound and the isocyanate group contained in the isocyanate compound A). Moer than). More specifically, 'Comparative Sample 4 is a mixture of a polyfunctional permeation-containing compound a 1 part by mass and an isocyanate compound A 6 parts by mass based on 100 parts by mass of the polyimine A, thereby making a hydroxyl group and an isocyanate The molar ratio of the base is prepared by a resin composition having a hydroxyl group/isocyanate group = 1.4. Comparative Example 5 was prepared by adding 10 parts by mass of a polyfunctional hydroxyl group-containing compound A to an amount of the polyisocyanate a 1 part by mass, and an isocyanate compound a 20 mass> part by weight' to thereby form a hydroxyl group and an isocyanate group. The molar ratio is a resin composition having a hydroxyl group/isocyanate group = 0.4. The production method or evaluation method of the comparative samples 4 and 5 was the same as in the first embodiment. [Comparative Sample 6] Comparative Sample 6 was produced by using a resin composition containing a polyfunctional hydroxyl group-containing compound a and isocyanate 158118.doc-126-201237101 Compound A. Namely, Comparative Sample 6 was produced by using a resin composition containing no polyimine. The production method, evaluation method, and the like of Comparative Sample 6 were the same as in Example 1. [Comparative Sample 7] Comparative Sample 7 used a polyamidimide having a ruthenium iodide ratio of 100% containing a polyfunctional ketone-containing compound and a toxic isocyanate embedded in a skeleton (without a polyaminic acid structure) Polyimine; a resin composition hereinafter referred to as polybendimimine H). The polyfunctional hydroxyl group-containing compound and the isocyanate are embedded in the polyamidoxime, so that the polyfunctional content-containing compound and the blocked isocyanate are not contained as a component of the resin composition. The production method or evaluation method of the comparative sample 7 was the same as in the first embodiment. [polyimine]

The synthesis method of polyimine oxime is as follows. First, a nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation well were attached to a three-neck separable flask. It was loaded with DURANOL® 5651 (molecular weight: 1000) 78.88 g, hexamethylene diisocyanate 26.91 g, and γ-butyrolactone (GBL) 177 g manufactured by Asahi Kasei Chemicals Co., Ltd. After stirring at 200 rpm for 15 minutes at room temperature under a nitrogen atmosphere, the temperature was raised to 140 ° C and stirred for 1 hour. Then, 62.04 g (200 mmol) of 4,4·-oxydiphthalic dianhydride and 176 g of GBL were added, and the mixture was reacted at 170 ° C for 2 hours while stirring at 2 rpm. Further, it was cooled to room temperature, and BPDA 5.88 g, APB 40.55 g, GBL 353 g, toluene 70 g, Y-valerolactone 2.2 g, and a ratio of 3.5 g were added, and the mixture was stirred at 200 rpm at 17 TC. The reaction was carried out for 3.5 hours. In the reaction, the by-produced water was azeotroped with toluene, and dehydrated under reflux using a spherical type 158118.doc -127-201237101 condenser having a moisture separation trap. The reflux was stopped, and all of the toluene was removed. Secondly, the product was subjected to pressure filtration by a filter of 5 μπ1, whereby a polyamidimide varnish having a ruthenium iodide ratio of 1% was obtained. The polyimine oxime is equivalent to the fact that the polyamidene in the resin composition does not contain a polystyryl structure, and the polyfunctional ketone-containing compound and the blocked isocyanate are not used as the resin composition. The components were embedded in the skeleton of the polyimide. The evaluation results of the comparative sample 1 to the comparative sample 7 are shown in the following Table 4. By comparing the samples 1 to 3 and 6, it was confirmed: Any of the polyimine, polyfunctional hydroxyl-containing compounds, and isocyanate S compounds In the absence of the case, a good hardened material was not obtained. Further, by comparing the samples 4 and 5, it was confirmed that the isocyanate compound became excessive in the hydroxyl group/isocyanate group = 0.4 because of the isocyanate compounds between each other. The reaction is warped, and in the hydroxyl group/isocyanate group in which the polyfunctional hydroxyl group-containing compound is excessively changed, the unreacted product is increased and the chemical resistance is lowered. That is, it is confirmed that it is not a hydroxyl group/isocyanate group = 〇.5 to 1 In the case of the case, a good cured product could not be obtained. Further, by comparing the sample 7, it was confirmed that the polyfunctional hydroxyl group-containing compound and the isocyanate compound were embedded in the skeleton and did not contain the polyfunctional hydroxyl group-containing compound and the isocyanate compound. In the case of the components of the resin composition, a good cured product cannot be obtained. 158118.doc -128- 201237101 [!<] Example <s 〇r·^ ο 〇ON 〇120°C 60 minutes 180°C 30 minutes〇 〇〇<< 〇〇〇〇〇omm 〇\ d 〇〇<< 〇〇〇〇〇〇ο 沄〇\ 〇180°C60 minutes 180°C60钟〇〇◎ <<< 〇〇〇〇〇00 ο ο 〇〇〇〇 ◎ <<< 〇〇〇〇〇 o o ο 寸 Os 〇 120 ° C 60 minutes 180 ° C 30 minutes 〇〇 ◎ 〇Ο 〇 〇〇〇〇o T—M ο 〇\ σ> 〇〇〇◎ 〇〇〇〇〇〇〇o in »r> d 〇〇◎ 〇〇〇〇〇〇〇 inch o FH Os ο 〇〇〇〇〇 〇〇〇〇〇ot··^ 0\ c> 〇〇〇〇〇〇〇〇〇〇(N o Os d 〇〇〇〇〇〇〇〇〇〇o 〇〇oo 〇〇◎ 〇〇〇〇〇 〇〇〇or—i 〇ON d 〇〇◎ 〇〇〇〇〇〇〇σ\ ο § § OS d 〇〇◎ 〇〇〇〇〇〇〇00 ο oo 〇〇◎ 〇〇〇〇〇〇〇卜ο ο 〇Os o 〇〇◎ 〇〇〇〇〇〇〇VO ο VO o 〇〇◎ 〇〇〇〇〇〇〇o ο VJ o 〇〇◎ 〇〇〇〇 〇〇o νη On O 〇〇◎ 〇〇〇〇〇〇〇mo ο ο Os 〇〇〇◎ 〇〇〇〇〇〇〇<N o »〇On 〇〇〇◎ 〇〇〇〇〇〇〇 Or**H in Os 〇〇〇◎ 〇〇〇〇〇〇〇1 sample<PQ < CC1 UQ ω Ρ-. < CQ U thiol/isocyanate (mol ratio) Heating condition 1 Heating condition 2 120 ° C ~ 220 ° C viscosity elastic region and plastic region bending resistance solder resistance chemical resistance at 85 ° C, humidity 85% under insulation resistance interlayer insulation resistance through hole buried thermal shock test Resin fluidity (a) Polyimine (parts by mass) (Β) Polyfunctional hydroxy compound (parts by mass) (c-1) Isocyanate compound (parts by mass) 158118.doc • 129· 201237101 [Table 2] '-- --__ f Example sample 22 23 24 25 26 27 28 29 (a) Polyimine (parts by mass) C 100 100 100 100 100 D 100 E 100 F 100 (B) Polyfunctional hydroxy compound (parts by mass) A 15 15 15 15 15 15 18 18 (c-1) Isocyanate compound (parts by mass) A 15 15 15 15 15 15 18 18 Meridyl/isocyanate group (mol ratio) 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Flame retardant A 23 23 27 27 B 18 18 Catalyst A 0.18 B 0.18 Heating condition 1 120 ° C 60 Minute 120 °C1 [0 minutes heating condition 2 180 °C 30 minutes 200 °C 15 minutes 120 °C ~ 220 °C viscosity 〇〇〇〇〇〇〇〇 elastic region and plastic region 〇〇〇〇〇〇〇〇 Zhao Qu ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Solder resistance, chemical resistance, insulation resistance at 85 ° C and 85% humidity 〇〇〇〇〇〇 〇〇 interlayer insulation resistance 〇〇〇〇〇〇〇〇 through hole buried 〇〇〇〇〇〇〇〇 thermal shock test 〇〇〇〇〇〇〇〇 resin fluidity 〇〇〇〇〇〇〇〇 158118. Doc 130-201237101 [Table 3] ~~ ----- Example Sample 30 31 32 33 34 35 (4) Polyimine (parts by mass) C 100 100 100 G 100 100 100 (B) Polyfunctional hydroxy compound ( Parts by mass) A 15 18 18 10 G 5 Η 6.2 (c-1) Isocyanate compound (parts by mass) A 15 18 18 D 4.4 4.4 E 2 Hydroxy/isocyanate group (mol ratio) 0.9 0.9 0.9 0.9 0.9 0.9 Flame retardant A 23 27 27 B 18 18 Catalyst A 0.18 B 0.18 Heating conditions 1 120 ° C 60 minutes 120 ° C 1 0 minutes 120 ° C 60 minutes heating conditions 2 180 ° C 60 minutes 200 ° C 15 minutes 180 ° C 60 minutes 120 ° C ~ 220 ° C viscosity 〇〇〇〇 〇〇 Elastic region and plastic region 〇〇〇〇〇〇 曲 ◎ ◎ ◎ ◎ ◎ ◎ Solder resistance 〇〇〇〇〇〇 Chemical resistance 温度 at 85 ° C, humidity 85% Insulation resistance 〇〇〇〇〇〇 interlayer insulation resistance 〇〇〇〇〇〇 through hole buried 〇〇〇〇〇〇 thermal shock test 〇〇〇〇〇〇 resin fluidity 〇〇〇〇〇〇 158118.doc 131 · 201237101 [Table 4]

