JP2013107934A - Resin composition - Google Patents

Abstract

The present invention relates to a resin composition that can reduce warpage during curing, has excellent insulation reliability, and can be suitably used as a material for a surface protection film of a semiconductor element, an interlayer insulation film, a protective insulation film for a printed wiring board, an interlayer insulation film, etc. To provide a resin film using a resin composition and a wiring board using them.
The resin composition of the present invention comprises (A) a polymer compound obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component having a polyether structure and at least two terminal amine structures; (B) An antioxidant, and the polymer compound is characterized by having no ester structure and no sulfonic acid group in the molecule.
[Selection figure] None

Description

  The present invention relates to a resin composition, for example, a resin composition used as an insulating material for a flexible printed wiring board.

  A polyimide resin composition having excellent heat resistance and insulation reliability is used as a material for the surface protective film of semiconductor elements, interlayer insulating films, and protective insulating films for printed wiring boards. When a polyimide resin composition is used as an insulating material for a flexible printed wiring board, it is required that there is little warpage after curing in addition to insulation reliability. A resin composition containing a polyimide having a polyether structure has been proposed as a low-elasticity polyimide-based resin composition that can reduce warping after curing (see, for example, Patent Document 1). In addition, as a resin composition excellent in heat resistance and flexibility, a polyimide having an ester structure and a sulfonyl group (for example, see Patent Document 2), or a resin composition in which a polyimide having an ester structure and an antioxidant are combined. It has been proposed (see, for example, Patent Document 3).

JP 2011-153325 A JP 2006-22302 A JP 2010-77382 A

  However, when the resin composition described in Patent Document 1 is used as an insulating material for a flexible printed wiring board, the polyimide polyether structure is subjected to thermal oxidation in a process at a high temperature such as a solvent distillation process or a lamination process. Insulation reliability may decrease.

  Moreover, in the resin compositions described in Patent Document 2 and Patent Document 3, since the polyimide has an ester structure in the molecule, the ester structure portion is easily subjected to hydrolysis, and the insulating reliability may be lowered. . Moreover, in the resin composition of patent document 2, since the polyimide which has a sulfonyl group is used, impurities, such as a sulfonic acid, exist in a resin composition, and insulation reliability may deteriorate by the impurity.

  The present invention has been made in view of the above points, and can reduce warping during curing, has excellent insulation reliability, a surface protection film for semiconductor elements, an interlayer insulation film, a protective insulation film for printed wiring boards, and an interlayer insulation. It aims at providing the resin composition which can be used conveniently as materials, such as a film | membrane, the resin film using the resin composition, and a wiring board using them.

  As a result of intensive studies, the present inventors have found that (1) a polymer compound having excellent insulation reliability can be obtained by not containing an ester structure or a sulfonyl group in the molecule, and (2) a polyether as a diamine component. By using a diamine having a structure, a polymer compound having excellent flexibility can be obtained, and (3) by further containing an antioxidant, thermal oxidation is suppressed and the polymer has excellent insulation reliability. The inventors have found that a compound can be obtained, and have completed the present invention. That is, the present invention is as follows.

  The resin composition of the present invention comprises (A) a polymer compound obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component having a polyether structure and at least two terminal amine structures, and (B) an oxidation. An inhibitor, and the polymer compound has no ester structure and no sulfonyl group in the molecule.

  The resin composition of the present invention contains (C) a polyfunctional crosslinkable compound having two or more crosslinkable functional groups that react with a hydroxyl group and / or a carboxyl group to form a crosslink, and the polymer compound is It preferably has a hydroxyl group and / or a carboxyl group.

  In the resin composition of the present invention, the polymer compound and / or the polyfunctional crosslinkable compound is trifunctional or more, and three-dimensional crosslinking is formed between the polymer compound and the polyfunctional crosslinkable compound. It is preferable to obtain.

  In the resin composition of the present invention, (C) a polyfunctional crosslinkable compound having two or more crosslinkable functional groups that react with a hydroxyl group and / or a carboxyl group to form a crosslink, and (D) two or more hydroxyl groups It is preferable to contain a polyfunctional hydroxyl group-containing compound having

  In the resin composition of the present invention, the polyfunctional crosslinkable compound and / or the polyfunctional hydroxyl group-containing compound is trifunctional or more, and three-dimensional between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound. It is preferred that crosslinks can be formed.

  In the resin composition of this invention, it is preferable that the polyfunctional isocyanate compound which has a 2 or more isocyanate group is included as the said polyfunctional crosslinkable compound.

