TW201107418A - Resin composition, cured product, and circuit board using same - Google Patents

Abstract

Disclosed is a resin composition which is suppressed in warping and rebound properties after thermosetting, and provides a cured film having excellent chemical resistance, heat resistance and flame retardancy. Specifically disclosed is a resin composition containing a polyimide precursor that has a polyether structure and a compound that has a thermally crosslinkable functional group, said resin composition being characterized in that the polyimide precursor has an imidization ratio of 40-98% (inclusive).

Description

[Technical Field] The present invention relates to a heat-resistant resin composition which is effective as a surface protective film for a semiconductor element, an interlayer insulating film, a bonding sheet, and a protective insulating film for a printed wiring board, A cured product and a circuit board using the same. [Prior Art] The surface protective film, the interlayer insulating film, and the protective insulating film for printed wiring boards of the semiconductor device are excellent in heat resistance. Therefore, a resin composition containing polyimine has been used. In particular, when applied to a flexible wiring circuit, it is required that the resin composition has less surface curvature after hardening. As a resin composition which is excellent in heat resistance and prevents warpage after curing, a resin group of a polyimide ink including an ester terminal oligomer and an amine terminal oligomer is disclosed (for example, see Patent Document). However, such a resin composition must be heat-treated at a temperature of at least 25 η or more for the imidization, and the formed polyimide resin has a large shrinkage and has a problem in workability. In the case of circuit materials, 'there is a reaction between the county and the wiring material, and the oxidation of the wiring material occurs. ~ Feng can harden at a low temperature on the one hand 4 V ip.J ^ /JQ ^ ^ Bao Qu, and reveal There is a polyacrylonitrile oxime precursor which is triamine-based (tetra)-fired as a diamine component (for example, refer to Patent Document 2 and Patent Document 3). However, the polyimide-based oxime oxime precursor is coated. When the ruthenium is imidized on the circuit board to form a protective film of the circuit, there is a problem of the connection between the protective film and the succeeding sheet in the prepreg or bonding step thereof. 148610.doc 201107418 Revealing the use of m amines, A non-polyoxygenated polyimine precursor which reduces a hydrazine imidization temperature and is partially yttrium-imided in the use of a photosensitive dry anti-knocking agent (for example, refer to the patent document... However, the semi-animed imidization is included The softening property of the cured product of the polyimide precursor is insufficient. When the component is mounted on the surface of the circuit board, a circuit protection film for preventing solder adhesion or the like is formed in a portion other than the portion where solder is required. In the case of a film and a photosensitive anti-material, at this time, since the jade, the exposure step, the development step, and the like are required to be laminated, the process becomes complicated. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. DISCLOSURE OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for suppressing distortion and resilience after thermosetting, and chemical resistance. A resin composition of a cured film having excellent heat and flame retardancy. [Technical means for solving the problem] The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found that 'containing a specific structure and having a specific range of imidization The resin composition of the polyimine precursor and the compound having a heat-crosslinkable functional group can be suitably used to solve the above problems, and based on this finding, the present invention is completed by 148610.doc 201107418. That is, the present invention is as follows The resin composition of the present invention is characterized by comprising a polyimine precursor having a polyether structure, a compound having a heat crosslinkable functional group, and a brewed imine of the above-mentioned polyanilin precursor. The conversion rate is 40% or more and 98% or less. • In the resin composition of the present invention, it is preferred that the ruthenium imidization ratio of the above polyimide precursor is 40% or more and 95% or less. In the resin composition of the present invention, it is preferred that the polyimine precursor comprises a polyimine moiety having a structure of the following formula (1): [Chemical Formula 1]

(In the formula (1), ZjZ2 represents a tetravalent organic group, and Ri, R2, R3, and the core represent a C 1 to C 5 alkyl group, which may have a side chain; m, 11 and (1 represents 1 to 50) In the resin composition of the present invention, it is preferred that the content of the diamine having the structure of the following formula (7) among all the diamines in the above polyimine precursor is 15 mol%. Above 8 5 m. /. The following: [Chemical 2] R1 + 〇 - R2 is long. _R3 is good. - (In the formula (2), Rl, r2, r3, ~ and ^ represent carbon number and carbon number 5 1486l0.doc 201107418, which may have a side chain; 1«, 11 and 9 represent an integer of 1 to 50) (> In the resin composition of the present invention, it is preferred to have the structure of the above formula (2) In the diamine, the alkylene group represented by 'R.2, R3, R4 and Rs has two or more kinds of stretching groups. In the resin composition of the present invention, it is preferred to have the structure of the above formula (2). The weight average molecular weight of the diamine is in the range of 4 〇〇 to 2,000. In the resin composition of the present invention, it is preferred that the weight average molecular weight of the diamine having the structure of the above formula (2) is 6 〇〇. 2〇〇 In the resin composition of the present invention, it is preferred that the polyimine precursor comprises a polylysine moiety having a poly-proline structure and a polyimine moiety having a polyimine structure. The diamine having the structure of the above formula (2) is more contained in the polyimine portion than the polyamino acid moiety. In the resin composition of the present invention, preferably the above 4 and Z2 of the general formula (1) are a tetravalent organic group represented by the following formula (3): [Chemical 3]

(In the formula (3), R丨7 represents _0_, -S02- or _c〇_). It is preferable that the above-mentioned polyimine precursor is higher than the above, and the sulfonium imidization ratio D% and the content of the di-sodium relative to the total acid component are not in the resin composition of the present invention, and the preferred one is The ruthenium iodide ratio is 50% or more, and the relationship between the 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride and the 矣% is satisfied (Eg 0.6D-30). In the resin composition of the invention, it is preferred that the above formula (1) and the I486I0.doc 201107418 Z2 are contained in the removal of 3,3,4,4,-diphenylsulfonetetracarboxylic dianhydride x^#. The tetravalent organic residue of the monoanhydride structure and the tetravalent organic residue of the dianhydride structure are removed from the 3,3',4,4'-dipyridyl 7-acid dianhydride. In the resin composition of the present invention, it is preferred that the above formula (1) 4 and z2 comprise a dianhydride structure removed from 3,3·,4,4·-diphenylsulfonetetracarboxylic dianhydride L ^ 昕. The tetravalent organic residue and the tetravalent organic residue of the dianhydride structure are removed from the 4,4'-oxybis-o-diphenyl __T'-monoanhydride. In the resin composition of the present invention, the preferred polyimine precursor contains a polyimine moiety having the structure of the following formula (4): [Chemical 4]

(In the formula (4), 'I and & represents a tetravalent organic group, 'is an alkyl group having a carbon number of 2 to a carbon number, and h represents an integer of 1 to 50). In the resin composition of the present invention, it is preferred that the content of the diamine having the structure of the following formula (5) in all the diamines in the above (iv) imine precursor is 15 mol% or more and 85 mol. ear. /. The following: [Chemical 5]

(In the formula (7), 'R1S represents an alkyl group having a carbon number of 2 to a carbon number of 1 Å, and h is an integer of 148610.doc 201107418). The diamine group diamine in the present invention: [Chem. 6] In the composition of the tree a composition, it is preferred that the polyimine precursor further contains at least one of the following formula (6). aromatic

Nh2

Rl9 is represented by the following formula (7) or the following formula (8); (in the formula (6) [Chemical 7]

-0

(In the formula (8), R2? represents a single bond, and in the resin composition of the present invention, bis(3-aminophenoxy) is stupid. -S〇2- or -C(CH3)2-). It is preferred that the above aromatic-amine is a resin which is not invented-'. It is preferred that the compound having a thermally crosslinked fluorenyl group is flammable by a resin formed by polymerization of a saponin. The compound of the functional group in the resin composition of the present invention is selected from the group consisting of a compound, an epoxy compound, and at least one compound blocked. Preferably, the above-mentioned group having a heat crosslinkable tillage compound and a benzoindole compound isocyanate compound is 148610.doc 201107418. In the resin composition of the present invention, the 鲂τ is preferably 热. The compound of the linking functional group does not substantially require a compound having a thermal crosslinking functional group of a thermal crosslinking accelerator. In the tree residual towel of the present invention, it is preferred to contain the above-mentioned compound having a thermally crosslinkable functional group in an amount of from i part by mass to 4 parts by mass based on 1 part by mass of the above-mentioned polyimide precursor. In the tree assay of the present invention, it is preferred that the ruthenium imidization ratio of the above polyimide precursor is 40% or more and 90% or less. In the resin composition of the present invention, it is preferred that the acid value of the above (IV) imine precursor is 16 mg KOH/g or more. In the resin composition of the present invention, it is preferred that the resin composition is stored for 3 months, and the change in viscosity is 2 〇 0 / 〇 or less. In the resin composition of the present invention, it is preferred that the acid value of the polyimine precursor is i6 mg KOH/g or more to 7 〇 mg K 〇 H/g or less and the resin composition is stored in the stagnation month. After that, the change in viscosity is 1% or less. In the combination of the present invention, it is preferred that the terminal end of the polymer backbone of the (iv) imine precursor is at least one selected from the group consisting of a monoamine derivative or a carboxylic acid derivative. End agent) end capping. In the resin composition of the present invention, (4), after the thermal curing, the elastic modulus was 0H4 GPa, and in the solder bath, it was immersed for 6 sec seconds in the 26th generation, and there was no swelling or charring. In the resin composition of the present invention, it is preferred to further contain a flame retardant, and the content of the elemental element is not more than ppm, and the flame retardancy of vtm〇 is obtained according to the standard of _94. I48610.doc 201107418 The resin composition for screen printing according to the present invention is characterized in that it is a resin composition and has a solid content concentration of 45% or more, which is printed on a substrate by screen printing, and dried when dried. The film thickness is 15 μηηα and the penetration is 40 μπι or less.

The material for forming a protective film of the present invention is characterized in that it comprises the above-mentioned resin composition D. The cured product of the present invention is characterized in that it is obtained by thermally curing the above resin composition. The circuit board of the present invention is characterized by comprising a base material having wiring and a cured material covering the surface of the base material. In the printed wiring board of the present invention, the flexible printed wiring board having the component mounting portion is used in the resin composition for screen printing, which is characterized in that it includes a joint portion necessary for mounting a component by screen printing. It is obtained by the step of printing the resin composition in a part other than that. The polyimine precursor of the present invention is characterized in that it comprises a tetracarboxylic dianhydride represented by the following formula (9) and an alkyl ether group represented by the following formula (2). The amine and a polymer of at least one aromatic diamine represented by the following formula (6), and the ruthenium imidization ratio of the polyimide precursor is 4% or more and 98% or less: [Chem. 8]

148610.doc 10· 201107418 (in the formula (9) ’ R_2! indicates,).

[Chemistry 9]

HgM _______R1 _又_ __ 〇——— 3, Han 4 and Κ·5 represent the carbon number 1 to carbon number 5, the alkylene η and q represent the integer of 50); (in the formula (7) 'R!, R base' Can have side chains; m, [10]

Mh2 (Formula (6) + ' Rl9 is represented by the following formula (7) or the following formula (8)); [Chemical 11] · 〇-- 0

0-- (in the formula (8), r20 represents a single bond, _〇_, _s〇2K(CH3)2_). In the polyimine precursor of the present invention, it is preferred that the above tetracarboxylic dianhydride further includes 3,3',4,4,-benzophenonetetracarboxylic dianhydride. In the polyimine precursor of the present invention, it is preferred that the ruthenium iodide ratio is 50% or more, and the oxime imidization ratio is D%, and 3,3,4,4,-diphenyl sulfone. The relationship between the two needles of tetracarboxylic acid relative to the total acid component content E mole % satisfies the relationship of (E $ 〇6D_3〇) 148610.doc 11 - 201107418. In the diamine having the structure of the polyiminoimine precursor (2) of the present invention, R2, an alkylene group or more is represented. In the 'family car, the alkylene group having the above formula, the rule 4 and the Rs has 2, and the imine precursor of the invention is preferably a diamine having the structure of the above formula (2). The weight average molecular weight is in the range of _~. In the polyimine precursor of the present invention, it is preferred that the diamine having the structure of the above formula (2) has a weight average molecular weight of 6 Å to 2 Å (9). In the "imine precursor" of the present invention, it is preferred that the amine having the structure of the above formula (7) is more contained in the polyimine than the polyimine precursor. [Effects of the Invention] According to the present invention, it is possible to provide a resin composition which is formed into a cured film which is excellent in chemical properties, heat resistance and flame retardancy, and which is excellent in chemical properties, heat resistance and flame retardancy. [Embodiment] Hereinafter, the present invention will be specifically described. The resin composition of the present invention comprises a polyimine precursor having a polyether structure and a compound having a heat crosslinkable functional group, and the polyimide imidization ratio of the polyimide precursor is 40% or more and 98% or less. . The resin composition of the present invention can control the glass transition temperature and the elastic modulus of the cured product after thermosetting by containing a polyimine precursor having a polyether structure, and has less warpage and can exhibit low resilience. Further, the resin composition of the present invention forms a crosslink of 148610.doc -12- 201107418 which forms a compound having a heat crosslinkable functional group after thermosetting. In the resin composition of the present invention, the polyamidiamine precursor having a poly-imidazolium precursor having a structure and a compound having a heat crosslinkable functional group forms a chemical parent pair and has a polyether structure. Since the polyoxyalkylene chain is formed, a three-dimensional network structure is formed by local interaction between the polymer chains, and thus heat resistance can be exhibited. χ, if the imidization ratio of the polyimide precursor is 98% or less, the poly-imine before cross-linking with the compound having a heat-crosslinkable functional group remains sufficiently, and after hardening, Out of ί chemical properties, heat resistance. In addition, when the ruthenium imidization ratio of the polyimide precursor is 40% or more, the reductive residue which can be dissolved in the alkaline solution after curing is reduced, and chemical resistance and heat resistance can be exhibited. Here, the imidization ratio of the polyimide precursor is preferably 95% or less, more preferably 90% or less. Further, the ruthenium iodization ratio was measured by the method described in the following Example (Measurement of oxime iodization ratio). (Α) Polyimine precursor The polyimine precursor has no particular limitation if it has a polyether structure. Further, it is preferred to use a polyimine precursor comprising a polyimine moiety having a structure of the following formula (1): [Chemical 12] 0 0 Ο