-'--_ Comparative Example Comparative Sample 1 2 3 4 5 6 7 (a) Polyimine (parts by mass) A 100 100 100 100 100 Η 100 (B) Polyfunctional hydroxy compound (parts by mass) A 5 10 10 10 (cI) isocyanate compound (parts by mass) A 5 6 20 10 thiol/isocyanate group (mol ratio) - - - 1.4 0.4 0.9 - Heating condition 1 20 ° C 60 minutes heating condition 2 180 ° C 30 minutes 120 ° C ~ Viscosity at 220 °C XXXXXXX Elastic region and plastic region XXXXXXX Distorted XXX 〇X 〇X Solder resistance XX 〇XXXX Chemical resistance Δ X 〇X 〇XX Insulation resistance XX at temperature 85 ° C, humidity 85% XX 〇〇 interlayer insulation resistance XX 〇 XX 〇〇 through hole embedding XXXXXXX thermal shock test XXXXXXX Resin fluidity XXXXXXX It can be seen from Table 1 to Table 4 that the evaluation results according to Example 1 and Comparative Example 1 can be confirmed by using Polyimine, polyfunctional hydroxyl-containing compound, isocyanate compound having a polyfluorene imide structure and a polyamic acid structure as a structural unit, and a hydroxyl group contained in the polyfunctional hydroxyl group-containing compound The resin composition having a hydroxyl group/isocyanate group = 0.5 to 1 in the molar ratio of the isocyanate group contained in the isocyanate compound is a cured film which is sufficiently suppressed in distortion and has excellent heat resistance. Further, as is clear from Tables 1 to 3, in the resin films of Samples 1 to 35 in which the resin composition of Example 1 was used, the viscosity at 120 ° C to 220 ° C and the elastic region of the resin film were controlled. Since the plastic region is formed, it is understood that the resin fluidity, the through-hole embedding property, and the thermal shock resistance are improved. Therefore, in the case of use in the manufacturing steps of the wiring board, the embedding property in the through hole can be simultaneously achieved, and the resin composition can be prevented from flowing out from the end portion of the wiring board. The resin composition of the second embodiment of the present invention will be described with reference to the following Examples 2 to 12 and Comparative Examples 2 to 6. Further, the following Examples 2 to 12 are the resin compositions of the second aspect. <Reagents> The reagents used in the examples and comparative examples are as follows. Further, in the following Examples 2 to 12 and Comparative Examples 2 to 6 and Tables 5 and 6, the abbreviations of the following reagents are described. (a) Polyimine component: BPDA (manufactured by Mitsui Chemicals, Inc.), APB (trade name: APB-N, manufactured by Mitsui Chemicals, Inc.), diamine represented by the general formula (5): polyetheramine (trade name: Polyetheramine D-400 (hereinafter simply referred to as "D-400"), manufactured by BASF Corporation, m+n+p=6.1), JEFFAMINE (trade name: JEFFAMINE D-230 (hereinafter only described as "D-230") ), manufactured by Huntsman, m+n+p=2.5), JEFFAMINE (trade name: JEFFAMINE XTJ-542 (hereinafter only described as "XJT-400"), manufactured by Huntsman, m+n+p = 15), JEFFAMINE (trade name: JEFFAMINE D-2000, manufactured by Huntsman, m+n+p=33). (b) Bifunctional hydroxyl group-containing compound: polycarbonate diol (trade name: DURANOL T5651 (hereinafter simply referred to as "T5651"), manufactured by Asahi Kasei Chemical Co., Ltd.), polycarbonate diol (trade name: DURANOL Τ 4671 (hereinafter only It is described as "Τ4671"), manufactured by Asahi Kasei Chemicals Co., Ltd.). (c-1) Isocyanate compound: Block isocyanate (trade name: Duranate SBN-70D (hereinafter simply referred to as "SBN-70D"), Asahi Kasei 158118.doc • 133-201237101 manufactured by Seiko Chemical Co., Ltd.), blocked isocyanate ( Product name: Duranate τρΑ· Β80Ε (hereinafter only described as γτρα_Β8〇ε), manufactured by Asahi Kasei Chemicals Co., Ltd.). (D) Photosensitizer 1 (compound having two double bonds): E〇 modified double age a dimethacrylate (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.). (D) Photosensitizer 2 (compound with more than 3 double bonds): trimethylpropane-p-modified triacrylate (trade name: AR0NIX M_3 i〇 (hereinafter only s is contained as "M-3 10" ), manufactured by the East Asian Synthetic Company, equivalent to a compound having three double bonds). (E) Photopolymerization initiator: ethyl ketone^[9·ethyl_6_(2-methylbenzhydryl)_9H-indol-3-yl]-l-(〇-acetamidine) ( Trade name: IRGAcuREOXE-02, manufactured by Ciba Japan KK). (F) Disc compound. Disc nitrile compound (trade name: Fp_3〇〇, manufactured by Fushimi Pharmaceutical Co., Ltd.). (Others). Toluene (manufactured by Wako Pure Chemical Industries, Ltd., organic synthesis), γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.), sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.). &lt;Measurement of Weight Average Molecular Weight&gt; Gel permeation chromatography (GPC), which is a method for measuring the weight average molecular weight, can be measured by the following conditions. As a solvent, Ν, ν-dimethyl decylamine (manufactured by Wako Pure Chemical Industries, Ltd., high-speed liquid chromatography) was used, and 24.8 mmol/L of brominated clock monohydrate was added before the measurement (and pure light) Manufactured by Pharmaceutical Industries, with a purity of 99.5%) and 63.2 mm〇i/L of 158118.doc

S 201237101 (manufactured by Wako Pure Chemical Industries, Inc., for high-speed liquid chromatography). Pipe column: Shodex KD-806M (made by Showa Denko)

Flow rate: 1.0 mL/min Column temperature: 40 °C Pump: PU-2080Plus (manufactured by JASCO) Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) UV-2075Plus (UV-VIS: UV Visible light meter, manufactured by JASCO Co., Ltd.) The calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation). &lt;Measurement of film thickness&gt; The film thickness measurement of the cured body was carried out using a film thickness meter (manufactured by Mitutoyo Co., Ltd., ID-C112B). &lt;Manufacturing Method of Photosensitive Film&gt; The method of applying the photosensitive resin composition is carried out by a doctor blade forming method using FILMCOATER (manufactured by TESTER S ANGYO Co., Ltd., PI 1210). The photosensitive resin composition was dropped on a PET film (manufactured by Teijin DuPont Film Co., Ltd., G2), and coated with a gap of 150 μm. The coated film was dried at 95 ° C for 12 minutes using a drier (manufactured by ESPEC Co., Ltd., SPHH-101) to obtain a photosensitive film. &lt;Lamination conditions&gt; The lamination was carried out using a vacuum press (manufactured by Naji Seisakusho Co., Ltd.). The pressing temperature was 70° (:, the pressing pressure was 0.5 MPa, and the pressing time was 30 seconds. &lt;Developability evaluation&gt; 158118.doc -135-201237101 The developability evaluation can be stopped by the following In the case of a copper pig laminate, the laminate is immersed in the laminated γ/ 2 ', under the cow with a photosensitive film, and is not exposed at 30~3〇{] mJ/cm. Then proceed. (7) Use 1% by mass aqueous sodium carbonate solution for shoulder-shoulder treatment and use water to clean the skin. After drying, the pattern is evaluated by optical microscopy. In the mask, a circle with a diameter of 100 μm is used. Shape pattern (interval between 100 μm). The film is pulled out by the developer and the copper surface is exposed in the unexposed portion, and the residual film rate is 90%, and HA ☆ ^ is not found. In the case of 〇, the residual film ratio is 9〇%, and the deformation of the pattern is found on the day after the 彳 记 记 记 A 〇 lt lt lt lt 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定 测定After lamination on Kapton (registered trademark) (12 μιη), it was carried out for 2 hours under l8〇t: Satin burning. The film is cut out at 5 Cm square. The case where the height of the end portion is within 5 sides is denoted by 〇, and the case where 5 to 1 inch is inside is denoted by Δ, and the case where the height of the ridge is greater than <Parent reliability> (I) evaluation of insulation reliability is carried out in the following manner: on a comb-shaped substrate having a line and a gap of 20 μm / 20 μm, in the above layer After laminating the photosensitive film under pressure conditions, exposure and development were carried out under the above conditions, and calcination was carried out for 2 hours at 18 ° C. The cable of the electron mobility measuring device was welded to the film, and the insulation was reliably performed under the following conditions. Test. Insulation deterioration evaluation system: SIR-12 (manufactured by Nanben Chemical Co., Ltd.) IM chamber: EHS-211M (manufactured by ESPEC)