  In the resin composition of this invention, it is preferable to contain the polyfunctional oxazoline compound which has a 2 or more oxazoline group as said polyfunctional crosslinkable compound.

  In the resin composition of the present invention, the polyfunctional hydroxyl group-containing compound is preferably a polycarbonate polyol.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^７、Ｒ^８、Ｒ^１０、Ｒ^１１、Ｒ^１３、及びＲ^１５は、それぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表す。Ｒ^３、Ｒ^６、Ｒ^９、Ｒ^１２、及びＲ^１４は、それぞれ独立して炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐは、それぞれ独立して０以上１００以下の整数を表す。Ｒ^１６は、４価の有機基を表す。） In the resin composition of the present invention, the polymer compound preferably has a repeating structure represented by the following general formula (1).

(In formula (1), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹³ , and R ¹⁵ are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, R ³ , R ⁶ , R ⁹ , R ¹² , and R ¹⁴ each independently represents a tetravalent organic group having 1 to 20 carbon atoms; , N and p each independently represents an integer of 0 to 100. R ¹⁶ represents a tetravalent organic group.)

  In the resin composition of the present invention, the polymer compound preferably has a weight average molecular weight of 20,000 to 200,000.

  In the resin composition of this invention, it is preferable to contain 0.1 mass part-10 mass parts of said antioxidant with respect to 100 mass parts of said high molecular compounds.

  In the resin composition of the present invention, the antioxidant is preferably an antioxidant having a hindered phenol structure.

  The resin film of the present invention comprises a base material and the resin composition provided on the base material.

  In the resin film of the present invention, the substrate is preferably a carrier film.

  In the resin film of this invention, it is preferable to comprise the cover film provided on the said resin composition.

  In the resin film of this invention, it is preferable that the said base material is copper foil.

  The wiring board of this invention comprises the base material which has wiring, and the said resin composition provided so that the said wiring might be covered.

  According to the present invention, warpage during curing can be reduced, insulation reliability is excellent, and it can be suitably used as a material such as a surface protection film of a semiconductor element, an interlayer insulation film, a protective insulation film for a printed wiring board, an interlayer insulation film, etc. A resin composition, a resin film using the resin composition, and a wiring board using them can be provided.

It is a figure which shows the outline of the manufacturing process of the multilayer flexible wiring board which concerns on this Embodiment.

  Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The resin composition according to the present embodiment comprises (A) a polymer compound obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component having a polyether structure and at least two terminal amine structures; B) an antioxidant, and the polymer compound has no ester structure and no sulfonyl group in the molecule.

  According to this resin composition, since the polymer compound does not have an ester structure in the molecule, hydrolysis of the polymer compound based on the ester structure can be suppressed, so that the insulation reliability of the resin composition is improved. In addition, since the polymer compound does not have a sulfonyl group in the molecule, the mixing of impurities such as sulfonic acid into the resin composition can be suppressed, so that the insulation reliability is improved. In addition, since the polymer compound has a polyether structure based on a diamine component and at least two terminal amine structures, the polymer compound is imparted with appropriate flexibility and can reduce warping during curing of the resin composition. It becomes. Furthermore, since an antioxidant is contained, it is possible to suppress a decrease in insulation reliability due to oxidation of the polyimide polyether structure. Therefore, it is possible to realize a resin composition that can be suitably used as a material for a surface protective film, an interlayer insulating film, a printed wiring board protective insulating film, an interlayer insulating film, and the like of a semiconductor element.

  The resin composition according to the present embodiment contains (C) a polyfunctional crosslinkable compound having two or more crosslinkable functional groups that react with a hydroxyl group and / or a carboxyl group to form a crosslink, and is a polymer. The compound preferably has a hydroxyl group and / or a carboxyl group. With this configuration, as will be described in detail later, a crosslinking bond is formed between the crosslinkable functional group of the polyfunctional crosslinkable compound and the hydroxyl group and / or carboxyl group of the polymer compound. The shrinkage of the polymer compound at the time can be suppressed, and the warp at the time of curing of the resin composition can be further reduced.

  In the resin composition according to the present embodiment, (C) a polyfunctional crosslinkable compound having two or more crosslinkable functional groups that react with a hydroxyl group and / or a carboxyl group to form a crosslink, and (D And a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups. As described in detail later, this structure forms a cross-linking bond between the crosslinkable functional group of the polyfunctional crosslinkable compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound. It becomes possible to suppress the shrinkage of the molecular compound, and it is possible to further reduce the warpage during curing of the resin composition.