Ri -ο-r2 ^〇^R4^〇_Rs_nX\z/

ο (In the formula (1), Ζ! & Ζ 2 represents a tetravalent organic group, R, R _ _ 2 Κ 3, R 4 , and Rf . and the q table represents a carbon number of 1 to a carbon number of 5 Has a side chain; m 'no 148610.doc -13· 201107418 1 to 50 integer). Further, it is preferred that the content of the diamine having the structure of the following formula (2) among all the diamines in the polyimine precursor is 15 mol% or more and 85 mol% or less: ] h2n—Ri+. minus 2 *. —3 *〇—r七一一 2 (In the formula (2), R丨, R2, R3, r4, and Rs represent a carbon number 丨~carbon number 5 alkylene group, which may have a side chain; m, η and q represents an integer of 1 to 5 )). From the viewpoint of the adhesion to the substrate, it is preferred that in the above formula (2), 'R2, & R4 and Rs have two or more kinds of alkylene groups. Specific examples of the diamine represented by the above formula (2) include polyoxyethylene diamine, polyoxypropylene diamine, and other polyoxyalkylene diamines having an oxygen alkyl group having a different carbon chain number. Wait. Examples of the polyoxyalkylene diamines include polyoxyethylenediamines such as jeffamine ED-600, ED-900, and ED-2003 manufactured by Huntsman Corporation of the United States, or Jeffamine D-230, D-400, and D-2000. Polyoxypropylenediamine such as D-4000, or Jeffamine XTJ-542, XTJ-533, XTJ-536, etc. having a polytetradecyl group-extended ethyl group. Among them, 'EdR-丨48, D-230, D-400, HK-511, etc. having a relatively low molecular weight can form a polymer having a relatively high glass transition temperature' and thus can be preferably used for necessary heat resistance, Chemical resistant use. On the other hand, it is excellent in flexibility such as 〇_2〇〇〇 having a relatively high molecular weight, solubility in a solvent having a low boiling point, and the like. These may be used alone or in combination of two or more types 148610.doc -14- 201107418. Further, in terms 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 2,000, particularly preferably from 600 to 2 Å. Hey. As the polyoxyalkylene diamine having such a weight average molecular weight, it is preferred to use -6 〇〇, ED-900, and XTJ-542. Among them, polyoxyalkylene diamines having an oxygen-extended alkyl group having a different number of carbon chains, for example, ED-6GG and ED-9G0 having a polyethylethylenediamine having an extended ethyl group and a stretching propyl group, The propyl and tetramethylene = polyoxyethylene diamine XTU42, milk _533, solvent solubility further improved 'is particularly well used. Further, the diamine represented by the above formula (2) has a high purity, and it is easy to obtain a high molecular weight when it is made into polyamic acid and polyamidiamine. The purity of the diamine of the above formula is preferably 95% or more, more preferably 97. /. The above is particularly preferable to be 98.5% or more. The content of the diamine represented by the above formula (2) is preferably from 15 mol% to 85 mol% based on the entire diamine. It is better to be Momo%~6 one 莫 Moer%, especially good is 30 Mo%%~5〇 Moer%. When it is 15 mol% or more, it exhibits low warpage and low resilience, and when it is 85 mol% or less, it is excellent in solvent resistance and heat resistance. Other diamines which can be used other than the diamine represented by the above formula (2), such as, for example, 3,3'-diaminobenzophenone, 4,4,-diaminobenzidine Same, 3,3'-diaminodiphenyl ether, 4,4,-diaminodiphenyl ether, 1, bis-bisaminoamine phenyl, hydrazine, 4 bis (4-aminobenzene) Oxy)benzene, bis(3-(3-aminophenoxy)phenyl)ether, bis(4-(4-aminophenoxy)phenyl)ether, 1,3-bis(3-(3- Amine 14S6l〇.d〇c 15 201107418 phenoxy)phenoxy)benzene, 1,4-bis(4-(4-aminophenoxy)phenoxy)benzene, bis(3-(3- (3-Aminophenoxy)phenoxy)phenyl)ether, bis(4-(4-(4-aminophenoxy)phenyl)oxy)phenyl), 1,3-bis(3-(3) -(3-Aminophenoxy)phenoxy)phenyloxy)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-aminobenzene) Oxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2.bis[4-(3-aminophenoxy)phenyl]- 1,1,1,3,3 , 3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropanol, o-phenylenediamine, M-phenylenediamine, p-phenylenediamine, 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 (2-aminoethyl) poly ruthenium oxyn, α, ω bis (3-aminopropyl) polydidecyl oxane, α, ω-bis (4 -aminobutyl)polydimethyloxane, α,ω-bis(4-aminophenyl)polydimethyloxane, α,ω bis(3-aminopropyl)polydiphenyl Base oxane, etc.; but not limited to these. Preferred are 4,4,-bis(3-aminophenoxy)biphenyl, -aminophenoxy)phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene . As the polyimine precursor, a polyamine moiety having a polyglycine structure mainly in a molecular chain and a polyimide having a polyimine structure mainly can be used. (4) It is preferable to use a polyimine imide which is more contained in the polyimine portion than the polyamine having the structure of the above formula (2). The diamine having the structure of the above formula (7) is more contained in the polyimine moiety, and the stability of the polyimide precursor is excellent. 148610.doc -16·201107418 is different 0:: solubility aspect In the above formula (1), the tetravalent organic group represented by the following formula (3) is preferred: [Chemical Formula 14]

Rl7 represents -〇- -S〇2_ or -C0-) (The tetravalent organic group represented by the above formula (3) in the formula (3) may be exemplified by a tetravalent organic group removed from the tetrabasic acid Residues, etc. as such *valent organic residue 'specific JT list: from 3,3,,4,4,·diphenyl stone tetracarboxylic acid di-hepatic, benzoic acid tetracarboxylic dianhydride, 2,2' , 3,3,-benzophenone tetracarboxylic acid wild 3,3-oxybisphthalic dianhydride, 4,4,_oxydiphthalic acid dianhydride to remove the tetrabasic organic residue of the dianhydride structure Among the above, etc., as the above formula (1), in terms of solvent solubility, it is good to remove dianhydride and t-form from 3,3,4,4, diphenylsulfone tetradecanoic acid dianhydride. a tetravalent organic residue. Further, in terms of balance between solvent solubility and adhesion to a substrate, it is preferably from 3,3,4,4,-diphenylsulfone tetrahydrofuran I. a mixture of 3,3',4,4'-benzophenone tetraphthalic acid dianhydride to remove the tetravalent organic residue of the dianhydride structure, or from 3,3,4,4,diphenyltricarboxylic acid a mixture of dianhydride and 4,4'-oxybisphthalic acid dianhydride to remove the tetravalent organic residue of the dianhydride. The previously known four oxonic acid di if can be used within the range that does not impair the effects of the present invention. As such a ton of acid, it can be exemplified by aromatic tetrahedric acid 148610.doc ill -17-201107418 two needles, fat Two groups of tetracarboxylic acid. As the aromatic tetracarboxylic acid two needles, pyromellitic dianhydride, 3,3,4,4,-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2,,3,3,·biphenyltetracarboxylic dianhydride, 2,2_bis(3,4-di-repentylphenyl)propene, 2,2 _bis(2,3-dicarboxyphenyl)propane dianhydride ' 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 〖, bis-dicarboxyphenyl)ethane Anhydride, bis(3,4-dicarboxyphenyl)decane dianhydride, bis(2,3-dicarboxyphenyl)methane di-hepatic, l53_dihydro-[,3-dioxo-5-isobenzene And t-formic acid-Μ-benzophenone, 4-(2,5· dioxytetrahydrotetramine, tetrahydronaphthalene-1,2-monophthalic anhydride, ι, 2,5,6-naphthalene tetraindole Acid dianhydride, 2,3,6,7 naphthalenetetracarboxylic acid dijon, 2,3,5,6-t-tetracarboxylic dianhydride, 3,4,9,1〇4 tetracarboxylic acid-hepatic 2,2-double (3,4_-monophenyl) hexafluoropropane dianhydride, 2,2-bis (4_ (3,4·) Dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(4_(3 4_bis-sulfenylbenzyloxy)phenyl)hexafluoropropane dianhydride, 2,2,_double (trifluoromethyl)-4,4,-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride. Examples of the aliphatic tetracarboxylic dianhydride include cyclobutane tetraphthalic acid dianhydride. , ^3,4-cyclopentane tetradecanoic acid dianhydride, cyclohexane tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro_3·furanyl)_3•fluorenyl_3_cyclohexene ^2-Di-decanoic acid two-needle and cyclo[2,2,2]oct-7-ene-2,3,5,6-tetradecanoic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid needle. In the polyimine precursor of the present invention, in terms of storage stability, it is preferred that the sulfhydrylation ratio is 50% or more. When the imidization ratio D is 50% or more, the concentration of the polyamic acid is lowered, so that the storage stability is improved. Also, it is preferred that the relationship between the bismuth imidization ratio D% and the content of 3,3,4,4,-diphenylsulfone tetracarboxylic dianhydride relative to the total acid component E mole % satisfies 148610.doc The relationship of 201107418 (ES0.6D-30). In the above relationship, (iv) imidization rate of human π 3'3 '4,4-phenylene tetradecanoic acid dianhydride relative to the total acid component content will increase the strength of "this can make up (4) The solubility due to an increase in the imidization rate is lowered, and it is better to maintain solvent solubility even at a low temperature. The polyimine precursor having a polyether structure preferably contains a polylinimide moiety having the structure of the following formula (4):

(In the formula (4), Ζ3 and Ζ4 represent a tetravalent organic group, R1S represents a carbon number of 2 to a carbon number of 1 院, and h represents an integer of 1 to 50). In order to obtain a polyimine precursor containing a polyimine portion having a structure of the above formula (4), it is preferred to use a compound represented by the following formula (5):

(In the formula (5), R1S represents a charcoal number 2 to a carbon number of 1 烧, and h represents an integer of 5 )). 19: 148610.doc H; 201107418 Specific examples of the diamine represented by the above formula (5) include poly-1,4-butanediol bis(o-amino benzoate) and poly- 1,4-butanediol bis(m-amino benzoate), poly-1,4-butanediol bis(p-aminobenzoic acid ester), poly_1>3_propylene glycol bis(o-aminobenzene) The formic acid ester), the poly-1,3-propanediol bis(m-aminophenyl benzoate), the poly-1,3-propanediol bis(p-aminobenzoic acid ester), and the like are not limited thereto. Among them, those having a p-aminobenzoic acid ester group at both ends are preferred, and among them, poly-hydrazine, ‘butanediol bis(p-aminobenzoate) is preferably used. Further, two or more kinds of diamines can be used. The ear% or more of 85 mol% or less represented by the above formula (5) is 25 to 50 mol%, and most preferably 30, which exhibits low warpage, shelling resistance, and Excellent heat resistance.

The effect of birth. The diamine is preferably 丨5 莫' with respect to all of the diamines, more preferably from 25 to 60 mol%, particularly preferably from 30 to 50 mol%. If it is 15% by mole, if it is low resilience, if it is 85 mole% or less, the diamine has an aromatic ring and it is produced. The diamine in the flooding further contains the aromatic diamine of the following formula. Excellent heat resistance and solubility, because t β endures due to aromatic two [Chemistry 17]

(Formula (6) towel' below R19

Ut 18] The formula (7) or the following formula (8) Table 148610. (J〇q *20. 201107418 Ο- (in the formula (8), 'R20 represents a single bond, -〇-, -S02- or _c( CH3) 2-) Specific examples of the diamine represented by the above formula (6) include 1,3_bis(3-aminophenoxy)benzene, iota, 4-bis(4-amine) Benzophenoxy)benzene, 4,4,-bis(3-aminophenoxy)biphenyl, 4,4,-bis(4-aminophenoxy)biphenyl, bis[4_(4-amine Phenyloxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4_4_aminophenyloxy)phenyl]; ε wind, bis[4-(3 -aminophenoxy)phenyl]; 6 wind, 2,2_bis[4-(4-3⁄4 basic oxy)phenyl]propyl, 2,2-bis[4-(3-aminophenoxy) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]trifluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl] Trifluoropropane. It is preferable that ruthenium bis-aminophenoxy)benzene is preferred in terms of heat resistance. The content of the diamine represented by the above formula (6) is preferably from 15 mol% to 85 mol% based on the total of the diamine. More preferably 4 〇 耳 % ~ 75 莫 ❶, especially good is 50 摩尔 % ~ 70 摩尔 %. When it is 15 mol% or more, the solvent resistance is excellent. When it is 85 mol% or less, warpage and resilience can be suppressed. In the polyimine precursor of the present invention, in terms of crosslinking density after hardening, it is preferred that the acid value is 16 mg K 〇 H / g or more. If acid value = 16