Temperature: 85 ° C

158118.doc -136. S 201237101 Humidity: 85%

Applied voltage: 20 V Application time: 1000 hours Insulation resistance value: Write less than 1·〇χ106 Ω as X, and ^(10)(7)6 Ω~ less than ΟχΙΟ.ΟχΙΟ7 Ω as Δ, l.OxlO7 Ω~ insufficient Ι.Οχίο8 Ω is recorded as 〇, and Ι.ΟχΙΟ8 Ω or more is recorded as @. Appearance (dendritic crystal): Observing the comb-shaped substrate after the ruthenium test under the condition of an optical microscope (manufactured by ECLIPS LV100 Nikon), transmitted light, 200 times, 'The case where dendrites are produced is recorded as X, and will not be The situation found is recorded as 〇. Appearance (expansion and discoloration): The comb-shaped substrate after the IM test was observed under an optical microscope (manufactured by ECLIPS LV100 Nikon) and a field of view of 100 Å. The expansion and discoloration of the insulating film were recorded as X. It was found that only the expansion of the insulating film was recorded as Δ, and the case where no expansion and discoloration were observed was recorded as 〇. <Polyimine (1)&gt; In a separable flask equipped with a Dean-Stark apparatus and a reflux apparatus, γ-butyrolactone (255 g), toluene (51.0 g), and polyether were placed under a nitrogen atmosphere. The amine D_400 (86.8 g (201.9 mmol)) and BPDA (120 g (407.9 mmol)) were heated to 180 ° C and stirred at 180 ° C for 1 hour. After removing the terpene as an azeotropic solvent, the mixture was cooled to 40 ° C, and then APB-N (48.4 g (165.7 mmol)) was added thereto, and stirred at 40 ° C for 4 hours to obtain a polyimine (1). Solution. The weight average molecular weight of the obtained polyimine (1) is shown in Table 5 below. 158118.doc -137- 201237101 &lt;Polyimide (2)&gt; In a separable flask equipped with a Dean-Stark apparatus and a reflux apparatus, γ-butyrolactone (87.0 g) was placed under a nitrogen atmosphere. Toluene (17.0 g), polyetheramine \ D-400 (5.00 g (11.63 mmol)) 'BPDA (30.0 g (102.0 mmol)) 5 was heated to 180 ° C, and stirred under heating at 180 ° C for 1 hour. After removing the terpene as an azeotropic solvent, it was cooled to 40 ° C, and then ruthenium-iridium (23. 5 g (80.3 9 mmol)) was added, and stirred at 40 ° C for 4 hours to obtain a polyimine ( 2) The solution. The weight average molecular weight of the obtained polyimine (2) is shown in Table 5 below. &lt;Polyimine (3)&gt; In a separable flask equipped with a Dean-Stark apparatus and a reflux apparatus, γ-butyrolactone (99.0 g) and toluene (20.0 g) were placed under a nitrogen atmosphere. Polyetheramine D-400 (32.0 g (74.42 mmol)) 'BPDA (30.0 g (102.0 mmol)) &gt; The temperature was raised to 1800 ° C and stirred at 1800 ° C for 1 hour. After removing toluene as an azeotropic solvent, it was cooled to 40 ° C, and then APB-N (5.00 g (17.10 mmol)) was added, and stirred at 40 ° C for 4 hours to obtain a solution of polyimine (3). . The weight average molecular weight of the obtained polyimine (3) is shown in Table 5 below. &lt;Polyimine (4)&gt; In a separable flask equipped with a Dean-Stark apparatus and a reflux apparatus, γ-butyrolactone (80_0 g), toluene (16.0 g), and poly were charged under a nitrogen atmosphere. Ether amine D-230 (16.8 g (73.04 mmol)) &gt; BPDA (30.0 g (102.0 mmol)) &gt; The temperature was raised to 180 ° C, and the mixture was heated and stirred at 180 ° C for 1 hour. After removing the benzene as an azeotropic solvent, it was cooled to 40 ° C, and then ΑΡΒ-Ν (5·60 -138-158118.doc 201237101 g (19.16 mmol) was added, and stirred at 40 ° C for 4 hours to obtain A solution of the polyimine (4). The weight average molecular weight of the obtained polyimine (4) is shown in the following Table 5. <Polyimine (5)&gt; Under a nitrogen atmosphere, A separable flask of Dean-Stark apparatus and reflux was charged with γ-butyrolactone (107 g), toluene (21.0 g), JEFFAMINE XTJ-542 (25.7 g (25.70 mmol)) 'BPDA (30.0 g (102.0) Methyl)), the temperature was raised to 180 ° C, and the mixture was heated and stirred at 180 ° C for 1 hour. After removing the toluene as an azeotropic solvent, it was cooled to 40 ° C, followed by the addition of APB-N (18.9 g (64.65 mmol), at 40 The solution of the polyimine (5) was obtained by stirring for 4 hours at ° C. The weight average molecular weight of the obtained polyimine (5) is shown in the following Table 5. &lt;Polyimine (6) </ RTI> γ-butyrolactone (120 g), toluene (24.0 g), JEFFAMINE D-2000 (27.4 g) were placed in a separable flask equipped with a Dean-Stark apparatus and a reflux apparatus in an air atmosphere. (13.70 mmol) BPDA (30.0 g (102.0 mmol)), the temperature was raised to 180 ° C, and the mixture was heated and stirred at 180 ° C for 1 hour. After removing the toluene as an azeotropic solvent, it was cooled to 40 ° C, and then APB-N was added (22.2). g (75.94 mmol) was stirred for 4 hours at 40 ° C to obtain a solution of polyimine (6). The weight average molecular weight of the obtained polyimine (6) is shown in Table 5 below. [Example 2] T5651 (6 parts by mass), SBN_70D (6 parts by mass), ΒΡΕ-500 (40 parts by mass), Μ-310 (20 158118) were mixed with 100 parts by mass of the polyimine (1). .doc - 139 - 201237101 parts by mass), 〇XE-G2 (1 part by mass), and fp_3gq (25 parts by mass) to prepare a photosensitive resin composition. The obtained photosensitive resin composition is dried by the above method, The photosensitive film was obtained, and the developability of the photosensitive film, the warpage after firing, and the insulation reliability (resistance evaluation) were evaluated by the above methods. The results are shown in Table 6 below. [Example 3] Relative to polymerization For the mass fraction of quinone imine (i) ioo, mix T467l (6 parts by mass), SBN-70D (6 parts by mass), BPE_5 〇〇 (4 〇f parts), M 3i 〇 (2 〇 Parts), 〇XE-02 (1 part by mass), Fp_3〇〇 (25F is parts by weight) to prepare a photosensitive resin composition. The obtained photosensitive resin composition was dried by the above method to obtain a photosensitive film. The developability of the photosensitive film, the warpage after firing, and the insulation reliability (resistance) were evaluated by the above methods. The results are shown in Table 6 below. [Example 4] Τ565 1 (6 parts by mass), ΤΡΑ-Β80Ε (6 parts by mass), βΡΕ_5〇〇 (4 parts by mass), Μ_ 3 were mixed with 100 parts by mass of the polyimine (1). 10 (20 parts by mass), ΟΧΕ-Ο2 (1 part by mass), and FP-300 (25 parts by mass), and a photosensitive resin composition was prepared. The obtained photosensitive resin composition was dried by the above method to obtain a photosensitive film. The developability of the photosensitive film, the warpage after firing, and the insulation reliability (resistance to corrosion) were evaluated by the above methods. The results are shown in Table 6 below. [Example 5] T565 1 (6 parts by mass), SBN_70D (10 parts by mass) 'BPE-500 (40 parts by mass), μ-158118.doc were mixed with respect to 100 parts by mass of the polyimine (1). -140-201237101 310 (20 parts by mass), OXE_02 (1 part by mass), and Fp_3〇〇 (25 parts by mass), and a photosensitive resin composition was prepared. The obtained photosensitive fat composition was dried by the above method to obtain a photosensitive film. The developability of the photosensitive film, the warpage after firing, and the insulation reliability (resistance evaluation) were evaluated by the above methods. The results are shown in Table 6 below. [Example 6] Relative to polyimine (1) 100 parts by mass, Τ5651 (6 parts by mass), SBN-70D (6 parts by mass), BpE_500 (40f parts), 〇XE〇2 (1 part by mass), FP-3〇0 (25 parts by mass) The photosensitive resin composition is prepared by the above method, and the obtained photosensitive resin composition is dried to obtain a photosensitive film. The developability of the photosensitive film, the warpage after firing, and the insulation are obtained by the above method. The reliability (IM resistance) was evaluated. The results are shown in the following Table 6. [Example 7] T5651 (6 mass damage) was mixed with 1 part by mass of the polyimine (1), SBN-70D (6 parts by mass), μ_3 10 (20 parts by mass), 〇ΧΕ-02 (1 parts by mass), and FP-300 (25 parts by mass) were prepared to prepare a photosensitive resin composition, which was obtained by the above method. The photosensitive resin composition is dried to obtain a photosensitive film, and the developability of the photosensitive film, the warpage after firing, and the like are obtained by the above method. The edge reliability (IM resistance) was evaluated. The results are shown in the following Table 6. [Example 8 to Example 12] Each of the polybenzamine (2) to (6) was used in an amount of 1 part by mass. T5651 (6 parts by mass), SBN-70D (6 parts by mass), bpe_5 〇〇 (4 parts by mass), m_310 (20 parts by mass), ΟΧΕ-Ο2 (1 part by mass), Fp_3 〇〇 (25 parts by mass) The photosensitive resin composition is prepared, and the photosensitive resin composition 158118.doc-141-201237101 is dried by the above method to obtain a photosensitive film. The developability of the photosensitive film by the above method, The warpage after the calcination and the insulation reliability (IIvU± resistance) were evaluated. The results are shown in the following Table 6. [Comparative Example 2] The mixture was mixed with respect to 100 parts by mass of the polyimine (1).匕5〇〇 (4〇 parts by mass), M-310 (20 parts by mass), OXE_〇2 (1 parts by mass), Fp_3〇〇Q5 parts by mass) 'Preparation of photosensitive resin composition>> by the above method The obtained photosensitive resin composition was dried to obtain a photosensitive film. The developability of the photosensitive film, the warpage after firing, and the insulation reliability (IM resistance) were evaluated by the above method. The results are shown in Table 6 below. [Comparative Example 3] T565 1 (6 parts by mass), BPE-500 (40 parts by mass), m_310 (20 parts by mass), and OXE_〇2 were mixed with respect to 100 parts by mass of the polyimine (1). 1 part by mass), FP-300 (25 parts by mass), and a photosensitive resin composition was prepared. The obtained photosensitive resin composition was dried by the above method to obtain a photosensitive film. The developability of the photosensitive film, the warpage after firing, and the insulation reliability (IM resistance) were evaluated by the above method. The results are shown in Table 6 below. [Comparative Example 4] SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE- were mixed with 100 parts by mass of the polyimine (1).感光 2 (1 part by mass) and FP-300 (25 parts by mass) were prepared to prepare a photosensitive resin composition. The obtained photosensitive resin composition was dried by the above method to obtain a photosensitive film. The developability of the photosensitive film, the distortion after satin burning, and the insulation reliability (IM resistance) were evaluated by the above methods. The results are shown below 142· 158118.doc