  Furthermore, in the resin composition according to the present invention, the polymer compound and / or the polyfunctional hydroxyl group-containing compound is trifunctional or more, and three-dimensional crosslinking can be formed between the polymer compound and the polyfunctional crosslinkable compound. It is preferable. In this case, since the polymer compound and / or the polyfunctional hydroxyl group-containing compound is trifunctional or more, a plurality of cross-linking bonds between the polymer compound and / or the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound. Are formed, and a three-dimensional network (three-dimensional bridge) can be formed. Thereby, since shrinkage | contraction of the high molecular compound at the time of hardening of a resin composition can further be suppressed, the curvature at the time of hardening of a resin composition can be reduced especially.

  Further, in the resin composition according to the present invention, the polyfunctional crosslinkable compound and / or the polyfunctional hydroxyl group-containing compound is trifunctional or more, and 3 between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound. It is preferred that dimensional crosslinks can be formed. In this case, since the polyfunctional crosslinkable compound and / or the polyfunctional hydroxyl group-containing compound is trifunctional or more, a plurality of crosslinks are formed between the polyfunctional crosslinkable compound and the polyfunctional crosslinkable compound, A three-dimensional network can be formed. Thereby, since shrinkage | contraction of the high molecular compound at the time of hardening of a resin composition can further be suppressed, the curvature at the time of hardening of a resin composition can be reduced especially.

  Furthermore, the resin composition according to the present invention preferably contains a polyfunctional isocyanate compound having two or more isocyanate groups as the polyfunctional crosslinkable compound. With this configuration, since a urethane bond is formed between the isocyanate group of the polyfunctional isocyanate compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound, and a three-dimensional network is formed, the polymer compound at the time of curing the resin composition The shrinkage of the resin composition can be suppressed, and the warpage of the resin composition during curing can be further reduced. In particular, when the polymer compound has a hydrogen bonding functional group (for example, a hydroxyl group, an amide group, an imide group, a carboxyl group, etc.), a mutual bond due to hydrogen bonding between the urethane bond and the hydrogen bonding functional group. An effect occurs. Thereby, the low resilience of the resin composition can be improved, and appropriate fluidity is imparted to the resin composition by combining the plasticity of the polymer compound and the elasticity of the resin composition. As a result, it is possible to achieve both conflicting physical properties (fluidity and viscosity) required when the resin composition is used as an interlayer insulating film of a flexible printed wiring board.

  The resin composition according to the present invention preferably contains a polyfunctional oxazoline compound having two or more oxazolines as the polyfunctional crosslinkable compound. With this configuration, the oxazoline group of the polyfunctional oxazoline compound reacts with the hydroxyl group or carboxyl group of the polymer compound and the hydroxyl group of the polyfunctional hydroxyl compound to form an amide bond and / or a crosslink containing an amide ester structure. And a three-dimensional network can be formed. In particular, when the polymer compound has a hydrogen bondable functional group, an interaction or chemical bond is formed between the cross-linked bond and the hydrogen bondable functional group. Thereby, the curvature at the time of hardening of a resin composition can further be reduced. Hereinafter, each component of the resin composition according to the present embodiment will be described in detail.

(A) Polymer Compound First, the polymer compound in the resin composition according to the present embodiment will be described. As the polymer compound, a tetracarboxylic dianhydride component having no ester structure and sulfonyl group in the molecule and a diamine component having at least one polyether structure and at least two terminal amine structures are polymerized. As long as it can be obtained, various polymer compounds can be used within the scope of the effects of the present invention.

  By using a polymer compound that does not have an ester structure in the molecule, hydrolysis of the polymer compound can be suppressed, and a decrease in insulation reliability when used in a resin composition can be suppressed. Further, by using a polymer compound that does not have a sulfonyl group, it is possible to suppress a decrease in insulation reliability when used in a resin composition. In general, in the production of a raw material for a polymer compound having a sulfonyl group, a by-product having a sulfonic acid group or a sulfonic acid component such as a sulfonic acid itself may be generated with the sulfonylation of the raw material. . When this sulfonic acid component is mixed in the resin composition, it is considered that the insulation reliability is deteriorated. In the case where a polymer compound having no sulfonyl group in the molecule is used, it is considered that the deterioration of the insulation reliability of the resin composition can be suppressed because such mixing of the sulfonic acid component can be suppressed.