When g H/g or more, chemical crosslinking is carried out between the compound having a thermal crosslinkable functional group after thermosetting, and sufficient (four) density is obtained, and the chemical resistance is excellent. X is in the polyimine precursor of the present invention in terms of storage stability. I48610.doc 201107418 L, preferably having an acid value of 70 mg or less. If the acid value is 7 〇 K 〇 H / w, it is easy to obtain a balance between storage stability and solvent solubility. More preferably, the acid value is in the range of 50 mg K0H/g or less, and particularly preferably in the range of 40 mg KOH/g or less. The method for producing a polyimine precursor is described. The method for producing the imine precursor of the present invention includes a known method, and all methods capable of producing a polyimide precursor can be applied. The reaction is carried out in an organic solvent. Examples of the solvent used for such a reaction t include: N,N-dimercaptomethylamine, glycopyylamine, and methylene-2_'i'2 _Dimethoxyethyl sulphide 'tetrachloro hydride, alkane, 1,4-dioxane, dimethyl sulfoxide, benzene, toluene, dinonylbenzene, mesitylene, phenol, phenol, decyl benzoate And ethyl benzoate, butyl benzoate, etc. These may be used singly or in combination of two or more. The concentration of the reaction raw material in the reaction is usually from 2% by mass to 6% by mass, preferably 3〇. The mass % to 50% by mass. The molar ratio of the acid dianhydride to the diamine to be reacted is in the range of 8 to 12. In the case of the inside, the molecular weight can be increased, and the elongation is excellent. 0.9 to 1.1, more preferably 0.95 to 1.05. The weight average molecular weight of the chitoimine precursor is preferably 5〇〇〇 100000 or less. Here, the weight average molecular weight refers to a molecular weight determined by gel permeation chromatography using a known number of polystyrenes having an average molecular weight, and a weight average molecular weight is better. It is 10,000 or more and 6 〇〇〇〇 or less, and the best is 2 〇〇〇〇 or more and 50,000 or less. If the weight average molecular weight is 5 〇〇〇 or more and 1 〇〇〇〇〇 to 148610.doc • 22- 201107418, Further, it is possible to improve the warpage of the protective film obtained by using the resin composition, and it is excellent in low resilience and heat resistance. Further, it can be printed without bleeding by a desired film thickness at the time of coating printing, and the resulting protective film is The mechanical properties are excellent such as elongation. The polyimine precursor can be obtained by the method described below. First, a polybendylene precursor is produced by subjecting the reaction raw material to a polycondensation reaction at room temperature. In this case, the number of equivalents is set to an acid anhydride > diamine compound. Then, the polyimine precursor is heated to preferably 1 〇 (rc 〜 4 〇〇 而 而 醯 , , ,, or use acetic anhydride or the like 醯Imine The chemical agent is subjected to chemical hydrazine imidation, whereby an acid anhydride terminal polyimine having a repeating unit structure corresponding to polyglycolic acid is obtained, and when heated, the hydrazine imidization is used to remove the by-product water A boiling agent (preferably toluene or diphenylbenzene) coexists, and Dean-Stark type dehydration unit is preferably used for dehydration under reflux. Further, it is preferred that the temperature below the air is 'better. (4) Adding a diamine compound component to a temperature of the following temperature to carry out an addition polymerization reaction for 5 hours to ..., which can be used for the polyimine precursor of the invention. Further, 'polyimine imine precursor The end of the polymer backbone is preferably capped by a blocking agent comprising an early amine derivative or a slow acid derivative. By blocking the end of the polymer backbone of the polyimine, the barrier properties are excellent. Examples of the blocking agent for the single derivative of the package 3 include aniline, o-toluidine 1 toluidine, p-toluidine, 2,3-dimethylaniline, decyldimethylamine, M-dimethylaniline, and 3,5. _Dimethylamine, o-chloroaniline, m-benzene benzene!: p-chloroaniline, o-aniline, aniline, p-amine, o-basic L-succinylamine, p-nitrostamine, o-aminobenzene 、, m-aminobenzene 148610.doc •23· 201107418 phenol, p-aminophenol, o-decyloxyaniline, m-anisidine, p-methoxyaniline, o-ethoxyaniline, m-ethoxyaniline, P-ethoxyaniline, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2- Aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-amino group Diphenyl fluorenone, 3-aminobenzophenone, 4-aminodibenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfonate, 4-aminobenzene Phenyl thioether, 2-aminophenyl phenyl sulfone, 3-amino basic phenyl hydrazine, 4-aminophenyl Base, α-naphthylamine, decylamine amine 1-amino-2-naphthol, 5-amino-1-naphthol, 2-amino group _.丨-naphthol, 4-amino group- 1-naphthol' 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-naphthol, 8-amino-2-naphthol, 1-aminoindole An aromatic monoamine such as 2-amino oxime or 9-amino hydrazine, wherein a derivative of aniline is preferably used. These may be used alone or in combination of two or more. The horse contains a slow acid derivative, which may be exemplified by phthalic anhydride, maleic anhydride, 2,3-dione ketone dicarboxylic anhydride, 3,4-dibenzophenone dicarboxylic anhydride, 2,3_ Dicarboxy phenyl ether ether anhydride, 3,4-dicarboxyphenyl phenyl ether liver, 2,3 bis phthalic acid 2 3,4-biphenyl phthalic anhydride, 2,3-dicarboxyphenyl phenyl Anthraquinone anhydride, 3,4-diphenylphenyl hard anhydride, 2,3-dicarboxyphenyl phenyl thioether anhydride, 3}'4-diphenyl stearyl thioether anhydride, 1,2-naphthalene Anhydride, 2,3-naphthalene phthalic anhydride naphthalene dicarboxylic anhydride, phthalic anhydride, 2,3· phthalic anhydride, H formic acid, etc., bis(tetra)anhydride, such materials, group II (four) liver , is the use of phthalic anhydride. These can be used alone or in combination with 2 148610.doc •24· 201107418. The obtained polyimine can be directly prepared into the resin composition of the present invention without desolvation, or a solvent, an additive or the like which is required to be further prepared to prepare the resin composition of the present invention. (B) A compound having a heat crosslinkable functional group as a compound having a heat crosslinkable functional group is not particularly limited as long as it has a heat crosslinkable functional group, and is preferably formed by polymerization of a monomer. The resin is flame retardant. When the resin formed by the polymerization of the monomer has flame retardancy, it contributes to the flame retardancy of the resin composition, and the flame retardancy of the resin composition can be easily exhibited. Further, as the compound having a heat crosslinkable functional group, it is preferably selected from the group consisting of a tri-tillage compound, a benzofluorene compound, an epoxy compound, and a blocked isocyanate m compound. At least one compound. The compound having a heat crosslinkable functional group such as a triphenyl compound, a benzophenanthene compound, an epoxy compound, and a blocked isocyanate compound exhibits high elasticity by being combined with a resin. A compound, and has a property of being highly flexible (four). The inventors of the present invention have focused on a combination of a polyimide precursor having a low warpage property and a compound having a heat crosslinkable functional group which is easily warped due to high elasticity. Further, by adjusting the ruthenium imidization ratio of the polyimide precursor to ～98%, it is possible to improve the chemical resistance while maintaining the low warpage of the polyimide precursor. As the three-tillage compound, it is preferred that the compound having two or more of the three wells in one molecule is preferably a trimeric gas amine and the following formula (! 〇) or the following formula (11) Compounds, melamines and melamine cyanide 148610.doc II: -25- 201107418 Class, etc.: [Chem. 19] r6 X--R7

(In the formula (10), X, Y, and Z respectively represent a hydrogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom; and R6 to Ri1 are each a hydrogen atom or a carbon number i to a carbon number of 5, and the carbon number is 1 to carbon. When 5, Y, and z are hydrogen atoms: Since the hydrogen atom does not have a substituent, Re~Rh does not exist in the structural formula).

[Chem. 20]

(In the formula (11), each represents a hydrogen atom, an alkyl group having a carbon number 丨 to a carbon number of 5, or an alkoxyalkyl group having a carbon number of 1 to a carbon number of 5). Specific examples of the compound represented by the above formula (1 〇) include hexamethyl melamine, hexahydroxybutyl melamine, partially methylolated melamine and alkylate thereof, and tetramethylolbenzimidazole. Amines, partially methylolated benzoguanamines and alkylates thereof. Specific examples of the compound I486 丨0.doc •26-201107418 represented by the above formula (U) include isomeric cyanuric acid, isocyanuric acid triacetate, and iso-cyanuric acid triethyl sulphate. Tris(n-propyl) vinegar, iso-p-cyanate, methyl iso-cyanate, and the like. Examples of the melamine type include melamine, a melamine derivative, a compound having a structure similar to melamine, and a melamine compound. Specific examples of the melamines include, for example, hydroxylated melamine, melamine, amelamine, ammeline, and meglumine (f〇rm〇guanamine). ), guanyl melamine, cyano melamine, melamine, melieme, honey, and the like. Examples of the melamine cyanurate include a molar reactant such as cyanuric acid and melamine. Further, several of the amine groups or hydroxyl groups in the melamine cyanurate may be substituted by other substituents. Among them, melamine cyanurate can be obtained, for example, by mixing an aqueous solution of cyanuric acid with an aqueous solution of melamine, reacting it under stirring at 9 〇〇c~丨〇〇, and then filtering. Precipitated; used as a white solid, which can be used as it is, or it can be pulverized into a fine powder. Further, the compound having a thermally crosslinkable functional group is more preferably a compound having a thermally crosslinkable functional group which does not substantially require a thermal crosslinking accelerator. Since the thermal crosslinking accelerator is not required, the resin composition is excellent in storage stability. Specific examples thereof include a three-tillage compound, a benzofluorene-based compound, and a blocked isocyanate-based compound. These compounds having a thermally crosslinkable functional group may also be used in combination. Among them, in terms of good dispersibility, it is preferred that melamine is different from 148610.doc <1; -27- 201107418 polycyanate adduct, tricot thiol diol, isomeric cyanuric acid (2-hydroxyethyl). As the benzopyrene lining compound, a compound having a benzofluorene ring represented by the following formula (12) is preferably used: [Chem. 21]

(In the formula (12), 'Ru is a chain alkyl group having a carbon number of 1 to a carbon number of 12, a cyclic alkyl group having a carbon number of 3 to a carbon number of 8, a phenyl group, or a chain having a carbon number of 〜2 carbon number 丨2 An alkyl-substituted base group or a halogen-substituted phenyl group; further, the ortho position of the carbon atom in the aromatic ring to which the oxygen atom is bonded is bonded to the carbon atom at at least one position of the para position to have hydrogen). Examples of the chain alkyl group having a carbon number of 1 to a carbon number of 2 in hs include a mercapto group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, and an isobutyl group. Examples of the cyclic alkyl group having a number of 3 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group. Further, examples of the phenyl group substituted with a chain alkyl group having 1 to 12 carbon atoms or the halogen group substituted with a halogen include an ortho-ylphenyl group, m-decylphenyl group, p-methylphenyl group, and O-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, o-phenyl, o-bromobenzene Base. Among these, in terms of achieving good workability, Rls is more preferably decyl, ethyl, propyl, benzene 148610.doc -28. 201107418 base, o-nonylphenyl. As the compound represented by the benzoindole compound (13): For example, it is more preferable to use the T formula