S 201237101 is described in Table 6. [Comparative Example 5] T5651 (6 parts by mass), SBN-70D (15 parts by mass), ΒΡΕ-500 (40 parts by mass), and Μ-310 were mixed with 100 parts by mass of the polyimine (1). 20 parts by mass), ΟΧΕ-Ο2 (1 part by mass), and FP-300 (25 parts by mass), and a photosensitive resin composition was prepared. The obtained photosensitive resin composition was dried by the above method to obtain a photosensitive film. The developability of the photosensitive film, the charm after calcination, and the insulation reliability (IM property) were evaluated by the above method. The results are shown in Table 6 below. [Comparative Example 6] T565 1 (15 parts by mass), SBN-70D (6 parts by mass), ΒΡΕ-500 (40 parts by mass), Μ-31 were mixed with 100 parts by mass of the polyimine (1). 0 (20 parts by mass), ΟΧΕ-Ο2 (1 part by mass), and FP-300 (25 parts by mass), and a photosensitive resin composition was prepared. The obtained photosensitive resin composition was dried by the above method to obtain a photosensitive film. The developability of the photosensitive film, the warpage after firing, and the insulation reliability (IM resistance) were evaluated by the above methods. The results are shown in Table 6 below. [Table 5] Diamine (A+B)/(A+B+C) represented by the formula (5) Weight average molecular weight Polyimine (1) D-400 0.55 23000 Polyimine (2) D -400 0.12 21000 Polyimine (3) D-400 0.81 25000 Polyimine (4) D-230 0.79 22000 Polyimine (5) XTJ-542 0.28 26000 Polyimine (6) D-2000 0.15 26000 158118.doc -143- 201237101 Insulation reliability (resistance to stagnation) i expansion and discoloration 〇〇〇〇&lt;〇〇&lt;〇〇&lt;&lt; X 〇〇&lt; dendritic 〇〇〇〇〇 〇〇〇〇〇〇XX Ο Ο X Insulation resistance value ◎◎◎◎〇◎◎◎〇〇&lt;&lt;&lt; @@ &lt;00000&lt;&lt;0&lt;00 X〇XX〇 developability〇〇〇〇 〇&lt;&lt;&lt;〇〇&lt;〇〇〇&lt;&lt;(F&gt;filling compound i mass parts Csl (N&lt;N(N&lt;N&lt;N(N(N(N(S&lt;N ηη *η 〇ιηιη ό &lt;Ν &lt;Ν &Ν;Ν (Ν (Ν 贱 Township FP-300 FP-300 FP-300 FP-300 FP-300 FP-300 FP-300 FP-300 FP-300 FP-300 FP- 300 FP-300 FP-300 FP-300 FP-300 FP-300 (E) Photopolymerization initiator i parts by mass i OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 OXE- 02 OXE-02 OXE-02 OXE-02 OX E-02 OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 (D) Photosensitizer 2 Φ) SSSSS 骇乡 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 M-310 (D) Photosensitive 剤1 i part by mass ooooo, ooooo inch, inch to 兮Tf to inch 々 wear?? § Type i ooooo ooooo ooooo ooooo 1 1 1 1 1 k 1 1 1 1 1 Pl, cu CL, 0L. CU CL| pL. CX4 CL) PQ CQ CQ CQ CQ CQ CQ CQ CQ BPE-500 BPE-500 BPE- 500 BPE-500 BPE-500 (c-1) Isophthalate compound i mass parts \〇\〇\〇^ \〇\〇s〇^ ^0 1 · VO 2 v〇 type i QQgQQQQQQQQ 〇〇§〇〇 〇〇〇〇〇〇卜卜卜&quot;卜卜卜卜1 · (JU 1 1 1 1 1 1 1 1 PQCQScQCQCQQQfflfflfflffi C/50〇Pc/3WCOC/3C/3C/20000 QQQ 000 Bu Bu 1 ' έ έ i: PQ CQ CQ C/3 C/3 ¢/3 (b) 2-functional hydroxyl-containing compound i part by mass Ό S〇S〇V〇S〇\〇\〇S〇V〇V〇Ό 1 SO 1 S〇^ Type i T5651 T4671 T5651 T5651 T5651 T5651 T5651 T5651 T5651 T5651 T5651 T5651 T5651 T5651 (a) Polyimine i mass parts 00000000000 00000000000 ooooo ooooo鞔乡/—s /—V /—S /~S »&lt;—S /*—V /—VV ——&lt;S (7) inch*Λ Ό S_&gt;^ S_/ Sm/ «w· 隹Mo 甾 甾甾 甾 钼 接 接 接 锺 锺 锺 锺 锺 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ^ NW* ^ ^ ta ta «η κη «n 琏 琏餹琏 琏餹琏 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 12 Example 12 m ^ m &lt;〇# #猫锚#

158118.doc - 144-S 201237101 According to the results shown in Tables 5 and 6, it is understood that the developing examples, warpage, and insulation reliability are good in comparison between Examples 2 to 12 and Comparative Examples 2 to 6. . In particular, in the case of Example 2 to Example 2, in any case of 〇. 1 〇 $ (A + B) / (A + B + C) $ 0.85, both have developability, warpage, and insulation reliability. . On the other hand, in the photosensitive composition containing no bifunctional hydroxyl group-containing compound and isocyanate compound, warpage and dendritic crystals were generated (refer to Comparative Example 2). In addition, even in the case of containing a bifunctional hydroxyl group-containing compound, dendritic crystals are produced in the photosensitive resin composition containing no isocyanate compound, although the warpage is improved (refer to Comparative Example 3). Further, even In the case of containing an isocyanate compound, the dendritic crystal was found to be improved in the photosensitive resin composition containing no bifunctional hydroxyl group-containing compound, but the warpage was caused (see Comparative Example 4). These results are due to the absence of a bifunctional hydroxyl-containing compound having a boating effect or a isocyanate compound which forms a crosslinked structure with a polyimine and a difunctional hydroxyl-containing compound to produce warpage and dendrites. Further, even in the case of containing a bifunctional hydroxyl group-containing compound and an isocyanate compound, warpage occurs in the photosensitive resin composition in which the hydroxyl group of the difunctional hydroxyl group-containing compound and the isocyanate group of the isocyanate compound are less than 0.5. As a result (refer to Comparative Example 5), the dendritic crystal was produced in the photosensitive resin composition exceeding 1.0 (refer to Comparative Example 6). These results are due to the fact that the proportion of the bifunctional hydroxy compound having a warpage reducing effect is small, so that warpage occurs or the ratio of the isocyanate compound is small, so that a crosslinked structure which cannot form a sufficient crosslinked structure with polythenimine is produced 158118.doc - 145- 201237101 Dendritic crystals. The resin composition of the third embodiment of the present invention will be described with reference to the following Examples 13 to 24, Comparative Example 7, and Comparative Example 8. Further, the following Examples 13 to 24 are the resin compositions of the second aspect. &lt;Reagent&gt; In the examples and comparative examples, polyfluorene diamine (manufactured by Shin-Etsu Chemical Co., Ltd., KF-8010) and 1,3-bis(3-aminophenoxy) as reagents to be used Benzene (manufactured by Mitsui Chemicals, Inc., APB-N), polyoxytetramethylene-di-p-aminophenyl phthalate (manufactured by IHARA CHEMICAL INDUSTRY CO., LTD., abbreviated as PMAB, the following formula (22) , 4,4'-oxydiphthalic dianhydride (manufactured by MANAC, abbreviated as ODPA), 3,3·,4,4·-biphenyltetraphthalic acid dianhydride (manufactured by Mitsui Chemicals, Inc.) BPDA), pyromellitic acid dianhydride (manufactured by Daicel Chemical Industry Co., Ltd., abbreviated as PMDA), ethylene glycol bis(trimellitic acid monoester anhydride) (manufactured by Shinji Ryo Chemical Co., Ltd., RIKACID TMEG-100, Abbreviated as TMEG), tris(butoxyethyl) phosphate (manufactured by Daihatsu Chemical Co., Ltd.), phosphazene compound (Manufactured by Fushimi Pharmaceutical Co., Ltd., Rabitle (registered trademark) FP-300, abbreviated as FP-3 00 Ethylketone 1-[9-ethyl-6-(2-mercaptobenzylidene)-9H-indazol-3-yl]-1-(0-acetamidine) (Ciba Japan Κ·Κ · Record, trade name: IRGACURE Ο ΧΕ 02, abbreviated as ΟΧΕ-02), 2,2-bis(4-(mercaptopropenyloxypentaethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: ΒΡΕ-500), Ethylene oxide (ΕΟ) modified bisphenol quinone dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: BPE-500), heptapropanediol dimethacrylate. (Manufactured and branded by Shin-Nakamura Chemical Industry Co., Ltd. Name: 9PG), Penta-146- 158118.doc 201237101 Tetrahydrin tri/tetrakis (meth) acrylate (manufactured by Toagosei Co., Ltd., trade name: ARONIX M-3 06, abbreviated as M-306), trioxindole Propane EO modified triacrylate (manufactured by Toagosei Co., Ltd., trade name: ARONIX M-350, abbreviated as M-350), trimethylolpropane PO modified triacrylate (manufactured by Toagosei Co., Ltd., trade name: ARONIX M-3 1 0, abbreviated as M-3 1 0), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMMT), EO-modified glycerol tris(decyl) acrylate (new Made in Nakamura Chemical Industry Co., Ltd., A-GLY-9E (EO modified 9 mol)) polycarbonate diol (Asahi Kasei Chemicals Co., Ltd. Manufacture, DURANOL T5651), hexamethylene diisocyanate block isocyanate (made by Asahi Kasei Chemical Co., Ltd., Duranate SBN-70D), benzene (manufactured by Wako Pure Chemical Industries, Ltd., organic synthesis), γ-butyrolactone (and pure light) Triethylene glycol dimethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) and sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) can be used in the reaction without performing special purification. General formula (22) Η2Ν -0 and Η2〇Η2〇Η2〇Η2〇-〇|~&lt;^ 〉~~ΝΗ^ &lt;Measurement of weight average molecular weight&gt; In the second embodiment The conditions were determined under the same conditions. &lt;Photosensitive film production method&gt; It was produced in the same manner as in the examples of the second embodiment described above. &lt;Lamination conditions&gt; 158118.doc -147-201237101 The same as the embodiment of the second embodiment described above. <Insulation reliability (HAST resistance) evaluation> The insulation reliability evaluation was performed as follows. On a comb-shaped substrate having a line and a gap of 2 μm η / 20 μm, a photosensitive dry film was laminated under the above-mentioned laminating conditions, and then exposed and developed under the above conditions, and subjected to five hours at 18 〇t: Burn it all. The cable for soldering the electron mobility measuring instrument on the photosensitive dry film was subjected to an insulation reliability test under the following conditions. Insulation deterioration evaluation system: SIR-12 (manufactured by Nanben Chemical Co., Ltd.) HAST chamber: EHS-211M (manufactured by ESPEC) Temperature: llOt: Humidity: 85%