  Examples of the polymer compound include polyamide, polyamideimide, polyamic acid, polyimide obtained by imidizing polyamic acid, and the like. In the present embodiment, the term “polyimide” includes both a polyimide precursor in which a part of polyamic acid is imidized with all polyamic acids and a polyimide in which all polyamic acids are imidized.

  The polyimide is obtained, for example, by polymerizing a tetracarboxylic dianhydride component and a diamine component. When polyimide is used as the polymer compound, for example, polyimide having mainly a polyimide structure as a repeating structural unit may be used, or polyimide having a polyimide structure and a polyamic acid structure as repeating structural units may be used.

  Moreover, as a high molecular compound, it is preferable to use what has a polyimide structure represented by following General formula (1) as a repeating structural unit from a viewpoint of reducing the curvature at the time of hardening of a resin composition. By having a polyether structure in the molecule of the polymer compound, warpage during curing can be reduced.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^７、Ｒ^８、Ｒ^１０、Ｒ^１１、Ｒ^１３、及びＲ^１５は、それぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表す。Ｒ^３、Ｒ^６、Ｒ^９、Ｒ^１２、及びＲ^１４は、それぞれ独立して炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐは、それぞれ独立して０以上１００以下の整数を表す。Ｒ^１６は、４価の有機基を表す。）

(In formula (1), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹³ , and R ¹⁵ are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, R ³ , R ⁶ , R ⁹ , R ¹² , and R ¹⁴ each independently represents a tetravalent organic group having 1 to 20 carbon atoms; , N and p each independently represents an integer of 0 to 100. R ¹⁶ represents a tetravalent organic group.)

  Examples of the tetracarboxylic dianhydride component include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as “BPDA”), benzophenone-3,3 ′, 4,4 ′. -Tetracarboxylic dianhydride (hereinafter abbreviated as "BTDA"), oxydiphthalic dianhydride (hereinafter abbreviated as "ODPA"), pyromellitic anhydride, bis (3,4-dicarboxyphenyl) ether Dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3 4-tetra Rubonic acid dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl)- 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Tetracarboxylic acids such as 5,5 ′-[1-methyl-1,1-ethanediylbis (1,4-phenylene) bisoxy] bis (isobenzofuran-1,3-dione) (hereinafter abbreviated as “BISDA”) And dianhydrides. As the tetracarboxylic dianhydride component, the above-described tetracarboxylic dianhydrides may be used alone or in admixture of two or more. From the viewpoint of insulation reliability, it is preferable to use BPDA, ODPA, BTDA, BISDA.

  The diamine component is not particularly limited as long as it is a compound having a polyether structure and at least two terminal amine structures, and various diamines can be used as long as the effects of the present invention are exhibited. Note that at least one polyether structure may be present in the molecular chain. The polyether structure may be an aliphatic polyether structure such as polyalkylene ether, or an aromatic polyether structure such as polyphenylene ether.

  As a diamine component, it is preferable that the diamine represented by following General formula (2) is included.

（式（２）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^７、Ｒ^８、Ｒ^１０、Ｒ^１１、Ｒ^１３、及びＲ^１５は、それぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表す。Ｒ^３、Ｒ^６、Ｒ^９、Ｒ^１２、及びＲ^１４は、それぞれ独立して炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐは、それぞれ独立して０以上１００以下の整数を表す。）

(In formula (2), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹³ , and R ¹⁵ are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, R ³ , R ⁶ , R ⁹ , R ¹² , and R ¹⁴ each independently represents a tetravalent organic group having 1 to 20 carbon atoms; , N and p each independently represent an integer of 0 to 100.)

  Examples of the diamine represented by the general formula (2) include polyoxyethylenediamine compounds such as 1,8-diamino-3,6-dioxyoctane, and polyoxyethylenes such as Huntsman's Jeffamine EDR-148 and EDR-176. Alkylene diamine compounds, Jeffamine D-230, D-400, D-2000, D-4000, polyoxypropylene diamine compounds such as polyetheramine D-230, D-400, D-2000 manufactured by BASF, HK- And compounds having different oxyalkylene groups such as 511, ED-600, ED-900, ED-2003, and XTJ-542. Warpage can be reduced by using a compound having these oxyalkylene groups.

  Moreover, as a diamine component, as long as it does not have an ester structure and a sulfonic acid group in a molecule | numerator, you may use together and use the diamine represented by the said General formula (2), and another diamine. . Examples of other diamines include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4 -Diaminobenzene (hereinafter abbreviated as "PPD"), 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diamino Biphenyl, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4-aminophenyl) sulfi 4,4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9 -Bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as “APB”), 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′- Bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane (hereinafter abbreviated as “BAPP”), 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3 , 3′-dihydroxy-4,4′-diaminobiphenyl, 1,3-bis (4-aminophenoxybenzene), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as “6FAP”) For example).