(In the formula (13), r16 is preferably a group of the divalent organic groups represented by the following formula group (丨4)). -CH2~ -〇 - CH2CH2 - -S02 - -CH (CH3)2- -CH2(CH3)2- As a benzo, cultivating compound, it may be composed of only monomers. A number of 'knifes are polymerized to form an oligomer state. X ’ can simultaneously use a benzo " oxime compound having a different structure. Specifically, it is preferred to use a two-year benzopyrene p well. 148610.doc 201107418 Oxygen: ==:: = Various compounds known in the W. Ring As the epoxy compound, it is preferred to use two or more ruthenium/ophthalene compounds in one knives. As an epoxy compound having two or more epoxy groups in one molecule, for example, a ketone lane de + phenol A dust nucleus oxy-resin, a bisphenol S-ring lacquer, a bisphenol phenol F-type epoxy resin, etc. Bisphenol type epoxy resin; phenol novolac 2 oxo resin, W secret varnish type epoxy resin, (4) age-old broth L-I-lacquer type epoxy resin; dicyclopentadiene and various kinds of reactions Various -% pentane: epoxide of olefin-modified benzene resin. The heat resistance of the thermosetting resin of 'double-type A epoxy resin, aged acid varnish type epoxy resin, modified age varnish type epoxy resin and dicyclopentadiene type epoxy resin in epoxy resin It is excellent in properties, solvent resistance, and electric mineral liquid resistance. More specific products of the dicyclopentadiene type epoxy resin include "XD_i_" manufactured by Seiko Chemical Co., Ltd., and "Hp 72〇〇" manufactured by DIC Corporation. More specific products of the novolak-type epoxy resin include "NC-7〇OOL" manufactured by Sakamoto Chemical Co., Ltd., and "EPICLON N-680" manufactured by Die Company. A more specific product of the modified novolac type epoxy resin is exemplified by r NC_3000 manufactured by Nippon Kayaku Co., Ltd., and the like. These epoxy resins may be used singly or in combination of two or more. In the thermosetting resin composition of the present invention, a ring for curing an oxygen resin may be blended as needed. The epoxy resin curing agent is not particularly limited as long as it has an effect of hardening or hardening the epoxy resin, and a commercially available epoxy resin curing agent can be widely used. Specific examples of the epoxy resin curing agent include an age-based resin, a salivary compound, an acid anhydride, an aliphatic amine, an alicyclic polyamine, an aromatic polyamine, a tertiary amine, and a di-cyclodecylamine. , anthraquinones, or such epoxy adducts or microencapsulated; in addition, organic phosphine compounds such as triphenylphosphine, tetraphenyl scale, tetraphenylboronic acid vinegar, etc. 'DBU (1,8) - diaza heterocycle [5, 4, fluorene] eleven _7) or a derivative thereof; the curing agent or the curing accelerator is not limited, and two or more kinds thereof may be used alone or in combination. When such an epoxy resin hardener is used, the amount thereof is usually in the range of 1 part by weight to 2 parts by weight, particularly preferably from 1 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. The blocked isocyanate is a compound obtained by reacting a blocking agent with isocyanic acid having two or more isocyanate groups in the molecule. Examples of the isocyanate s can be exemplified by 1,6-hexamethylene diisocyanate, 4,4,-diphenylmethane diisocyanate, 2,4-nonyl diisocyanate, 2,6-toluene diisocyanate, and xylene Isocyanate, 4,4,-dicyclohexyldecane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4,-diphenyl diisocyanate, 1,3-double ( Isocyanate methyl) cyclohexane, hydrazine, 4-phenylene diisocyanate, 2,6-benzene diisocyanate, i,3,6-hexamethylene triisocyanate, or hexamethylene diisocyanate. As a blocking agent, it can be used: alcohol_, phenols, ε_caprolactam, anthracene, reactive methylene, thiol 'amines, quinones, acid amides, imidazoles, Urea, amine silicate, imine, or sulfurous acid 148610.doc Η; 201107418 salts and the like. As a more specific product of the above-mentioned blocked isocyanate compound, for example, Asahi Kasei Chemicals Co., Ltd., which is a hexamethylene diisocyanate (hereinafter also referred to as "HDI"), is used to block isocyanate. The name of the product is 〇1^3仙16173-60?乂,丁? Eight-: 880 £, Ding? Eight-B80X, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, K6000. Further, as a product manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., a trade name of Β-882Ν or a trade name of sulfonium diisocyanate-blocking isocyanate ΤΑΚΕΝΑΤΕ-830 or 4 may be used. 4·-Diphenylmethane diisocyanate is a trade name of 封-815Ν for blocking isocyanate, and ΤΑΚΕΝΑΤΕ-846Ν which is a 1,3-bis(isocyanate fluorenyl)cyclohexane-blocking isocyanate. Further, a product name: Coronate AP-M, 2503, 2515, 25 07, 2513, or Millionate MS-50 manufactured by NIPPON POLYURETHANE INDUSTRY, which may be used alone or in combination, may be mentioned. The above combination is used. Further, in order to exhibit low-temperature curability at 200 ° C or lower, it is preferred to use an HDI-blocking isocyanate having a low curing temperature as described above. (C) Resin composition resin composition 100 parts by mass relative to polyimide. It is preferred to contain a compound having a heat crosslinkable functional group in a range of from 1 part by mass to 40 parts by mass. When the compound having a heat crosslinkable functional group is in the range of 1 part by mass to 40 parts by mass, heat resistance (solder heat resistance), low warpage property, and flexibility are not impaired, which is preferable. Among them, if the compound having a heat crosslinkable functional group is 148610.doc -32 - 201107418 5 parts by mass or more, it is particularly excellent in terms of crosslink density, and if it is 2 parts by mass or less, warp and rebound Very good in terms of sex. It is preferred that the resin composition has a viscosity change of 2% or less after storage for 3 months. A preferred 疋' resin composition is a resin composition comprising a polyimine precursor having an acid value of 16 mg g/g or more and 70 70 KOH KOH/g or less and a compound having a heat crosslinking functional group, and After 1 month of storage, the viscosity change was 10 ° /. Within. More preferably, when the acid value of the polyimine is 7 KOH/g or less, the reaction does not occur at the storage temperature, and the viscosity change is 1 〇〇/0 or less after storage for 1 month. . When the viscosity change is 1% or less after one month of storage, the storage stability is excellent, and it can be suitably used as an ink which can be stably printed. It is preferred that the resin composition of the present invention satisfies the elastic modulus after heat curing of 0.3 GPa to 1.4 GPa, and is immersed for 6 sec. at 26 〇〇c in a solder bath without swelling or charring. According to the resin composition which satisfies the above-mentioned elastic modulus and the impregnation test in the solder bath, it is possible to provide a resin composition which can provide a cured film which is excellent in heat resistance after heat curing and which has low warpage and low resilience. Among them, it is more preferable that the elastic modulus after hardening is 〇4 GPaq 〇 Gpa, and by forming a resin composition satisfying this characteristic, it further exhibits low warpage, low resilience, and heat resistance. The resin composition may contain a flame retardant in addition to the polyimide precursor and the compound having a heat crosslinkable functional group. The flame retardant is not particularly limited, and a flame retardant of an elemental compound is preferred from the viewpoint of environmental protection or biological toxicity. As the non-pyro-type flame retardant, a lining compound, an inorganic flame retardant, and the like can be listed. Preferably, the composition of the (4) composition is from 148610.doc • 33· 201107418. The elemental element content is 1000 ppm or less, and the flame retardancy of ¥1^_〇 is obtained according to the standard of ^^. Phosphorus compounds, such as phosphazene, phosphine, phosphine oxide, phosphate, and phosphite, may be used as the phosphorus-containing compound in which one or more of these flame retardants may be used. Compound. Particularly, in terms of compatibility with the polyimide composition, phosphazene, phosphine oxide or phosphate can be preferably used. The inorganic flame retardant as a flame retardant may, for example, be a compound or a metal hydroxide. Examples of the cerium compound include antimony trioxide and antimony pentoxide. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide and the like. The amount of the flame retardant to be added is not particularly limited and may be appropriately changed depending on the type of the flame retardant to be used. It is usually preferred to use it in the range of 5% by mass to 50% by mass based on the content of the polyimine. When an inorganic flame retardant is used, since it is insoluble in an organic solvent, the particle diameter of the powder is preferably 100 μm or less. When the particle size of the powder is at most μηη, it is easy to be incorporated into the polyimide composition without impairing the transparency of the cured resin. In order to further improve the flame retardancy, the particle diameter of the powder is preferably 50 μm or less, and particularly preferably ι〇^ below the nail. The resin composition may contain an organic solvent in addition to the polyimide precursor and the compound having a heat crosslinkable functional group. It can be preferably used by making a varnish in a state of being dissolved in an organic solvent. Examples of such an organic solvent include hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine, diethyl acetamide, hydrazinyl carbamide, Ν'Ν·diethylformamide, Ν·Methyl 2 is equal to 1486I0.doc •34· 201107418 Amine solvent, γ-butyrolactone, decanolide, etc. _ inch 1^ S hydrazine solvent, dimercapto sulfoxide, diethyl amide Sulfur-containing solvent such as sulfone, phenolic solvent such as T-tablet, phenol, diglyme, triethylene glycol _ tri 趟 趟 tri tri tri tri tri tri tri tri tri tri tri tri The handsome etraglyme), the second burning, the tetrahydrogen material and the like are benzoic acid butyl vinegar, benzoic acid ethyl vinegar, benzoic acid, and other I-based solvents. In particular, the high boiling point and low water absorption are called 5', and N-mercapto-2-pyrrolidone, γ-butyrolactone, trimethyl ether, butyl benzoate, and ethyl formate can be preferably used. . In addition, the 箄 can be used in the temple, and it can be used in combination. When the coating film is produced, the viscosity and thixotropic (th_〇Py) are adjusted according to the coating method. Fillers or thixotropic agents may also be added as needed. Further, an additive such as a known antifoaming agent or leveling agent may be added. Film formation using a resin composition can be carried out on the surface of a flexible printed circuit board or a semiconductor wafer by a known screen printing or precision dispensing method. The resin composition for screen printing of the present invention is a resin composition, and has a solid content concentration of 45% or more, which is printed on a substrate by screen printing, and when dried, has a dry film thickness of 15 μm or more and infiltration. It is below 4 pm. When the solid content concentration of the resin composition is 45% or more, it is easy to obtain a desired dry film thickness. When the dry film thickness is 15 μπχ or more, when printing is performed on a circuit board to form a protective film, a sufficient film thickness can be obtained on the circuit, and the reliability is excellent. Further, if the penetration after the formation of the film is 4 Å, the printing accuracy is improved, and the resolution of the patterned protective film can be highly obtained. 148610.doc 201107418 The resin composition can fully achieve the ruthenium imidization reaction of polyimine at 150 ° C ~ 220 ° C. Therefore, although depending on the thickness of the coating film, the maximum temperature is set to l5 (rc~22〇<»c using an oven or a heating plate', and it is heated for 5 minutes in an inert gas atmosphere such as air or nitrogen. After a minute, the bathing agent is removed, and the temperature can be maintained at a fixed temperature or slowly while the temperature is raised. The resin composition exhibits excellent heat resistance by thermal curing, and thus is effectively used as a semiconductor. A surface-hardened film, an interlayer insulating film, a bonding sheet, or a protective insulating film for a printed wiring board is suitable for various electronic parts. Further, a resin composition can be preferably used as a surface of a printed circuit board having an electronic circuit. For example, Espanex® (the thickness of the κ insulating layer manufactured by Nippon Steel Chemical Co., Ltd. is 25 (four), and the conductor layer is copper (four) ws^ _) is used as the flexible printed circuit board, and the resin is coated on the circuit board. The composition is used by electroplating gold-gold on the uncoated portion by ^ ^ ^ ^ ^ ^ ^. The surface protective film exerts good insulating properties. ^, using Esp_x M (manufactured by Nippon Steel Chemical Co., Ltd.) (thickness of insulating layer), 25, double-sided copper foil with conductor layer of copper foil F2-WS (18 雔; e; &雔品帝& μΐΏ) The board-side parts are mounted on the circuit board, and the parts other than the parts mounting part of the outer board of the m-th board are used. The resin composition is used as a surface protective film, and the resin composition is used as a surface protective film. In the object * ^, Zen has good insulation properties. J: Bu Hu, the surface protection film is thicker than the s^. Note here, the shape / the wilderness of 疋 1 μπι ~ 5 (), then operate It is easier, if Asn is right-handed; if it is 1 pm and the right is 50 μηι or less, then Xuan Dan becomes easy. j Heyi folds and assembles the following examples in order to clarify the effects of the present invention and The present invention will be specifically described by comparing the examples, but the present invention is not limited by the following examples and comparative examples. (1) Evaluation of polyimine precursors (醯imination) Determination of the rate) The imidization rate is determined by the IR method, based on the peak of the benzene ring around 1480 cm·1, based on The ratio of absorbance at the vicinity of 1380 cm·1 based on the peak of the quinone ring formed is obtained. The yttrium imidation ratio is determined before and after the peaks, and the baseline is drawn by connecting the valleys of the peaks to the valleys. The height at which the peak of the peak falls from the baseline to the point of the baseline to the height of the peak is defined as the absorbance of each. The composition of each is at 50. (: The next synthetic polyimide precursor, which will be dried at 8 (TC) The absorbance of the polyimide precursor at 1480 cnT1 was set to A1, and the absorbance at 1380 cm·1 was set to B 1. Further, the atmosphere was at 22 Torr. (The absorbance of the polyimide precursor at 60 ° C for 1 minute is set to A2 at 1480 cm·1, the absorbance at 1380 cm_1 is set to B2, and the absorbance at 1480 cm·1 at any temperature is set to A3. When the absorbance at 1380 cm·1 is B3, the imidization ratio C at any temperature is set to 1 醯 at a heat treatment at 220 ° C for 60 minutes, according to the yttrium imine. The conversion rate C=((B3/A3-B1/A1)/(B2/A2-B1/A1))) x 100 (%) is calculated. (Measurement of weight average molecular weight) The weight average molecular weight is permeated by gel Chromatography (GPC) was carried out under the following conditions: n, n-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) was used as a solvent, and was added before the measurement. 24.8 mmol/L of brominated monohydrate (I486l0.doc -37-201107418, manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) and 63.2 mmol/L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., high-efficiency liquid) For the purpose of phase chromatography, the calibration curve for calculating the weight average molecular weight is made of standard polystyrene (manufactured by Tosoh Corporation). For column:. Shodex KD-806M (manufactured by Showa Denko), TSK-GEL SUPERHM-H (manufactured by Tosoh Corporation) 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 absorbometer, manufactured by JASCO) (Measurement of acid value) Accurately weigh about 2 g of the synthesized polyimine varnish, which is made of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd., special grade) 40 g and ethanol (Wako Pure Chemical Industries, Ltd.) , special grade) 10 g diluted, according to JIS K0070-1966, using an automatic titration device (Mitsubishi Chemical Analytech), GT-100, titration 0.1 mol / L ethanol potassium hydroxide solution (Wako Pure Chemical Industrial company manufacturing, capacity analysis). The acid value was measured by conversion to the purity of polyimine. (HAST test evaluation) The HAST (Highly Accelerated Temperature and Humidity Stress Test) test evaluation was carried out in the following manner. The comb-shaped copper wiring pattern of the test wiring substrate on which the insulating layer derived from the polyimide precursor is formed is attached to the wire/148610.doc •38·201107418 gap=30 μπι/30 μηι comb A voltage of 5 V was applied between the teeth and placed under high temperature and high humidity of 130 ° C · 85% RH. After the lapse of %, the insulation resistance between the comb teeth was measured. (2) Evaluation of Resin Composition (Storage Stability) The evaluation of storage stability was carried out by measuring changes in weight average molecular weight (Mw) and changes in viscosity. After the resin composition was stored in a refrigerator of _2 〇 for one month, the change in weight average molecular weight (Mw) was ι〇〇/. The following situation is good, set to 〇, more than 10. /. In the case of a defect, it is set to χ, and the change in viscosity is 10% or less is good, and it is set to 〇, and when it exceeds 1%, it is set to X. (Viscosity measurement) The viscosity was measured at 23 t T in a Β-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE_8 5R) using a cone-and-plate viscometer (rotor code (Cai (7) heart) 05, 3° x Rl2). Measurement of Weight Average Molecular Weight) The measurement was carried out in the same manner as the item of measurement of the weight average molecular weight of the above (1) Polyimine precursor. (3) Evaluation of characteristics of cured film (manufacturing of cured film) The resin composition was applied onto a substrate by a bar coater at room temperature: minute to 1 minute to leveling '(4) hot air oven heated under thief The 30-minute buckle was then dried and hardened at 180 c for 6 minutes. Using Dongli 'DuPont... Qiao Dup °nt) company made Κ 〇 ( (registered 148610.doc -39- 201107418 used in the above test for the following test) 100EN as a substrate, 廿 廿 „ Coating on one side, and then leveling, drying and hardening under the same conditions, the sample is examined. The film thickness after drying and hardening is about 2 〇μηι (warping evaluation); 23C, humidity 5G% environment The above sample is cut into a distance of 5 cm x 5 cm with respect to the central part of the fascination as a surface curve. If the distortion is m or less, it is set to be good, and it is better to be 5 _ or less. Super (4) is bad, set to ° and (rebound evaluation) Under the environment of grasping and humidity 5G%, 'use the above sample, fold the laminate to the hardened (4) (four) (four), and add the parallel plate (4) to the parallel plate door. After 4 minutes, the load was measured at a bending radius of 5 Μ. After the load was only 1 嶋n, the load was increased by 10% or less. For the case of (4), the shape of the 凊 is better, and the situation is set to XX, and the rebound force is increased. (Heat resistance evaluation) 2 Heat resistance The test was performed by cutting the sample exx3 (10) and baking it in a solder bath at ♦ C for 60 seconds. According to the JpcA_BM〇2 standard, the S surface was not expanded. In the case of an abnormality such as coke, it is assumed to be Q, and the case where the above abnormality is present is set to X. (Chemical resistance evaluation) ^ The drug is obtained by cutting the above sample into 8 () mm x 1 80 mm. It was carried out as a 4 test piece, and it was immersed for 15 minutes in an aqueous solution of KOH 148610.doc 40·201107418, and the weight change before and after the immersion was measured, and the weight of the Kapton as a substrate was removed to calculate the weight. Reduction rate: If the weight reduction rate is 10% or less, it is good, and it is set to 〇. If it is 4/°, it is better from the bottom, and it is set to ◎. If it exceeds 10%, it is bad, and it is set to χ. Flammability evaluation) The double-coated sample was cut into · mmx5() mm and rolled into a cylinder having a length of 200 mm and a diameter of 12.7 mm, which was used as an evaluation scale for flame retardancy according to the US UL standard. The vertical burning test specified in UL_94 is evaluated. (Measurement of glass transition temperature (Tg)) A hardened film was formed on the substrate in the same manner as described above using a copper box (18 ^ unKFWs, manufactured by Circuit Foil Co., Ltd.) as a substrate. The obtained "layered body was immersed in an aqueous solution of ferric chloride ( 4〇波美 'Crei's manufactured by Cao Da Co., Ltd.), etching is performed, and only the hardened film layer is obtained. After etching, after standing at night at a temperature of 23 ° C and a humidity of 5 〇 %, the glass transition temperature and the elastic mode are measured. The glass transition temperature (Tg) is obtained by using a thermal stress/strain measuring device (TMA/SS6100, Seiko Instruments, manufactured by Seiko Instruments, Ltd.) in an atmosphere (flow rate: 250 cc/min). The Tg was measured under the conditions of a measurement range of 3 ° C to 2 ° ° C. (Elastic Modulus Measurement) The above-mentioned sample of only the cured film layer was cut out to be 5 mm x 100 mm as a test piece. The obtained test piece was measured by a tensile tester (manufactured by RTG-1210/A & D) to obtain an elastic modulus. 148610.doc 41 201107418 (Elongation measurement) It is said that only the sample of the hardened film layer is cut out of 5 mmxl 〇〇 来 ▲ using the tensile tester (Rtg_12i〇/a & D company) for the test, the test The film is measured and the elongation is obtained. The case where the elongation is (10) or more is good, and it is preferable that the case where Δ is 30% or more is preferable, and it is set to be 〇, and it is particularly preferable that it is 50/〇 or more, and it is set to ◎, which is smaller than the case of cutting. Set to X. [1 ♦ Synthesis of water-yield imine precursor], in a three-neck separable flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, and charged with poly-indole-butanediol bis(p-aminobenzoate) pmaB) (IHARA CHEMICAL industry company trade name. ELASMER 1000, weight average molecular weight 13〇5) 65 25 gi bis (3-aminophenyloxy) benzene (apb) 14.62 g, γ-butyrolactone 320 g, under the room Mix until it becomes a homogeneous solution. Then, adding 4,4,_oxydiphthalic dianhydride (ODPA) 29.47 g and phthalic anhydride i 48 g, and introducing nitrogen into the 'ice bath for 1 hour, then stirring at 5 ° C. hour. The product was then pressure-filtered through a 5 μηη filter to obtain a polyimide precursor. [Example 1] Further, the polyimine precursor obtained in Synthesis Example 1 was heated at 180 ° C, and a partial oxime was imidized so that the ruthenium iodide ratio was 51%. Among them, 20 parts by mass of NIKALAC MW-390 (manufactured by Sanwa-Chemical Co., Ltd.) as hydroxylated melamine was added as a thermal crosslink in 1 part by mass of the polyimide precursor. Compounds of the functional groups 148610.doc • 42·201107418 Thermal cross-linking agent)) (The following is a summary of the evaluation results of the resin composition of the g / /0 method. The results are shown in Table 1 below. The amine precursor reached 3 enamel. A cured film was prepared and evaluated. [Example 2 to Example 5] The imidization rate of the hydrazine and the heat exchange