Applied voltage: 2 V Application time: 528 hours Insulation resistance value: Write less than 1 〇 xl 〇 6 ports as x, and 丨〇χ 1 〇 6 less than 1. Ox 1 〇 7 Ω as a, 1 〇xi〇7 q~The case of less than 1 〇χ丨〇8 Ω is denoted by 〇, and the case of 1·〇Χίο8 Ω or more is denoted as ◎. Appearance (dendritic crystal): The comb-shaped substrate after the HAST test was observed under an optical microscope (manufactured by ECLIPS LV100 Nikon) and transmitted light 200 times, and the case where dendritic crystals were produced was recorded as X, which was not The situation found is recorded as 〇. Appearance (expansion and discoloration): Observing the comb-shaped substrate after the HAST test under the condition of an optical microscope (manufactured by ECLIPS LV100 Nikon), bright field, 100 times, 'Insulation film with a diameter of 50 μηι φ or more will be found. The case of expansion and/or discoloration is denoted by X, and it is found that 膨胀μΓη φ or more, not 158118.doc -148· 201237101, the expansion and/or discoloration of the insulating film of the foot 50 _Φ is recorded as Δ, and the expansion and The case where the discoloration is 10 μπι Φ or less is denoted as 〇. &lt;Measurement of warpage after calcination&gt; The resulting sensation ### _~9 dry film was laminated on apt0n (° main article trademark) under the above laminating conditions, and then subjected to 1 hour at 18 °C. Satin burning. The photosensitive dry cocoon is cut out to 5 em square 'the shape of the end portion is less than 5 claws, the It shape 5 is ◎, and the case where 5 to less than 1 〇 is described as 〇, which will have the above ridge height. The situation is recorded as X. &lt;Resolution Evaluation&gt; The resolution evaluation can be as follows. The photosensitive dry film was laminated on the copper backing layer plate under the lamination conditions 7, and then exposed to light at 30 to 270 mJ/cm2. Then use 1 mass ° /. The alkaline development treatment of the aqueous sodium carbonate solution and the rinsing with water 'after drying, the pattern was &lt; Line and gap (L/s) patterns of 5〇 gm~i〇〇 are used in the mask. The portion where the residual film ratio in the exposed portion (hardened portion) due to development is 1 〇〇 0 / 〇 and the copper surface of the unexposed portion (dissolved portion) appears is read. The case where the L/S pattern of 7 〇 μπι can be solved is denoted by ◎, and the case where the resolution of 1 〇〇 pmiL/s can be solved is denoted by 〇', and the case where 1 〇〇 μΓη cannot be solved is denoted by X. ' Polyimine (7)&gt; • In a separable flask, triethylene glycol dioxime (15 g), γ-butyrolactone (35 g), toluene (20.0) were placed under a nitrogen atmosphere. g), polyoxydiamine (1^-8010 (11.30 g (13.78 mmol)), 〇DPA (10.86 g (35,00 mm〇l)), heated and stirred at 120 ° C for 1 hour. The Dean-Stark apparatus and the refluxer were connected and heated and stirred at 180 ° C for 1 hour. The toluene as azeotropic solvent 158118.doc -149·201237101 was removed and cooled to 25. (:, then APB-N (6.00 g ( 20.52 mmol) was stirred at 25 ° C for 8 hours to obtain a solution of polyimine (7). The weight average molecular weight of the obtained polyimine (7) is shown in Table 7 below. Yttrium (8)&gt; In a separable flask, triethylene glycol dimethyl ether (15 g), γ-butyrolactone (35 g), toluene (20.0 g), were placed under a nitrogen atmosphere. Polyoxydiamine #?-8010 (11.00 g (l3.41 mmol)), BPDA (10.30 g (35.00 mmol)), heated and stirred at 120 ° C for 1 hour. Then connected to Dean_Stark device and refluxer' Stirring at 180 ° C for 1 hour with heating. Removal as an azeotropic solvent After toluene, it was cooled to 25. (:, then APB-N (6.10 g (20.87 mmol) was added and stirred at 25 ° C for 8 hours to obtain a solution of polyimine (8). 8) The weight average molecular weight is shown in the following Table 7. &lt;Polyimine (9)&gt; In a gas-liquid environment, a separable plate was charged with triethylene glycol dioxime (15 g). ), γ-butyrolactone (35 g), toluene (20.0 g), polyoxydiamine (KF_ 8010 (9.50 g (ll.59 mmol)), PMDA (7.63 g (35.00 mmol)), at 120 C The mixture was heated and stirred for 1 hour, and then connected to a Dean_Stark apparatus and a reflux vessel, and heated and stirred at 1880 C for 1 hour. The toluene as an azeotropic solvent was removed, and then cooled to 25 ° C, followed by addition of ΑΡΒ·Ν (6.65 g ( 22.75 mmol) was stirred at 25 C for 8 hours to obtain a solution of polyimine (9). The weight average molecular weight of the obtained polyimine (9) is shown in Table 7 below. Amine (10)&gt; In a separable flask, triethylene glycol dioxime 158118.doc was placed under a nitrogen atmosphere.

S-150· 201237101 (15 g), γ-butyrolactone (35 g), toluene (20.0 g), polyoxydiamine (1&lt;^-8010 (13.15 g (16.04 mmol)), TMEG (14.36) g (35.00 mmol)), heating and stirring at 120 ° C for 1 hour, followed by connection with a Dean-Stark apparatus and a refluxer 'heating and stirring at 180 ° C for 1 hour. The benzene was removed as an azeotropic solvent and then cooled to At 25 ° C, APB-N (5.34 g (18.27 mmol) was added and stirred at 25 ° C for 8 hours to obtain a solution of polyimine (10). The average weight of the obtained polyimine (10) was averaged. The molecular weights are shown in the following Table 7. &lt;Polyimine (11)&gt; In a separable flask, triethylene glycol dioxime (15 g), γ-butyrolactone was charged under a nitrogen atmosphere. (35 g), toluene (20.0 g), PMAB ((12.00 g (9.69 mmol)) · 〇DPA (10.86 g (35.00 mmol)), heated at 120 ° C for 1 hour, then connected to Dean- The Stark apparatus and the refluxer were heated and stirred at 180 ° C for 1 hour. The toluene was removed as an azeotropic solvent and then cooled.