  Moreover, as a high molecular compound, that whose weight average molecular weight Mw is 30,000-200,000 is preferable, and what is 30,000-100,000 is more preferable. Here, the weight average molecular weight refers to the weight average molecular weight measured by the method described in the examples described later. From the viewpoint of excellent solder resistance and further suppressing the flowability of the resin, it is preferable that Mw is 30,000 or more. From the viewpoint of good embedding properties, Mw is preferably 200,000 or less.

  Next, a polyimide production method will be described as an example of a polymer compound production method. In the manufacturing method of the polyimide which concerns on this Embodiment, all the methods which can manufacture a polyimide including a well-known method are applicable. Among them, it is preferable to use a method of performing the reaction in an organic solvent. As a solvent used in such a reaction, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 1,3 -Dioxane, 1,4-dioxane, dimethyl sulfoxide, benzene, toluene, xylene, mesitylene, phenol, cresol, ethyl benzoate, butyl benzoate and the like. These may be used alone or in combination of two or more. In addition, the density | concentration of the reaction raw material in this reaction is 2 mass%-80 mass% normally, Preferably it is 30 mass%-70 mass%.

  The molar ratio of the tetracarboxylic dianhydride to be reacted and the diamine is in the range of 0.8 to 1.2. Within this range, the molecular weight can be increased, and the elongation and the like are excellent. Preferably it is 0.9-1.1, More preferably, it is 0.95-1.05.

  Polyimide is obtained by the following method. First, a polyimide having a polyamic acid structure is produced by subjecting a reaction raw material to a polycondensation reaction at room temperature. Next, this polyimide is preferably heated to 100 ° C. to 400 ° C. to imidize, or chemically imidized using an imidizing agent such as acetic anhydride, thereby having a repeating unit structure corresponding to polyamic acid. A polyimide containing a polyimide structure is obtained. In the case of imidization by heating, in order to remove by-product water, dehydration is carried out under reflux using a Dean-Stark type dehydrator in the presence of an azeotropic agent (preferably toluene or xylene). Is also preferable.

  In addition, it is also preferable to obtain a polyimide having both a polyimide structure and a polyamic acid structure by carrying out the reaction at 80 ° C. to 220 ° C. to advance both the generation of a polyimide having a polyamic acid structure and the thermal imidization reaction. That is, a diamine component and a tetracarboxylic dianhydride component are suspended or dissolved in an organic solvent and reacted under heating at 80 ° C. to 220 ° C. to cause both generation of polyimide and dehydration imidization. It is also preferable to obtain polyimide.

  Moreover, the terminal of the polymer main chain of polyimide can be end-capped with an end-capping agent made of a monoamine derivative or a carboxylic acid derivative. By sealing the terminal of the polymer main chain of polyimide, the storage stability derived from the terminal functional group is excellent.

  Examples of the end capping agent comprising a monoamine derivative include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, and 3,5-xylidine. O-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, o-aminophenol P-aminophenol, m-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminobenzonitrile, p-aminobenzonitrile Lyl, m-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3 -Aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-aminophenyl phenyl sulfone , Α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 5-amino-1-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino Aromatic monoamines such as 2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene be able to. Among these, aniline derivatives are preferably used. These may be used alone or in combination of two or more.

  Examples of the terminal blocking agent made of a carboxylic acid derivative mainly include carboxylic anhydride derivatives. Examples of the carboxylic anhydride derivative include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-di Carboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalene Dicarboxylic anhydride, 1,2-anthracenedica Bon acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-aromatic dicarboxylic acid anhydrides such as anthracene dicarboxylic acid anhydride. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used. These may be used alone or in combination of two or more.

  The polyimide obtained by the above-described method can be used in the resin composition according to the present embodiment as it is or without further solvent mixing, without adding a solvent.

(B) Antioxidant In the resin composition according to the present embodiment, by adding an antioxidant to the polymer compound, thermal oxidation can be suppressed, and the insulation reliability is excellent. A resin composition with reduced warpage can be obtained.

  Examples of the antioxidant include an antioxidant having a phenol structure, an antioxidant having hydroxylamine, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Among these, an antioxidant having a phenol structure is preferable, and among the antioxidants having a phenol structure, an antioxidant having a hindered phenol structure is more preferable. Even if there are crosslinkable functional groups of the polyfunctional cross-linking compound, decomposition of the polymer compound cannot be prevented, and as a result, insulation reliability and solder resistance may decrease, but there is an antioxidant. By doing so, decomposition of the polymer compound can be suppressed, and a resin composition excellent in solder resistance and insulation reliability can be realized.