Joint agent. As shown in Table 1, the polyamidiamine coupling agent was set as shown in Table 1 below, and

Bis-F: bisphenol stupid and ploughed (made by Xiaoxi Chemical Industry Co., Ltd., Bis_F type benzopyrene) TPA-B: Blocked polyisocyanate of hexamethylene diisocyanate (made by Asahi Kasei Chemical Co., Ltd., Duranate TPA-B80E) [Example 6] The content of PMAB in all diamines was changed from 50 mmol to 35 mmol. The content of APB was changed from 50 mmol to 65 mmol, and the amination rate of the oxime was set to 5 1 °/. Except for this, a cured film was obtained in the same manner as in Example 1. The evaluation results are not shown in Table 1 below. [Example 7] A hardened film was obtained in the same manner as in Example 1 except that o-dodecanoic anhydride was not added at the time of the synthesis, and the ruthenium imidation ratio was changed to the following Table 1. The evaluation results are shown in Table 1 below. [Comparative Example 1] The content of PMAB in all the diamines was changed to 20 mmol, and 148610.doc -43 to 201107418 of APB was added. The evaluation results showed that the respective amounts were changed to 80 mm 〇l, and no thermal crosslinking agent was added, and other compounding and the like were the same as in Example 2, and a cured film was obtained in Table 2 below. [Comparative Example 2] The content of PMAB in all diamines was changed to 65 mm 〇] [, the content of ApB was changed to 35 mm 〇l, and no thermal crosslinking agent was added, and other preparations and the like were carried out. In the same manner as in Example 2, the cured film was obtained. The evaluation results are shown in the following Table 2. [Comparative Example 3] A cured film was obtained in the same manner as in Example 2 except that the thermal crosslinking agent was not added, and the evaluation results were shown in Table 2 below. [Comparative Example 4] A cured film was obtained in the same manner as in Example 1 except that the ruthenium amide ratio was changed to 3 8%. The evaluation results are shown in Table 2. 148610.doc 44-201107418 [ I<] Example 7 〇\ 50000 MW-390 (N 0.58 〇 ◎ ◎ 〇〇 ◎ 〇 Example 6 〇 \ rn in 44000 MW-390 0.86 〇〇〇〇〇 ◎ 〇 Example 5 〇 \ 48000 ΤΡΑ-Β m 0.48 〇〇〇〇〇 ◎ 〇 Example 4 in 48000 Bis-F Ο 0.51 〇 ◎ ◎ 〇〇 ◎ 〇 Example 3 in ON 50000 MW-390 m 0.59 〇 ◎ ◎ 〇〇 ◎ 〇 Example 2 yn a\ 48000 MW-390 0.56 〇〇〇〇〇◎ 〇Example 1 in 〇\ κη 44000 MW-390 0.67 1 〇〇〇〇〇 ◎ 〇 ODPA addition amount PMAB addition amount APB addition amount 醯 imidization rate (%) Weight average molecular weight (Mw) Crosslinking agent thermal crosslinking agent (parts by mass) Glass transition temperature (°c) Elastic Modulus (GPa) Confidence Evaluation Warpage Evaluation Rebound Evaluation Mw Change Viscosity Change Elongation Evaluation Chemical Resistance Evaluation Dihydride (mmol) (mmol) Storage Stability Evaluation -45- 148610.doc $ 201107418

[Table 2] - Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Two-needle (mmol) ODPA 95 95 95 95 Diamine PMAB 20 65 1 50 - 50 (mmol) APB 80 35 50 50 oxime imidization ratio ( °/〇) 77 77 77 38 Weight average molecular weight (Mw) 55000 40000 48000 31000 Crosslinking agent without or without MW-390 Thermal crosslinking agent (parts by mass) - - 20 Glass transition temperature (°c) 52 45 58 58 Elasticity Modulus (GPa) 0.91 0.22 0.43 0.78 Heat resistance evaluation XXX 〇 warpage evaluation X 〇〇〇 resilience evaluation X 〇〇〇 storage stability evaluation viscosity change 〇〇〇X Mw change 〇〇〇X elongation evaluation XXX 〇 Chemical property evaluation XXXX Gekou 1, Table 2 shows that when the polyimide imidization ratio of the polyimide precursor is 98% or less and the thermal crosslinking agent is contained (Examples 1 to 7), The warpage evaluation, the rebound property evaluation, the heat resistance evaluation, the elongation evaluation, and the chemical resistance evaluation are satisfied. Further, it has been found that when the sulfhydrylation ratio is in the range of 40% to 98%, good storage stability is exhibited. On the other hand, when the imidization ratio was less than 40% (Comparative Example 4) or when the thermal crosslinking agent was not contained (Comparative Example 沁 Comparative Example 3), warpage, resilience, heat-resistant property, and elongation were not obtained. Rate, resistance 148610.doc • 46· 201107418 Balance of various properties of chemical properties. [Synthesis Example 2: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. In the ice water bath ye, put

Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000) 40.0 g, 1,3_bis(3aminophenoxy)benzene (ApB) 8 77 g, azlactone 130 g, toluene 2 〇 g, 12 g of γ-valerolactone and 18 g of pyridine were stirred until the same sentence. Further, '3,3,4,4'-benzophenonetetracarboxylic dianhydride (BTDA) 30.61 g was added in small portions. After stirring for 0.5 hour, the temperature was raised to 17 Torr and heated for 2 hours. After cooling the system to i〇〇〇c, add 丨. Bis(3-aminophenoxy) stupid (APB) 8.77 g. After 5 hours, 1.48 g of phthalic anhydride was added and the mixture was cooled to room temperature. The water in the reaction was azeotroped with toluene, and dehydration was carried out under reflux using a spherical condenser having a moisture separation collector. The product was then pressure filtered by a 5 μηη filter to obtain a polyimide precursor. [& Example 3. Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a separable flask. Put it under the ice water bath and put it into

Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000) 40 g, 1,3-bis(3-aminophenoxy)benzene (APB) 14 〇33 g, γ_τ lactone (GBL) 43 g, stupid 43 g of ethyl citrate (BAEE), 2 g of toluene, 1.2 g of 丫_pental vinegar, and 1.8 g of acridine were stirred until uniform. Further, 3,3',4,4'-diphenylsulfone tetraphthalic acid dianhydride (DSE) a) 14.32 g, and 3,3',4,4'-diphenylfluorene_)tetrafene were added in small portions. Acid dianhydride (^丁〇8) 18.3 65 §. Stirring 〇.5 small 1486I0.doc -47- 201107418 After the time 'liter / orphan to 17 0 C ' heating for 4 hours. The water in the reaction is azeotroped with toluene. Using a spherical condenser having a moisture separation collector, 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, 1.03 g of 1,3 bis(3-aminophenoxy)benzene (APB) was added. After 5 hours, o-parabens 889 g was added and cooled to room temperature. The product was then pressure filtered by a 5 μηη filter to obtain a polyimide precursor. [Synthesis Example 4: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. Under ice water bath, Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000) 40 g, γ-butyrolactone (GBL) 43 g, ethyl benzoate (43 g), terpene 20 g, y were charged. - Pentolide ι·2 g,. ratio. Set 1.8 g and mix until uniform. Further, 3,3,4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA) 14.32 g and 3,3',4,4'-dibenzophenone tetradecanoic acid dianhydride were added in small portions ( BTDA) 18.365 g. After stirring for 5 hours, the temperature was raised to 17 Torr. (:, heating for 4 hours. The water in the reaction is azeotroped with toluene, and the dehydration is carried out under reflux using a spherical condenser having a moisture separation collector. After the removal of the by-product water, the reflux is stopped, and the toluene is completely After cooling the system to 60 ° C, 1,3-bis(3-aminophenoxy)benzene (hydrazine) 17·542 was added for 5 hours, then phthalic anhydride 0.889 g' was added and cooled to room temperature. Then, the product was subjected to pressure filtration through a 5 μηη 遽 而 而 获得 。 。 。 。 。 。 。 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ 148610.doc -48- 201107418 θ 77 is a hot phenolic bisphenol benzophenone p-cultivation (Bis_F type benzopyrene, J Western Chemical Industry Co., Ltd.), and the polyimine is 30 mass. The resin composition was prepared in the same manner, and a cured film was produced and evaluated. [Example 9] In the mass fraction of the polyimine precursor obtained in Synthesis Example 3, yt parts by mass were added as thermal crosslinking. Bisphenol benzopyrene (Bis_j^ Bis_F type benzoate well, manufactured by Xiaoxi Chemical Industry Co., Ltd., monomer Evaluation of flammability 〇) ^ Addition of 15 parts by mass of phosphazene-based flame retardant (the following general formula (15)), 2 parts by mass of magnesium hydroxide (average secondary particle size of 1 〇μιη, Tateh〇chemical Industries The resin composition was blended as a flame retardant, and the resin composition was blended in such a manner that the polyamidene precursor reached 3 〇 mass%. A cured film was produced and evaluated.