But to 25 ° C ', then add APB-N (7.20 g (24.63 mmol) and stir at 25 ° C for 8 hours to obtain a solution of polyimine (11). The resulting polyimine (11) The weight average molecular weight is shown in the following Table 7. [Example 13 to Example 15] Each of the polyimine (7), the polyimine (g), and the polyimine (9) In terms of parts by mass, 'mixed BPE-500 (20 parts by mass), M-310 (20 parts by mass), 〇xe-〇2 (i parts by mass), Fp_3〇〇 (25 parts by mass), ΤΒχρ (15 parts by mass) The photosensitive resin composition is prepared by dry film formation of the obtained photosensitive resin composition by the above-mentioned dry film production method, and the photosensitive film is obtained by laminating the photosensitive film under the above-mentioned lamination conditions. On the comb-type substrate, the insulation reliability of the obtained laminated film was evaluated. The results are shown in Table 8 below, 158118.doc-151·201237101. Further, in Example 13 and Example 14, the warpage was ◎. The resolution was ◎; in Example 15, the warpage was 〇 and the resolution was @. [Example 16] Mixing 2 Å with respect to 1 part by mass of the polynymine (7) _50 0 (40 parts by mass), ΟΧΕ-Ο2 (1 parts by mass), ρρ_3 〇〇 (25 parts by mass), hydrazine (15 parts by mass), and a photosensitive resin composition was prepared, and the obtained photosensitive resin composition was borrowed. The laminated film was produced in the same manner as in Example 13 to Example IS to evaluate the insulation reliability. The results are shown in the following Table 8. The warpage was ◎, and the resolution was X. [Examples] 17] Mixing μ_3 10 (40 parts by mass), 〇ΧΕ-〇2 (1 part by mass), Fp_3〇〇 (25 parts by mass), τΒΧΡ (1 5) with respect to 100 parts by mass of the polyimine (7). In the photosensitive resin composition obtained from the above, a laminate film was produced by the same method as in Example 13 to Example 15, and the insulation reliability was evaluated. Further, the warpage is 〇, and the resolution is 〇. [Example 18] 3 parts of ugly-900 (20 parts by mass) are mixed with 100 parts by mass of the polyimine (7), Μ-310 (20 parts by mass), 〇ΧΕ-02 (1 parts by mass), FP-300 (25 parts by mass), TBXP (15 parts by mass), modulating photosensitive resin From the obtained photosensitive resin composition, a laminate film was produced by the same method as in Example 13 to Example 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The curve is ◎, and the resolution is 〇. [Example 19] • 152- 158118.doc

S 201237101 9pG (2 parts by mass), M-310 (2 parts by mass), 〇xe-〇2 (1 part by mass), FP- are mixed with 100 parts by mass of the polyimine (7). 300 (25 parts by mass) and TBXP (15 parts by mass) were prepared to prepare a photosensitive resin composition. A laminate film was produced by the same method as that of Example 13 to Example 15 from the obtained photosensitive resin composition, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, the warpage was ◎, and the resolution was 〇. [Example 20] With respect to 100 parts by mass of the polyimine (7), 8 ugly-500 (20 parts by mass), M-350 (20 parts by mass), and 〇xe-〇2 (1 part by mass) were mixed. FP-300 (25 parts by mass) and TBXP (15 parts by mass) were prepared to prepare a photosensitive resin composition. From the obtained photosensitive resin composition ', a laminate film was produced by the same method as in Example 13 to Example 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, the warpage was ◎, and the resolution was [Example 21] 3 parts of ugly-500 (20 parts by mass) and M-306 (20 parts by mass) based on 100 parts by mass of the polyimine (7). ), xe-〇2 (1 part by mass), FP-300 (25 parts by mass), and TBXP (15 parts by mass) were prepared to prepare a photosensitive resin composition. From the obtained photosensitive resin composition, a laminate film was produced by the same method as in Examples 13 to 15 to evaluate the insulation reliability. The results are shown in Table 8 below. Further, the warpage is ◎, and the resolution is ©. [Example 22] BPE-500 (20 parts by mass), A-TMMT (20 parts by mass), 〇xe-02 (1 part by mass), FP were mixed with 100 parts by mass of the polyimine (7). -300 (25 parts by mass), TBXP (15 parts by mass), and a photosensitive resin combination 158118.doc • 153-201237101. From the obtained photosensitive resin composition, a laminate film was produced by the same method as in Example 13 to Example 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, the warpage was ◎, and the resolution was ©. [Example 23] A mixture of 8 --500 (20 parts by mass), A-GLY-9E (20 parts by mass), 〇XE-02 (1 mass) with respect to 100 parts by mass of the polyimine (7) Parts), Fp_300 (25 parts by mass), and TBXP (15 parts by mass) were prepared to prepare a photosensitive resin composition. From the obtained photosensitive resin composition, a laminate film was produced by the same method as in Example 13 to Example 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, the warpage was ◎, and the resolution was ◎. [Example 24] BPE-500 (20 parts by mass), M-310 (20 parts by mass), 〇χΕ_〇2 (ΐ by mass), and 100 parts by mass of the polyimine (7) were mixed. Fp_300 (25 parts by mass), TBXP (15 parts by mass), Τ5651 (3 parts by mass), and SBN-70D (3 mass damage) were prepared to prepare a photosensitive resin composition. From the obtained photosensitive resin composition, a laminate film was produced in the same manner as in Example 13 to Example 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, the warpage was ◎' resolution was ◎. [Comparative Example 7 and Comparative Example 8] BPE-500 (20 parts by mass) and M_31 〇 (2) were mixed with 1 part by mass of each of the polyimine (1 〇) and the polyimine (11).感光质量份), 〇χΕ〇2 (1 parts by mass), FP-300 (25 parts by mass), ΤΒχρ〇 5 parts by mass), and a photosensitive resin composition was prepared. From the obtained photosensitive resin composition, a laminate film was produced by the same method as in Example 13 to Example 15, and the insulation reliability was evaluated in 158118.doc • 154 - 201237101. The results are shown in Table 8 below. Further, in Comparative Example 7 and Comparative Example 8, the warpage was ◎, and the resolution was ◎. [Table 7] Structure of acid dioxane diamine oxime (% by mass) Molecular weight (Mw) Type of addition (mole) Type of addition (mole) Addition amount (mole) Polyimine ( 7) ODPA 35.00 KF-8010 13.78 APB-N 20.52 40.0 40,000 Polyimine (8) BPDA 35.00 KF-8010 13.41 APB-N 20.87 40.0 30,000 Polyimine (9) PMDA 35.00 KF-8010 11.59 APB-N 22.75 40.0 35,000 Polyimine (10) TMECr 35.00 KF-8010 16.04 APB-N 18.27 40.0 35,000 Polyimine (11) ODPA 35.00 PMAB 9.69 APB-N 24.63 0.0 30,000 155- 158118.doc 201237101 Anger 5 Appearance (dendritic Crystallization) 〇〇〇〇〇〇〇〇〇〇〇〇XX Appearance (expansion and discoloration) 〇〇〇&lt;〇&lt; Ο 〇&lt;&lt;&lt; 〇XX Insulation resistance value 〇〇〇&lt; 〇〇〇 〇&lt;&lt;&lt;&lt; ◎ XX ! (F) Phosphorus compound addition amount i (parts by mass) 25.0 15.0 Ο 〇wS wS &lt;N - 25.0 15.0 25.0 15.0 25.0 15.0 25.0 15.0 25.0 15.0 25.0 15.0 ο ο ir&gt; w- &gt;&lt;N — ο ο fN — 25.0 15.0 Ο 〇uS wS CN — 25.0 15.0 25.0 15.0 Type FP-300 TB XP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP-300 TBXP FP -300 j TBXP (Η) Photopolymerization start 剤«W甶4 mpopppqqpp ρ ο p ρ q Type OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 OXH-02 OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 OXE-02 iS spoon 呛 呛 呛 蛛 蛛 蛛 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° 20.0 20.0 20.0 20.0 !Type M-310 M-310 M-310 * M-310 M-310 M-310 M-350 M-306 Α-ΤΜΜΤ A-GLY -9Ε M-310 M-310 M-310 m « ί^ ^ Perton δ·安*w甶| 20.0 1_ 20.0 20.0 40.0 • 20.0 20.0 20.0 20.0 20.0 _1 20.0 -1 20.0 20.0 20.0 Type BPE-500 BPE-500 BPE-500 BPE-500 1 BPE-900 9PG BPE- 500 BPE-500 BPE-500 BPE-500 BPE-500 BPE-500 BPE-500 (〇1) Addition amount of bismuth isophthalate compound (quality Dong) • 1 1 1 • 1 1 1 • o cW • « i type • 1 « 1 ' • 1 1 t 1 • SBN-70D • • (b) Addition amount of 2-functional hydroxy compound (parts by mass) • 1 • • 1 1 1 1 1 • o 1 &gt; i type 1_ I 1 * 1 1 1 1 1 1 « T5651 1 « (a) Polyimine 1_ Addition (parts by mass) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 0 100.0 100.0 Kinds of polyiminoimide...-(71-polyimine (8)_polyimine (9) Polyimine (7) Polyimine ω — Polyimine (Z) _ Polyimine Polyimine (7) Polyimine (7) - Polyimine (71... Polyimine - ω_ Polyimine (7) 隹 « s Polyimine ο υ Example 13 Example 14 Implementation Example 15 Example 16 Example π Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Comparative Example 7 Comparative Example 8 lS8118.doc -156-s 201237101 From Table 7 and Table 8 As a result, it is understood that Example 13 to Example of using a photosensitive resin composition containing the polyimine structure represented by the above formula (7) and the polyphthalic acid structure represented by the above formula (8) Among them, in comparison with Comparative Example 7 and Comparative Example 8, the insulation reliability (HAST resistance) was excellent. Further, when Example 13 and Example 20 are compared with Example 22 and Example 23, it is understood that the (fluorenyl) acrylate compound having three or more double bonds including the structure represented by the above formula (10) is obtained. The insulation reliability (HAST resistance) of the resin composition is further improved. The resin composition of the fourth embodiment of the present invention will be described with reference to the following Example 25, Example 26, and Comparative Example 9 to Comparative Example 11. Further, the following Example 25 and Example 26 are the resin compositions of the second aspect. [Example 25] In the present example, as the resin composition, the sulfhydrylation ratio was 100 ° /. A two-terminal phenol-modified polyoxoxime _22·1821 (hydroxyl value: 38 mgKOH/g) manufactured by Shin-Etsu Chemical Co., Ltd. as a bifunctional hydroxy compound, as an oxazoline compound, is added to the varnish of the polyamidene Z. i,3•bis(4,5-dihydro-2-oxazolyl)benzene (hereinafter referred to as Bp0) and flame retardant A (refer to Example 1). The use of a two-terminal phenol-modified polyoxoxene x_22_1821 5 parts by mass, a BPO 13 parts by mass, and a flame retardant a 33 parts by mass of the Shin-Etsu Chemical Co., Ltd. . The resin composition was applied to a copper foil at 95. The underlayer was dried for 12 minutes to obtain a resin film having a thickness of 30 μm. This resin film was used in the evaluation of alkali solubility. Further, the resin film was at 18 Torr. The underarm is heated for 6 minutes to obtain hardening 158118.doc -157- 201237101. This hardened material is used in the evaluation of the testability. Hereinafter, a method for synthesizing polyimine z will be described. [Polyimide Z] The synthesis method of polyimine Z is explained. First, a nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation well were attached to a three-neck separable flask. At room temperature 25 ° C, charged with triethylene glycol dioxime 15 g, γ-butyrolactone 35 g, toluene 20.0 g, 4,4'-oxybisphthalic acid dianhydride (MANAC) Manufactured, abbreviated as 〇DPA) 10.86 g (35.00 mmol), stirred until homogeneous. Thereafter, the temperature was raised to 80 ° C, and 12.05 g (14.7 mmol) of polyoxydeoxydiamine (manufactured by Shin-Etsu Chemical Co., Ltd., abbreviated as KF-8010) was added, and after further stirring for 0.5 hours, the temperature was raised to 17 Torr. (:, heating for 4 hours. In the reaction, the water produced by the by-product is azeotroped with benzene, and dehydrated under reflux using a spherical condenser having a water separation well. After the secondary water is removed, the reflux is stopped. The toluene was completely removed. After standing at room temperature for 25 hours, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 7.56 g (20.65 mmol), γ- was added after cooling for 12 hours. 35 g of butyrolactone and 20 g of toluene. After stirring for 5 hours, the temperature was raised to 170 ° C for 4 hours. In the reaction, the by-produced water was azeotroped with toluene, and a water separation well was used. The ball-shaped condenser is dehydrated under reflux, and after the removal of the by-produced water, the reflux is stopped to remove all the toluene. Next, the product is subjected to pressure filtration by a filter of 5 μm to obtain the ruthenium iodide. The polyimide varnish having a yield of 1% by weight. [Evaluation of warpage] The evaluation of warpage was evaluated by the ridge of the resin film at four corners, specifically, at 23 ° C and a humidity of 50%. 'Cut the above sample to 5 cmx5 cm, 158118.doc 158· 201237101 Geodesic angle relative to the central part The bulging distance is warpage, and the surface curvature is ι 〇 mm or less as good as 〇, the 5 mm or less is better as ◎, and the 15 mm or less is recorded as Δ, which is more than 15 111111 It is described as X as a defect. [Evaluation of solder resistance] The solder resistance is based on the JPCA-BM02 specification, and the cured product cut into 3 cm J c Π1 is immersed in a solder bath for 26 seconds (TC immersion for 60 seconds). The evaluation was carried out. The appearance was visually inspected, and the presence or absence of changes such as deformation and dissolution was confirmed. The overall area was 90 ❶ /. The above-mentioned no change was recorded as 〇, and 50% to 90% of the total area was found. In the case of Δ, the case where the area where no change was found was less than 50% was referred to as X. [Evaluation of alkali solubility] The resin film was immersed in a 3% aqueous sodium hydroxide solution at 48 ° C, and the film thickness was measured. The dissolution rate was evaluated for solubility. The case where the film thickness was dissolved at 2 degrees 〇·2 μΓη/sec or more was recorded as 〇, which would be less than 〇2: Lu Ji is X. [Evaluation of alkali resistance] The hardened material was immersed in an aqueous solution of sodium hydroxide at 48 ° C for 3 minutes to determine the pre-impregnation. The change in film thickness was evaluated for alkali resistance, and the case of being 2 μm or less was denoted by 〇, and the case of exceeding 2 μηη was denoted by X. [Through hole embedding property] Measured in the first embodiment The measurement was carried out under the same conditions as in Example 1 [Cold and Thermal Shock Test] 158118.doc • 159·201237101 The measurement was carried out under the same conditions as in the first embodiment of the first embodiment. [Resin fluidity] In the first embodiment described above The measurement was carried out under the same conditions as in Example 1. [Example 26] In the present embodiment, as the resin composition, a two-terminal phenolic modification manufactured by Shin-Etsu Chemical Co., Ltd. as a bifunctional hydroxy compound was added to 100 parts by mass of the polyimine. The polyorganophosphonium _22 ΐ 821 1 part by mass, 20 parts by mass of BP0 as the oxazoline compound, and 33 parts by mass of the flame retardant a. A resin film and a cured product were produced in the same manner as in Example 25 and evaluated. [Comparative Example 9] In the present embodiment, as the resin composition, 33 parts by mass of the flame retardant A was added without adding a bifunctional hydroxy compound to 100 parts by mass of the polyamidene Z. In the same manner as in Example 25, a resin film and a cured product were produced and evaluated. [Comparative Example 10] In the present embodiment, a two-terminal phenol-modified polyoxosiloxane manufactured by Shin-Etsu Chemical Co., Ltd., which is a bifunctional hydroxy compound, was used as a resin composition, without using the polyamidene Z. Χ_22_1821 1 part by mass, 20 parts by mass of BPO as an oxazoline compound, and 33 parts by mass of flame retardant a. In the same manner as in Example 25, a resin film and a cured product were produced and evaluated. [Comparative Example 11] 158118.doc