OH

RRR\ll 0, 0' or [Example 10] In the polybenzamine 1 part by mass obtained in Synthesis Example 4, 10 parts by mass of bisphenol benzopyrene as a thermal crosslinking agent was added (Bis- F : Bis-F type benzene and ploughing, manufactured by Xiaoxi Chemical Industry Co., Ltd., evaluation of monomer flame retardancy 〇). 15 parts by mass of a phosphazene-based flame retardant (the following general formula (15)) and 20 parts by mass of magnesium hydroxide (average secondary particle diameter 1·〇M·111, manufactured by Tateho Chemical Industries, Inc. 148610.doc tv 201107418) were added. As a flame retardant, the polyimine precursor reaches 30 mass. /. The resin composition is blended in the same manner. A cured film was produced and evaluated. The results of Examples 8 to 10 are shown in Table 3 below. [Table 3] Example 8 Example 9 Example 10 Synthesis Example----Formation 2 Synthesis Example 3 Synthesis Example 4 Diacid component DSDA-40 40 (mmol) BTDA 95 57 57 Diamine component XTJ- 542 40 40 40 (mmol) APB 35 60 60 Blocking agent aniline 10 - phthalic anhydride - 6 6 molecular weight number S average molecular weight (Μη) 19000 19800 18300 Weight average molecular weight (Mw) 41000 42700 38500 Acid value*-- ----- mg KOH/g - 18 70 酝imine (parts by mass) 100 100 100 Thermal crosslinker Bis-F Bis-F Bis-F Thermal crosslinker (parts by mass) 5 10 10 Elastic modulus (MPa) - 500 420 Storage stability evaluation - viscosity change - heat resistance evaluation - 〇〇〇 warpage evaluation ◎ ◎ ◎ anti-elastic evaluation ◎ 〇〇 flame retardancy evaluation ----- VTM-0 VTM-0 Elongation Evaluation 〇 ◎ ◎ Chemical Resistance Evaluation 〇〇〇 148610.doc • 50- 201107418 As shown in Table 3, when Jeffamine and thermal crosslinking agent are contained, warpage evaluation, rebound evaluation, and heat resistance are satisfied. Flame retardancy evaluation, elongation, and chemical resistance (Examples 8 to 1). [Synthesis Example 5: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. In an ice water bath at 0 ° C, Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight of 1000) 20.0 g, Jeffamine ED-600 (manufactured by Huntsman, weight average molecular weight of 600), 18.0 g, 1,3-double (3) was charged. -Aminophenoxy)benzene (APB) ll.llO g, γ-butyrolactone 130 g, toluene 20 g, γ-valerolactone 1.2 g, ° ratio of 1.8 g, and the mixture was uniformly mixed. Further, 3,3,4,4,-diphenylphosphonium tetraphthalic acid dianhydride (0808) 14.32 ly, and 3,3,4,4'-dibenzophenone tetradecanoic acid were added in small portions. Anhydride (BTDA) 17.721 g. After stirring for 0.5 hour, the temperature was raised to 170 ° C and heated for 2 hours. After cooling the system to 60 ° C, i.sub.3, bis(3-aminophenoxy)benzene (hydrazine) 3·508 g was added. After 5 hours, phthalic anhydride 1 · 4 8 1 g ' was added and cooled to room temperature. The water in the reaction was azeotroped with toluene, and a spherical condenser having a moisture separation collector was used for dehydration under reflux. The product was then pressure filtered by a 5 μηι filter to obtain a polyimide precursor. [Synthesis Example 6: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. In an ice water bath 〇°C, 10.0 g of Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight of 1000), 20.0 g, Jeffamine ED-600 (manufactured by Huntsman, weight: 148610.doc -51 - 201107418, average molecular weight of 600), 18.0 g, 1,3-bis(3-aminophenoxy)benzene (APB) 8.771 g, γ-butyrolactone 130 g, toluene 20 g, γ-valerolactone 1.2 g. It is more even than the bite 1.8 g'. Further, 3,3',4,4'-diphenylstilbenetetracarboxylic dianhydride (DSDA) 14.32 g and 4,4'-oxybisphthalic acid dianhydride (ODPA) 17.062 g were added in small portions. After stirring for 5 hours, the temperature was raised to 170 ° C and heated for 2 hours. After the system was cooled to 60 ° C, 丨^ bisamine basic oxy) (APB) 5.847 g was added. After 5 hours, 1.4 8 1 g of phthalic acid liver was added and cooled to room temperature. The water in the reaction was azeotroped with toluene, and a spherical condenser having a moisture separation collector was used to carry out dehydration under reflux. The product was then pressure filtered by a 5 μηη filter to obtain a polyimide precursor. [Synthesis Example 7: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. In an ice water bath at 0 ° C, Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000) 40.0 g, γ-butyrolactone 13 〇g, fluorene benzene 2 〇 g, γ-decalactone 1.2 g, ° The ratio is set to 1.8 g and the mixture is stirred until uniform. Further, 3,3',4,4'-benzophenone tetraphthalic acid dianhydride (BTDA) 19.332 g and 4,4,-oxydiphthalic dianhydride (ODPA) 12.409 g were added in small portions. After stirring for 0.5 hour, the temperature was raised to 170 ° C 'heating for 2 hours" and the system was cooled to 6 Torr. (: After adding 1,3 -bis(3-aminophenoxy)benzene (APB) 16.08 g. After 5 hours, add aniline 0.931 g ' and cool to room temperature. The water in the reaction is co-produced with toluene. The mixture was boiled and dehydrated under reflux using a spherical condenser having a moisture separation collector. The product was then pressure-filtered by a 5 μηη filter to obtain a polyimine pre-I48610.doc • 52-201107418. Synthesis Example 8: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation collector were attached to a three-neck separable flask, and Jeffamine XTJ-542 was placed in an ice water bath at °C. Manufactured by Huntsman, weight average molecular weight 1000) 18.6 g, Jeffamine ED-600 (manufactured by Huntsman, weight average molecular weight 600) 16.74 g, 1,3-bis(3-aminophenoxy)benzene (APB) 12.133 g, 130 g of γ-butyrolactone, 20 g of toluene, 1.2 g of γ-valerolactone, and a ratio of 1.8 g to ° °, and the mixture was uniformly mixed. Further, 3, 3, 4, 4, - 2 were added in small portions. Phenyl sulfone tetracarboxylic dianhydride (DSDA) 14.32 g, and 3,3',4,4·-benzophenonetetracarboxylic dianhydride (BTDA) 19.332 g After stirring for 0.5 hour, the temperature was raised to 170 ° C and heated for 3 hours. After cooling the system to 60 ° C, 1,3-bis(3-aminophenoxy)benzene (oxime) 1.462 g was added. After 5 hours, it was cooled to room temperature. The water in the reaction was azeotroped with toluene, and dehydrated under reflux using a spherical condenser having a moisture separation collector. The product was then pressurized by a filter of 5 μm. The polyimine precursor was obtained by filtration. [Synthesis Example 9: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation collector were attached to a three-neck separable flask. 〇 ° C, input: Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight of 1000) 18.2 g, Jeffamine ED-600 (manufactured by Huntsman, weight average molecular weight of 600) 16.38 g, 1,3-bis (3-amine Benzophenoxy)benzene (APB) 12.77 g, γ-butene g 13 〇 g, toluene 20 g, γ-valerolactone 1 2 g, ° ratio. Set 1.8 g, mix until uniform. Add a small amount of 148610.doc -53- 201107418 3,3',4,4'-diphenylsulfone tetraphthalic acid dianhydride (DSDA) 14.32 g, and 3,3,,4,4·-benzophenonetetracarboxylic dianhydride (BTDA) 19.332 g. After stirring for ο" hours, the temperature was raised to 170 ° C and heated for 3 hours. After the system was cooled to 60 ° C, 0.532 g of 1,3-bis(3-aminophenoxy)benzene (APB) was added. After 5 hours, it was cooled to room temperature. The water in the reaction was azeotroped with toluene, and a spherical condenser having a moisture separation collector was used for dehydration under reflux. The product was then pressure filtered by a 5 μηη filter to obtain a polyimide precursor. [Synthesis Example 10: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. In an ice water bath at C ° C, a solution of Jeffamine ED-900 (manufactured by Huntsman, weight average molecular weight of 900) 36.0 g, 1,3-bis(3-aminophenoxy)benzene (ΑΡΒ) 12·279 g, stirred Until even. Further, 3,3·,4,4·-diphenylphosphonium tetraphthalic acid dianhydride (DSDA) 14.32 g and 3,3',4,4'-diphenyl fluorenone tetracarboxylic dianhydride were added in small portions ( BTDA) 17.721 g. After stirring for 0.5 hour, the temperature was raised to 170 ° C and heated for 2 hours. After cooling the system to 60 ° C, 1,3-bis(3-aminophenoxy)benzene (ΑΡΒ) 5·262 g was added. After 5 hours, 1.481 g of phthalic anhydride was added and cooled to room temperature. . The water in the reaction is azeotroped with toluene, and dewatering is carried out under reflux using a spherical condenser having water as a separator. The product was then pressure filtered through a 5 μηι filter to obtain a polyimide precursor. [Synthesis Example 11: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. In an ice water bath 〇 ° C, put into Jeffamine D-2000 (manufactured by Huntsman, weight average molecular weight 148610.doc • 54- 201107418 2000) 40.0 g, 1,3-bis(3-aminophenoxy)benzene (APB) ) 18_126 g, search until evenly. Further, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA) 14.32 g, and 3,3',4,4,-benzophenonetetracarboxylic acid di-hepatic (BTDA) were added in small portions. ) 17.721 g. After stirring for 0.5 hour, the temperature was raised to i70 ° C and heated for 2 hours. After the system was cooled to 60 ° C, 1,3-bis(3-aminophenoxy)benzene (APB) 5.262 g was added. After 5 hours, 1.481 g of phthalic acid was added and allowed to cool to room temperature. The water in the reaction was azeotroped with the hydrazine, and dehydration was carried out under reflux using a spherical condenser tube having a moisture separation collector. The product was then pressure filtered by a 5 μηη filter to obtain a polyimide precursor. [Synthesis Example 12: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a water separation separator were attached to a three-neck separable flask. In an ice water bath at °C, put Jeffamine D-400 (manufactured by Huntsman, weight average molecular weight 2000) 32.0 g, 1,3-bis(3-aminophenyloxy)benzene (APB) 0.585 g, and mix Evenly. Further, 3,3,4,4,-diphenylsulfonetetracarboxylic dianhydride (DSDA) 14.32 g, and 3,3',4,4·-benzophenonetetracarboxylic acid dihydrate (BTDA) were added in small portions. ) 17.721 g. After stirring for 0.5 hour, the temperature was raised to n 〇 ° C and heated for 2 hours. After cooling the system to 60 ° C, i.sub.3,3-bis(3-aminophenoxy)benzene (APB) 5.262 g was added. After 5 hours, 1.481 g of phthalic anhydride was added and cooled to room temperature. The water in the reaction was azeotroped with toluene, and dehydration was carried out under reflux using a spherical condenser tube having a moisture separation collector. The product was then pressure filtered by a 5 μηη filter to obtain a polyimide precursor. [Synthesis Example 13: Synthesis of Polyimine] A nitrogen inlet tube, a thermometer, and a spherical condenser having water 148610.doc - 55 · 201107418 separate separator were attached to a two-neck separable flask. In the ice water bath. (3), Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000) 40 〇g, 1,3-bis(3-aminophenoxy)benzene (APB) 16.08 g, γ-butyrolactone 130 g曱 〇 〇 〇 、 、 、 y 、 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 (DSDA) 16.11 g, and 3,3',4,4'-dibenzophenone tetradecanoic acid dianhydride (BTDA) 17.721 g. After stirring for 0.5 hours, the temperature was raised to 170 ° C and heated for 5 hours. The by-produced water is azeotroped with toluene, and is dehydrated under reflux using a spherical condenser having a moisture separation collector, and then the product is pressure-filtered by a filter of 5 μηι to obtain a polyimine. Example 14: Synthesis of Polyimine Precursor] A nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation collector were attached to a three-neck separable flask, and charged into Jeffamine XTJ-542 (Huntsman) in an ice water bath at °C. The company manufactures 'weight average molecular weight of 1000) 35.0 g, γ-butyrolactone 130 g, toluene 20 g, γ-valerolactone 1.2 g, pyridine 1.8 g, and stirred until uniform Further, 3,3,4,4·-benzophenonetetradecanoic acid dianhydride (BTDA) 19.332 g and 4,4,-oxydiphthalic dianhydride (ODPA) 12.4〇 were added in small portions. 9 g. After stirring for 0.5 hours, the temperature was raised to 170 ° C and heated for 2 hours. After cooling the system to 6 ° C, Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight of 1000) 5.0 g' and 1,3_ were added. Bis(3-aminophenoxy)benzene (APB) 16.08 g. After 5 hours, add aniline·9 3 1 g, and cool to room temperature. The by-product water in the reaction is azeotroped with toluene. The spherical condenser tube of the separator was separated and dehydrated under reflux, and then the product was pressure-filtered by a filter of 5 μηι 148610.doc • 56·201107418 to obtain a polyimide precursor. [Example 11] In the mass fraction of the polyimine precursor obtained in Example 5, a bisphenol benzopyrene was added as a thermal crosslinking agent in a mass fraction of 15 (Bis_F: Bis_F type 笨 噚 噚 、, manufactured by Xiaoxi Chemical Industry Co., Ltd. The resin composition was blended in such a manner that the polyimine was 30% by mass, and a cured film was produced and evaluated. Example 12] In one part by mass of the polyimine precursor obtained in Synthesis Example 5, 20 parts of mercapto melamine (mw_39〇: NIKALAC MW-390, Sanwa-) was added as a thermal crosslinking agent. The resin group was blended in such a manner that the polyimide precursor was 30% by mass. A hardened film was produced and evaluated. [Example 13] In one part by mass of the polyimine precursor obtained in Synthesis Example 5, 20 parts by mass of a blocked polyisocyanate of hexamethylene diisocyanate as a thermal crosslinking agent was added ( TPA-B: Duranate TPA-B80E, manufactured by Asahi Kasei Chemicals Co., Ltd.) The resin bismuth compound was blended in such a manner that the polyimide precursor was up to 3% by mass. A cured film was produced and evaluated. [Example 14] 24 parts by mass of epoxy resin (dicyclopentadiene type epoxy resin HP7200, DIC manufactured by DIC Corporation) was added to 1 part by mass of the polyimide intermediate precursor obtained in Synthesis Example 5. And 0.8 mass-damage epoxy resin amine adduct (Amicure PN_23, manufactured by Ajinomoto Fine-Techno Co., Ltd.) as a thermal crosslinking agent, -57- 148610.doc