S.160·201237101 In the present embodiment, 'as a resin composition, a two-end type manufactured by Shin-Etsu Chemicals A, which is a bifunctional hydroxy compound, is added to 100 parts by mass of the polyacrylonitrile Z. Phenol modified polysulfide ISM plasmon flame retardant A 3 3 parts by mass. In the same manner as in Example 25, a resin film and a cured product were produced and evaluated. The evaluation results of Example 25, Example 26, and Comparative Example 9 to Comparative Example 11 are shown in Table 9 below. As is apparent from the following Table 9, the resin films using the resin compositions of Example 25 and Example 26 showed solubility, and the cured product showed durability, and thus was low in distortion and excellent in solder resistance, and was obtained as described above. The resin compositions of the other examples have the same effects. On the other hand, in Comparative Example 9 to Comparative Example 11, it was found that evaluation of solder resistance, warpage, and the like in the case where any of the polyimine, the bifunctional group-containing compound, and the oxetine compound were not contained. deterioration. 158118.doc -161 - 201237101 [Table 9]

--^~~~_ Example 25 Example 26 Comparative Example 9 Comparative Example 10 Comparative Example 11 (a) Polyimine (parts by mass) Z 100 100 100 100 (b) Bifunctional hydroxy compound (parts by mass) 5 10 10 10 (c-2) Oxazoline compound (parts by mass) 13 20 20 Flame retardant A 33 33 33 33 33 Heating conditions 1 95 ° C 12 minutes heating condition 2 180 ° C 60 minutes surface curvature ◎ ◎ X ◎ X resistance Solderability 〇〇 验 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 〇〇 埋 埋 埋 埋 埋 X 〇 X Thermal thermal shock test 〇〇 XXX Resin fluidity 〇〇 XXX Further, the present invention is not limited to the above The embodiment can be implemented with various modifications. In the above-described embodiments, the size, shape, and the like as illustrated in the drawings are not limited thereto, and can be appropriately changed within the range in which the effects of the present invention are exerted. Further, it can be carried out as appropriate without departing from the scope of the object of the invention. [Industrial Applicability] The present invention has an effect of realizing a resin composition which can achieve sufficient warpage at the time of curing and excellent heat resistance, and particularly can be used as a semiconductor element. The surface protective film, the interlayer insulating film, the adhesive sheet, the semiconductor package substrate, the protective layer of the circuit board, the protective insulating film for a printed wiring board, and the protective insulating film for a flexible printed circuit board are suitably used. This application is based on Japanese Patent No. 2011-007862, filed on January 18, 2011, and filed on March 18, 2011. This patent 2011-062186, -162-158118.doc

S 201237101 Japanese Patent No. 2011-107290, filed on May 12, 2011, and Japanese Patent No. 2 011-1 60730, filed on July 22, 2011. All of these contents are included. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A-F is a schematic view showing a small number of manufacturing of a multilayer flexible wiring board of the embodiment. [Main component symbol description] 11 Insulating substrate 12a, 12b, 15a Copper box 13 Through hole 14 Bond copper 15 Laminated body 15b Protective layer 16 Flexible portion 17 Protective film 158118.doc - 163-

Claims (1)

201237101 VII. Patent application scope: 1. A resin composition comprising (A) a polymer compound, (B) a polyfunctional hydroxyl group-containing compound having two or more groups, and (c) a polymer compound And/or a polyfunctional crosslinkable compound having two or more crosslinkable functional groups forming a crosslinkage bond between the polyfunctional hydroxyl-containing compounds, and the polyfunctional crosslinkable compound may be a polymer compound and/or A three-dimensional crosslink is formed between the aforementioned polyfunctional permeation-containing compounds. The resin composition of claim 1, wherein the polymer compound has a quinone imine group and/or a guanamine group, and the three-dimensional crosslinks comprise c=mercapto group and/or NH group. 3. The resin composition according to claim 2, wherein the polyfunctional hydroxyl group-containing compound and/or the polyfunctional crosslinkable compound is a trifunctional or higher functional group. 4. The resin composition according to any one of claims 1 to 3, wherein the polymer compound has a hydroxyl group and/or a carboxyl group. 5. The resin composition according to any one of claims 1 to 4, wherein the poly-B energy-containing hydroxy compound comprises a phenol-modified polyfluorene oxide, a polybutadiene polyol, and a hydrogenated polybutane selected from the two ends. At least one of a diene polyol and a polycarbonate polyol. 6. The resin composition according to any one of item 5, wherein the polyfunctional ketone-containing compound contains an aliphatic structure. 7. The resin composition according to any one of claims 1 to 3, wherein the polyfunctional group-containing compound is a polycarbonate polyol. The resin composition according to any one of items 1 to 7, wherein the polyfunctional crosslinkable compound comprises a plurality of or more isocyanate groups. 158118.doc 201237101 Functional isocyanate compound β The crosslinkable compound contains two of the above polyfunctional upper block isocyanate groups. 11. The resin composition according to any one of claims 1 to 1 wherein the polyphenyl group is capable of repeating a polyfunctional crosslinkable compound than a hydroxyl group/crosslinkable functional group, wherein 100 parts by mass of the same knife compound as described above is used. The content of the polyfunctional hydroxyl group-containing compound is from 5 parts by mass to 60 parts by mass. The resin composition according to any one of the items 1 to 11, wherein the content of the polyfunctional crosslinkable compound is from 5 parts by mass to 60% by mass based on 1 part by mass of the knive compound. Share. The resin composition according to any one of claims 1 to 12, wherein the number average molecular weight of the above-mentioned polycyclic guanidine 3-based compound is 500 to 3000 » 14. In the resin composition, the polymer compound has a repeating structure represented by the following formula (1): [Chemical Formula 1] Formula (1) Q Ο 158118.doc 201237101 (in the formula (1, Φ V * .' γι represents an organic group of 2 valence, Ζι denotes an organic group of 4 valence, a represents an integer of 1 to 50). As claimed in claims 1 to 14 t - The resin composition of any one of the above-mentioned polymer compounds, wherein the polymer compound is represented by the following formula (2), wherein the polymer compound is a resin composition according to any one of the above items (1). Repeating structure: [Chemical 2] General formula (2) Υι such as -Υ2ρ〇-γ,|4〇-γ4[ 0 Yjj a N 0 person 2 Y 〇 (in formula (2) 'Zl and Z2 represent 4 price The organic group, Υι, γ2, Υ3, Y, and 丫5 knives independently represent a carbon number of 1 to a carbon number of 5, and may also be 4; b, (: and (1 respectively independently represent Bu 5〇) The resin composition according to any one of claims 1 to 16, wherein the high tetra compound has a polyimine structure represented by the following formula (3) and a lower formula (4) The poly-proline structure is represented as a repeating structural unit: [Chemical 3] General formula (3) 158118.doc 201237101 General formula (4) r17n-^^n— η〇-τΓ f〇h ο ο (In equations (3) and (4), R, R2, R4, RR 7 , R1〇, Rn, Rn*!^4 each independently represent a hydrogen atom or a monovalent organic group having a carbon number 丨~carbon number of 2〇; R3, I, &amp;, R丨2 and 1^ respectively represent the number of fields 1~ The organic group 'm, n, and p of the carbon number of 4 carbon atoms independently represent an integer of 100 or more and 整数, and R!6 represents a tetravalent organic group, and represents an organic group having a field number of 1 to a carbon number of 90. ). 18. The resin composition of claim 17, wherein the diamine component constituting the polyimine represented by the above formula (3) comprises a diamine represented by the following formula (5): General formula (5) 2n 3 5 4 11 1 R1 - RIR. 1012~11 RIO^UO^τη ^丨^—^ ^Am /rs 13 2 ri-r—r H2 (in equation (5), Rl, R2, R4 ' R5, RR « R 8 R10, Rn, R And an organic group independently representing a hydrogen atom or a carbon number 丨 to a carbon number of 20; ^^ and ~ respectively represent an organic group having a carbon number of 20 carbon atoms, m, n, p respectively Independently equal to an integer less than 3〇, and satisfies l$(m+n+p)S30). l58H8.doc -4- 201237101 Sub-compound has the following pass:) = lipid combination: wherein the above "[5] shows the structure as a repeating unit: Formula (6) 'only ten. % (in the formula (9), Ri, R2, R4, r5, R7, r, 9 12 and Rl5 represent the base of the carbon number 1 to the carbon number of 4, and the claws, n, and 卩 are independent The ground indicates an integer of 30 or more; 丨6 indicates an organic group having a tetravalent value, and represents an organic group having a carbon number of 丨 to a carbon number of 2, and A, B, and c represent m〇1% of each unit, and satisfy 〇 A resin composition according to any one of claims 1 to 19, wherein the aforementioned polymer compound has the following formula (a) ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 7) The polyimine structure represented by the present invention and the polyamic acid structure represented by the following formula (8) are as structural units: [7] General formula (7) R1( -----/e 9 9 IewnD^ I ο / RtB_sl-—R1 \ 3 ΖΟΛ ΥΟ Ν tong 158118.doc 201237101 Γ^^ (In the formulae (7) and (8), Ζ1 2 and Ζ3 are derived from the following general formula (9), and the tetravalent organic group of the tetracarboxylic dianhydride may be the same or ^ ^ ^J is different; R is an organic group having a carbon number of 1 to a carbon number of 30, and R19 is an organic group having a valence of 1 to a carbon number of 30, and an integer of 1 or more and 20 or less. General formula (9) (D) 158118.doc -6- 1 1 · The resin composition according to any one of claims 1 to 20 has two or more photopolymerizable unsaturated double bonds (meth)acrylic acid Chemical character, (E) photopolymerization initiator. The resin composition of claim 21, wherein the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is a (meth) acrylate having three or more double bonds Ester compound. The resin composition of claim 22, wherein the (meth) acrylate compound having three or more double bonds includes a compound represented by the following formula (1): 201237101 Formula (10) R» CH2〇-(E-〇)rC— I 0 Rao H3C-CH2-C—CH2〇-(H-〇)7-C— &lt;^420为-0)^-? O Ri CH 2 /iS2-QH2 (In the formula (10), R 2 〇 represents a hydrogen atom or a fluorenyl group, and a plurality of E independently represent a C 2 to a C 5 alkyl group, which may be the same or different; It is an integer from 1 to 10.) The resin composition of any one of claims 21 to 23, wherein the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds as described above contains two double bonds (曱An acrylate compound and a (fluorenyl) acrylate compound having three or more double bonds. The resin composition according to any one of claims 1 to 24, which contains (1?) a phosphorus compound. 26. The resin composition of claim 25, wherein the phosphorus compound comprises a linonic acid ester compound and/or a scaly nitrile compound. 27. A resin composition' characterized by a temperature of 85. 〇, humidity 85 ° /. The interlayer insulation resistance in the insulation reliability test of 1 hour is ΙΟ9 Ω or more ’120. 〇220. The crucible has a viscosity of 5000 Pa·s to 100,000 Pa·s, and has an elastic region having an elongation of less than 20% and a plastic region having an elongation of 50% or more, and the film thickness of the interlayer insulating layer is 4 μm or less. 2 8. A hardened material' characterized in that the resin composition according to any one of claims 158118.doc 201237101 is heated at 100 ° C to 130 ° C for 5 minutes to 60 minutes. It is obtained by heating at 160 ° C to 200 ° C for 15 minutes to 60 minutes. A resin film comprising: a substrate; and a resin composition according to any one of claims 1 to 27, which is provided on the substrate. 30. The resin film of claim 29, wherein the aforementioned substrate is a carrier film. The resin film of claim 29 or 30, which comprises a cover film provided on the aforementioned resin composition. The resin film according to any one of claims 29 to 31, wherein the substrate is a copper foil. 33. A wiring board </ RTI> characterized by comprising: a substrate having a wiring, and a resin composition according to any one of claims 1 to 27, which is provided to cover the wiring. 158118.doc