S 201107418 The resin composition was blended in such a manner that the polyimide precursor was up to 3 〇 mass%. A cured film was produced and evaluated. [Example 15] In the polybenzazole precursor obtained in Synthesis Example 6, 1 part by mass of bisphenol was added as a thermal crosslinking agent, and Bis_F: Bis F type benzoic acid was added. The resin composition was blended in such a manner that the polyamidene precursor reached 30% by mass. A cured film was produced and evaluated. [Example 16] 10 parts by mass of a bisphenol benzobis bromide (Bis_F) as a thermal crosslinking agent was added to the mass fraction of the polyimine precursor obtained in Synthesis Example 7. : Bis_F type benzo gas cultivating, manufactured by Kosei Chemical Industry Co., Ltd.), and the resin composition was blended in such a manner that the polyiminoimide precursor reached 30% by mass. A cured film was produced and evaluated. [Example 17] In the mass fraction of the polyimine precursor obtained in Synthesis Example 8, 15 parts by mass of bisphenol benzo P was added as a thermal crosslinking agent (Bis..F : Bis_F Type benzopyrene, manufactured by Xiaoxi Chemical Industry Co., Ltd., with a concentration of 30% by mass of the polyimide precursor. The resin composition is blended in the same manner. A cured film was produced and evaluated. [Example 18] To a mass fraction of the polyimine precursor obtained in Synthesis Example 9, 15 parts by mass of bisphenol benzoic acid was added as a thermal crosslinking agent (Bis-F: Bis-F type) The benzopyrene, manufactured by Xiaoxi Chemical Industry Co., Ltd., and the resin composition was blended in such a manner that the polyamidimide reached 3〇1486IO.doc -58- 201107418% by mass. A cured film was produced and evaluated. [Example 19] To a mass fraction of the polyimine precursor obtained in Synthesis Example 10, 15 parts by mass of bisphenol benzopyrene (Bis_F: Bis-F type benzophenone) was added as a thermal crosslinking agent. The resin composition was blended in such a manner that the polyamidimide reached 30% by mass. A cured film was produced and evaluated. [Example 20] To a mass fraction of the polyimine precursor obtained in Synthesis Example 11, 15 parts by mass of bisphenol benzoic acid (Bis_F: Bis_F type benzoxanthine) was added as a thermal crosslinking agent. The resin composition was blended in such a manner that the polyamidimide reached 30% by mass. A cured film was produced and evaluated. [Example 21] To a mass fraction of the polyimine precursor obtained in Synthesis Example 12, 15 parts by mass of bisphenol benzoate as a thermal crosslinking agent was added to drink coffee (Bis_F: Bis_F type stupid and ploughed The resin composition was blended in such a manner that the polyamidimide reached 3% by mass. A cured film was produced and evaluated. The results of Examples 11 to 19 are shown in Table 4 below, and the results of Example 2 to Example 2 1 are shown in Table 5 below. Further, in the following Table *, the above epoxy resin and the above epoxy resin amine adduct are simply referred to as epoxy oxime. [Comparative Example 5] In 100 parts by mass of the polyimine obtained in Synthesis Example 13, 15 parts of 148610.doc 201107418 parts were added as a thermal crosslinking agent, and bisphenol was arbitrarily cultivated (Bis_F: Bis_F type stupid) , manufactured by Xiaoxi Chemical Industry Co., Ltd., and the resin composition was blended in such a manner that the polyamidimide reached 3 〇 mass 〇 / °. A cured film was produced and evaluated. [Comparative Example 6] In 100 parts by mass of the polyimine precursor obtained in Synthesis Example 5, a hot parent agent and the following acrylate mixture were added, and the resin was blended in such a manner that the polyamidimide reached 3 〇 mass%. combination. A cured film was produced and evaluated. Acrylate mixture: 40 parts by mass of acryl decanoate (Blemmer DP403 AU), 16 parts by weight of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 2-hydroxy-3-phenoxy acrylate 3.3 parts by mass of polyester acrylate (manufactured by Toagosei Co., Ltd., M-6100) 6.7 parts by mass [Comparative Example 7] Polypyrene obtained in Synthesis Example 14 1 part by mass of the imine precursor, 10 parts by mass of bisphenol benzene as a thermal crosslinking agent is added and ploughed (Bis_F: Bis-F type benzoxazine, manufactured by Xiaoxi Chemical Industry Co., Ltd.) The resin composition was blended in such a manner that the imine reached 30% by mass. A cured film was produced and evaluated. The results of Example 11 to Example 2 1 and Comparative Example 5 to Comparative Example 7 are shown in Table 4 below and Table 5 below. 148610.doc -60· 201107418 [Inch 实施 Example 19 | Synthesis Example 10 I yn 1 o 1 1 〇§ Ο 1 40000 00 19.2 v〇(Ν ι ι—Η Bis-F in T—^ 0 ◎ ◎ ◎ Implementation Example 18 Synthesis Example 9 § 1 o 18.2 27.3 1 45.5 I 1 37000 〇〇28.8 Ο m Ο Bis-F 0 〇 < 〇 Example 17 Synthesis Example 8 § 1 o 18.6 27.9 1 46.5 I 1 49000 »Τ) 〇\ Ο Bis-F ΙΤΪ r-^ 〇〇〇〇 Example 16 Synthesis Example 7 〇 drying o 1 1 vn vn 1 Ο i—Η 39000 〇1 ζ Ο Bis-F o H 〇0 ◎ ◎ Example 15 Synthesis Example 6 1 o 1 Ο 1 44000 〇 (Ν 1 - Η Ο Bis-F o 〇〇 ◎ ◎ Example 14 Synthesis Example 5 m 1 o 1 Ο 1 41000 00 〇〇 22.8 〇〇ο Η Epoxy 1 24.8 〇〇〇〇 Example 13 Synthesis Example 5 tn 1 o 1 Ο 1 41000 00 00 22.8 | οο ο τ-Ή TPA-B 〇〇 ◎ 〇 Example 12 Synthesis Example 5 1 o 1 Ο 1 41000 00 〇〇 22.8 | οο Ο rH MW -390 〇〇◎ 〇Example 11 Synthesis Example 5 in in 1 o 1 〇Ο 1 41000 〇〇00 22.8 οο Ο Bis-F ^Τ) ί—Η 〇 ◎ ◎ 〇 Synthesis Example BTDA ODPA DSDA XTJ-542 ED- 600 ED-900 APB phthalic anhydride aniline weight average molecular weight 醯 imidization rate (%) E (0.6D-30) acid value (mgKOH / g) polyimine (parts by mass) thermal crosslinker thermal crosslinker (quality Co., Ltd.) 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Mxl·^^^ 148610.doc -62- 201107418 As shown in Table 4 and Table 5, when the imidization ratio is 98% or less and contains Jeffamine and a thermal crosslinking agent, the evaluation of warpage and reboundability are satisfied. Heat resistance S was flat (Example 11 to Example 2). On the other hand, when the imidization ratio was more than 98% (Comparative Example 5), warpage, resilience, heat resistance, and chemical resistance were not obtained. The balance of the various properties of the drug. Further, when the acrylate mixture was used as the thermal crosslinking agent (Comparative Example 6), the balance of the properties of warpage, resilience, heat resistance, and drug αα resistance was not obtained. Further, when the imidization ratio was less than 40% (Comparative Example 7), the balance of each of the characteristics of warpage, resilience, and resistance to heat resistance was not obtained. [Example 22] (Evaluation of Protective Film of Printed Circuit Board) Using Espanex® (manufactured by Nippon Steel Chemical Co., Ltd.) (the thickness of the insulating layer was 25 μm, and the conductor layer was copper foil F2_ws〇8 μιη)) For the substrate of the printed wiring board, the line/gap: 3〇μηι/3〇μιη, 5〇μιη/5〇μηι 1 (9) Pm/1 〇〇μιη, 200 μιη/200 μπι comb-shaped wiring board. Applying the resin composition of Example 丨丨 to Example 丨6 on one part of the substrate of the hai circuit, the uncoated portion is formed in such a manner that the thickness of the nickel is about 5 Pm and the thickness of the gold is about 〇·〇5 μιη. Electroplating of nickel-gold was carried out, and as a result, it was confirmed by micro-zone fluorescent ray analysis that the penetration of electroplating in the portion coated with the resin composition was less than 20 μm. Further, it was confirmed by an electric resistance meter that the insulation state between the circuits was good. Further, the ink was printed on the comb-tooth portion of the comb-shaped wiring board, and the reliability test was carried out, that is, the resistance was measured while being placed under conditions of DC 50 v, 85 t, and humidity of 85% for 1000 hours, and all of them were kept above ΙΟ9 Ω. Resistance, and get good results. In addition, the ink is printed on the comb-shaped portion of the comb-shaped wiring board comb 148610.doc -63- 201107418, and the reliability test is performed, that is, the surface is 1) (: 5 v, 13 dying, humidity 8 5 % Under the condition that the resistance was measured for 9 to 6 hours, the resistance was exceeded at 108 Ω, and good results were obtained. Further, Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) was used (the thickness of the insulating layer was 25 μm, conductor) Double-sided steel foil sheet with steel foil F2_ws〇8 μηι)): Carbon dioxide laser drilled with a diameter of 100 μηι, copper plated to make a double-sided component mounting circuit board. The resin composition is applied to a portion other than the component mounting portion of the circuit board, and the component is fixed to the uncoated portion by solder paste, and then mounted on the ink surface and the circuit portion by a 260 t IR reflow furnace. No abnormality q was found, and the part non-mounting portion was bent (10) degrees into the electronic device 'at 85'. In the environment of 〇, humidity 85%, DC5〇 v, it runs well for more than 1000 hours. [Example 23] (Formation of a protective film patterned by a screen printing method) ESpanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (the thickness of the insulating layer was 25 μΐη, and the conductor layer was a copper box F2_ws〇8 (four)) Double-sided copper foil board, made straight! Drilling a 100 μm carbon dioxide laser, making a double-sided part after copper plating, mounting the circuit board. A patterned 17 μm protective film was formed by printing a resin composition on a portion of the component mounting portion of the circuit board. Protection = the resolution is better 'Infiltration to 4 () is called the following. Moreover, after the fixing member is fixed to the uncoated portion (〇.4 mmx〇.3 mm) by solder paste, the bonding strength between the part and the circuit substrate is performed by the 26 (TC IR reflow furnace) No abnormalities were found in the conduction, and the parts and the circuit parts were not found to be bent by 180 degrees and assembled to the electronic device 148610.doc •64·201107418 'at 85°c, humidity 85% In the environment of DC50 v, it was operated well for _hours or more. [Example 24] A nitrogen inlet tube, a thermometer, and a spherical condenser having a moisture separation collector were attached to a three-neck separable flask, and Jeffamine XTJ-542 was placed in an ice water bath. (manufactured by HUntsman, weight average molecular weight 1000) 400 g, 1,3-bis(3_aminophenoxy)benzene (ApB) 14〇33 g, “butyrolactone (GBL) 430 g, ethyl benzoate (BAEE) 43〇g, toluene 8〇g, 丫_valerolactone 12 g, pyridine 18 g 'stirred until uniform. Further, 3,3',4,4'-diphenyl stone was added in small amounts. Acid dianhydride (Dsda) 143.2 g, and 3,3',4,4,-dioxanone tetradecanoic acid dianhydride (btDA) 183.65 g. Stirring 0.5 After the hour, the temperature was raised to 17 CTC for 4 hours. The water in the reaction was dewatered under reflux by aspherical condenser with a moisture separation collector and azeotrope with toluene. Stop the reflux and completely remove the benzene. After cooling the system to 6 (TC, add 1,3-bis(3-aminophenoxy)benzene (APB) 35.08 g. Add phthalate after 5 hours. An acid anhydride of 8.89 g was cooled to room temperature, and then the product was pressure-filtered by a filter of 5 μm to obtain a varnish having a polyimine precursor content of 52% by mass (solid content concentration: 52% by weight). The obtained polyimine precursor was blended to a mass ratio of 3 〇 mass%, and a cured film was produced and evaluated. [Example 25] A nitrogen gas introduction tube, a thermometer, and a moisture separation collector were attached to a three-neck separable flask. Spherical condenser. In the ice water bath 〇 ° C, put into Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight -65-148610.doc

S 201107418 1000) 400 g, γ-butyrolactone (GBL) 430 g, ethyl benzoate (BAEE) 43〇g, toluene 80 g, γ-valerolactone 12 g, pyridine 18 g, stir until uniform . Further, 3,3',4,4'-diphenyl domain tetradecanoic acid dijon (DSDA) 143.2 g and 3,3',4,4'-dibenzophenone tetracarboxylic acid two needles were added in small portions ( BTDA) 183_65 g. After stirring for 0.5 hour, the temperature was raised to 170 ° C and heated for 4 hours. The water in the reaction is dehydrated by reflux using a spherical condenser having a moisture separation collector by azeotropy with toluene. After the removal of the by-produced water, the reflux was stopped and the stupid was completely removed. After the system was cooled to 60 ° C, 1,3-bis(3-aminophenoxy)benzene (APB) 175.42 was added for 5 hours, and then 8.89 g of phthalic anhydride was added, and cooled to room temperature. Then, the product was pressure-filtered by a filter of 5 μηι to obtain a varnish having a polyimine precursor content of 52% by mass (solid content concentration: 52% by weight). The obtained polyimine precursor was blended so as to have a mass percentage of 30% by mass to prepare a cured film and evaluated. [Comparative Example 8] The same procedure as in Example 24 was carried out except that Jeffamine XTJ_542 was not added and 1,3-bis(3-aminophenoxy)benzene (APB) was added in an amount of 283.59 g. The way to operate. [Comparative Example 9] 3,3',4,4,-diphenylsulfone tetraphthalic acid dianhydride (DSDA) and 3,3,4,4-dibenzophenone tetradecanoic acid dianhydride were synthesized ( The operation was carried out in the same manner as in Example 24 except that the conversion of btda) to 1,2-extended ethyl bis(dehydrated trimellitate) (TMEG) was 397.5 g. [Comparative Example 1 0] • 66· 201107418 No addition of 1,3-bis(3-aminophenoxy)benzene (APB) during the synthesis, and the addition amount of Jeffamine XTJ-542 was changed to 1000 g, Further, the operation was carried out in the same manner as in Example 24. The results of Examples 24 to 25 and Comparative Examples 8 to 10 are shown in Table 6 below. [Table 6]

Synthetic material composition (mol%) Example 24 Example 25 Comparative Example 8 Comparative Example 9 Comparative Example 10 Acid dianhydride component DSDA 40 40 40 - 40 BTDA 57 57 57 - 57 TMEG - - - 97 - Diamine component XTJ-542 40 40 - 40 100 ED-600 - - - - - APB 60 60 97 60 - Blocking agent aniline - - - - - Phthalic anhydride 6 6 6 6 6 Reaction solvent (g) GBL 430 430 430 430 430 BAEE 430 430 430 430 430 Solid content concentration wt% 52 52 52 52 50 Molecular weight number average molecular weight (Μη) 22700 19400 29600 Precipitate 14800 Weight average molecular weight (Mw) 48800 42500 89200 Precipitate 38500 醯 imidization rate (%) 86 41 86 86 86 Warpage evaluation ◎ ◎ X - ◎ HAST evaluation (Ω) > 2E+8 > 2E+8 > 2E+8 - Short-circuit storage stability evaluation 〇〇〇 - X As shown in Table 6, no addition is given The acid dianhydride of the base is used, and the polydiimide precursor of the acid dianhydride of the specific structure and the diamine of two specific structures is used to satisfy solvent solubility (storage stability), warpage evaluation, and insulation resistance (HAST test). (Examples 24 to 25). On the other hand, a polyamidiamine precursor containing no specific 148610.doc •67-201107418 structure of dianhydride (Comparative Example 9), or a polytetramine containing no one of the two specific structures of diamine Precursor (Precursor Comparative Example 8 and Comparative Example 10) did not achieve balance of various properties such as solvent solubility (storage stability), warpage evaluation, and insulation resistance (HAST test). [Industrial Applicability] The resin composition of the present invention can provide a cured film which exhibits excellent heat resistance by thermal hardening, and the cured film is excellent in heat resistance, and has less warpage and low rebound, so it is effectively used as a surface protective film and interlayer insulation of a semiconductor element. The protective insulating film for a film or a printed wiring board can be preferably used for various electronic parts. The present application is based on Japanese Patent Application No. 2009438076, filed on Jun. 9, 2009, and Japanese Patent Application No. 2 296969, filed on December 28, 2009. These are all included in this article. 148610.doc 68-

Claims (1)

201107418 VII. Patent Application Range: 1. A resin composition characterized by comprising a polyimine precursor having a polyether structure, and a compound having a heat crosslinkable functional group, and the above-mentioned polyimide precursor The imidization ratio is 40% or more and 98% or less. 2. The resin composition of claim 1, wherein the polyamidene precursor has a ruthenium imidation ratio of 40% or more and 95% or less. 3. The resin composition of claim 1 or 2, wherein the polyimine precursor comprises a polyimine moiety having the structure of the following formula (1): [Chemical Formula 1] 0 -^*0-R4~)*0-R5- (In the formula (1), 'acetyl and oxime 2 represent a tetravalent organic group, and R!, R2, r3, 4 and r5 represent a carbon number of 1 to a carbon number of 5. The alkyl group may have a side chain; m, η and q represent an integer of from 1 to 50). 4. The resin composition according to any one of the items 1 to 3, wherein the content of the diamine having the structure of the following formula (2) in all the diamines in the polyimine precursor is 15 mol% or more and 85 mol% or less: [Chemical 2] (In the formula (2), Ri, R2, R3, R-4, and R5 represent a carbon number of 1 to a carbon number of 5, and 148610.doc 201107418, the base ' may have a side chain; m, η, and q represent an integer of 1 to 50. ). 5. A resin composition according to the item 4, wherein the amine having the structure of the above formula has a stretching alkyl group represented by 'R2, R3, R4 and r5 and having two or more kinds of alkylene groups. 6. The resin composition of claim 4 or 5, wherein the diamine having the structure of the above formula (2) has a weight average molecular weight of from 400 to 2,000. 7. The resin composition according to any one of claims 4 to 6, wherein the diamine having the structure of the above formula (2) has a weight average molecular weight of 6 Å to 2 Å. The resin composition according to any one of the items 4 to 7, wherein the polyamidene precursor comprises a polylysine moiety having a polyproline structure, and a polyimine having a polyimine structure The diamine having the structure of the above-mentioned general formula (2) is more contained in the polyimine portion. 9. The resin composition according to any one of claims 3 to 8, wherein 21 and 22 of the above formula (1) are a tetravalent organic group represented by the following formula (3): [Formula 3] ) ' R17 means _〇_, ·3〇2 or _c〇_). The resin composition of any one of the items 1 to 9, wherein the polyi-imine precursor has a brewing imidization ratio of 5% or more, and the money imidization ratio (10), and 3, 3, , 4,4L diphenyl stone wind tetracarboxylic acid liver relative to the total acid component content ε 148610.doc 201107418 The relationship between the molar % satisfies the relationship (E2 0.6D-30). The resin composition according to any one of claims 3 to 10, wherein the oxime of the above formula (1) and the dianhydride structure are removed from the 3,3',4,4'-diphenyl sulphuric acid tetracarboxylic acid. The tetravalent organic residue and the tetravalent organic residue from the dianhydride structure are removed from the 3,3,4,4,-benzophenonetetracarboxylic dianhydride. The resin composition according to any one of claims 3 to 11, wherein Z丨 and Z2 of the above formula (1) are contained from 3,3,4,4,-diphenylsulfonetetracarboxylic dianhydride. The tetravalent organic residue of the di-hepatic structure and the tetravalent organic residue of the dianhydride structure are removed from the 4,4,-oxydiphthalic dianhydride. The resin composition of claim 1 or 2, wherein the polyimine precursor contains a polyimine moiety having a structure of the following formula (4): [Chemical 4] (In the formula (4), Z3 and Z4 represent a tetravalent organic group, and Ru represents a carbon number of 2 to a carbon number of 1 Å. The h represents an integer of 1 to 50). 14. The resin composition according to claim 13, wherein the content of the diamine having the structure of the following general formula (5) in all the diamines in the polyimine precursor is 15 mol% or more. Less than the ear: [Chemical 5] NH2 148610.doc 201107418 (In the formula (5), R represents an integer H 18 represents an alkyl group having a carbon number of 2 to a carbon number of 10, and h represents a polycondensation formula of the formula (6) of 1 50. Any of the 14 sap of the saplings of the saplings of the sapphire, wherein the __ amine further contains at least one of the following aromatic diamines: [Chem. 6] rv- The general formula (8) represents) (in the formula (6), 'Rl9 is represented by the following formula (7) or [Chemical 7] The resin composition of claim 14 or 15, wherein the above aromatic bis(3-aminophenoxy)benzene. A compound according to any one of claims 1 to i6, wherein the compound having a heat-coupling functional group is flame-retardant by a resin. The resin composition of any one of the items 1 to 17, wherein the compound having the parental functional group is selected from the group consisting of three well compounds, benzo i48610.doc And a resin composition according to any one of claims 1 to 18, wherein the above-mentioned hot-crossing is provided in the group of the compound of the present invention. The compound of the functional group is a compound having a heat-crosslinkable functional group, which is substantially free of the heat-crosslinking accelerator. The resin composition according to any one of claims 1 to 19, wherein The resin composition of any one of the above-mentioned items 1 to 20, wherein the above polyethylenimine is contained in an amount of the above-mentioned compound of the present invention. The imidization ratio of the hydrazine precursor is from 4% to 9% by weight. The resin composition according to any one of the preceding claims, wherein the acid value of the above-mentioned polyamidiamine precursor is 16 mg KOH/ g or more 23. As in any of claims 1 to 22 The resin composition, wherein the resin composition is stored in the resin composition for 3 months, the change in viscosity is 2% or less. The resin composition according to any one of claims 1 to 23, wherein the polyimine precursor The acid value is 16 mg K〇H/g or more and 7 〇 mg K〇H/g or less, and after the resin composition is stored for one month, the change in viscosity is 10% or less. The resin composition according to any one of 24, wherein the terminal of the polymer main chain of the above polyamidiamine precursor is at least an anthracene derivative selected from the group consisting of a monoamine derivative or a carboxylic acid derivative ( The resin composition according to any one of claims 1 to 25, wherein the elastic modulus after thermosetting is 0.3 to 1.4 GPa, and is immersed in a solder bath at 148610. .doc 201107418 The resin composition of any one of items 1 to 2, which further contains a flame retardant, the halogen element content is 1〇〇〇. Below ppm, it has a flame retardancy of VTM-0 according to the UL-94 specification. 28. A resin composition for screen printing, characterized in that The resin composition of any one of claims 1 to 27 and having a solid content concentration of 45% or more, which is printed on a substrate by screen printing and dried, and has a dried film thickness of 15 μm or more. And a resin composition for forming a protective film of a printed circuit board, comprising: the resin composition according to any one of claims 1 to 28, 30. It is characterized in that it is obtained by thermally hardening the resin composition of any one of claims 1 to 28. A circuit board comprising: a substrate having wiring; and a cured product of claim 3, which covers the surface of the substrate. A printed wiring board using the resin composition for screen printing as claimed in claim 1 and a flexible printed wiring board having a component mounting portion, characterized in that it comprises a part by screen printing method The step of printing the resin composition other than the portion necessary for the mounting is obtained. 33. A polyimine precursor, which comprises the acid reading term represented by the following formula (9) a polymer having a diamine having a fluorinated group represented by the following formula (7) and at least an old aromatic diamine represented by the following formula (6), and a polyethylenimine pre-existing + Λ ^ The imidization ratio of the makeup primer is 4% or more and 98% or less: [Chem. 8] 148610.doc 201107418 (In the formula (9), 'H2丨 means _s〇2_) [Chemical 9] H^N1 1 Ri ^Ra -R4-^- 〇-NH2 (in the formula (2), R, R group, may have a side chain [10] 2, . 3 4 and Rs represent a carbon number of 1 to a carbon number of 5 n and q represent integers of ι~5〇); h2n Nh2 (in the formula (6) [Chem. 7], R!9 or less, the genus (7) or the following formula (8)) - 〇 0— _ 0 0 - (in the formula (8), R20 represents a single bond, -Ο-, -S〇2- or -C(CH3)2-). 34. The gibberimide precursor of claim 33 wherein the above four oxonic acid bismuth comprises 3,3,4,4-dibenzophenone tetracarboxylic dianhydride. 35. The polyamidiamine precursor of claim 33 or 34, wherein the oxime imidization ratio is 148610.doc 201107418 50% or more, and the oxime imidization rate is D%, and 3, 3, 4, 4' The relationship between the content of diphenylsulfonium tetracarboxylic dianhydride and the total acid component E mole % satisfies the relationship of (Eg 0.6D-30). The polyimine precursor according to any one of claims 33 to 35, wherein in the diamine having the structure of the above formula (2), the alkylene group representing R2, r3, 4 and r5 has 2 More than the above alkyl group. The polyamidiamine precursor according to any one of claims 3 to 3, wherein the diamine having the structure of the above formula (2) has a weight average molecular weight of from 4 Å to 2,000. The polyanilin precursor according to any one of claims 3 to 3, wherein the diamine having the structure of the above formula (2) has a weight average molecular weight of from 6 〇〇 to 2,000. The polyimine precursor according to any one of claims 33 to 38, wherein the diamine having the structure of the above formula (2) is more contained in the polyfluorene than the polyimine precursor. In the imine. 148610.doc 201107418 IV. Designation of the representative representative: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 148610.doc