  The antioxidant having a phenol structure is not particularly limited as long as it has a phenol structure in the molecule. For example, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,4-dihydroxyanthraquinone, 2- Examples thereof include t-butyl-4-hydroxyanisole and 4-t-butylcatechol.

  The antioxidant having a hindered phenol structure is not particularly limited as long as it is a compound having an electron donating group and / or a substituent having 4 or more carbon atoms in the ortho position of the hydroxyl group. -Tris [[4- (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trione, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4-butylidenebis ( 3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 4,4 ′ Isopropylidenebisphenol, 2,4-dimethyl-6-tert-butylphenol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (hereinafter abbreviated as “IRGANOX1010”) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t) -Butyl-4-hydroxybenzyl) benzene, 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methyl) Benzyl) -4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 3-t-butyl-4-hydroxyl Sole, 2,4-dibenzoylresorcinol, 2,6-di-t-butyl-4-ethylphenol, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4- Methoxybenzophenone, 2,4,5-trihydroxybenzophenone, α-tocopherol, bis [2- (2-hydroxy-5-methyl-3-t-butylbenzyl) -4-methyl-6-t-butylphenyl] terephthalate Triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (hereinafter abbreviated as “IRGANOX245”), 1,6-hexanediol-bis [3- (3 , 5-di-t-butyl 4-hydroxyphenyl) propionate] (hereinafter “IRG It referred to as NOX259 "), and the like.

  Examples of the hydroxylamine antioxidant include dialkylamines such as dioctadecylhydroxylamine, N, O-dialkylhydroxylamine, 1-naphthohydroxamic acid, 4,5-dibromo-N-methoxy-N-methyl-2- Furan carboxamide, 4- (hydroxyamino) quinoline N-oxide, acetohydroxamic acid, benzenesulfohydroxamic acid, benzohydroxamic acid, hydroxyurea, L-canavanine sulfate hydrate, N, N'-dimethoxy-N, N'- Dimethyloxamide, N, N, O-triacetylhydroxylamine, N, N, O-tris (trimethylsilyl) hydroxylamine, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, O-bis (Trifluoroacetyl) Droxylamine, N, O-bis (trimethylsilyl) hydroxylamine, N, O-dimethylhydroxylamine hydrochloride, N- (diethylcarbamoyl) -N-methoxyformamide, N- (tert-butyl) hydroxylamine hydrochloride, N -Benzoyl-N-phenylhydroxylamine, N-carbobenzoxyhydroxylamine, N-cinnamoyl-N- (2,3-xylyl) hydroxylamine, N-hydroxyurethane, N-methoxy-N, O-bis (trimethylsilyl) Carbamate, N-methoxy-N-methyl-2-furancarboxamide, N-methoxy-N-methylacetamide, N-methoxydiacetamide, N-methyl-2-dimethylaminoacetohydroxamic acid, N-methyl-N, O- Bis (trimethylsilyl Vidroxylamine, N-methyl furohydroxamic acid, N-methylhydroxylamine hydrochloride, octanohydroxamic acid, salicylhydroxamic acid, sodium benzohydroxamic acid hydrate, sodium octanohydroxamic acid hydrate, N- (benzyloxy ) Tert-butyl carbamate, tert-butyl N-hydroxycarbamate, tert-butyl [bis (4-methoxyphenyl) phosphinyloxy] carbamate, 4,5-dibromo-N-methoxy-N-methyl-2 -Furancarboxamide, carboxymethoxylamine hemihydrochloride, hydroxylamine-O-sulfonic acid, L-canavanine sulfate hydrate, N, N'-dimethoxy-N, N'-dimethyloxamide, N, N, O-tri Acetylhydroxylamine, N, N, O -Tris (trimethylsilyl) hydroxylamine, N, O-bis (trifluoroacetyl) hydroxylamine, N, O-bis (trimethylsilyl) hydroxylamine, N, O-dimethylhydroxylamine hydrochloride, N- (diethylcarbamoyl) -N -Methoxyformamide, N-methoxy-N, O-bis (trimethylsilyl) carbamate, N-methoxy-N-methyl-2-furancarboxamide, N-methoxy-N-methylacetamide, N-methoxydiacetamide, N-methyl- N, O-bis (trimethylsilyl) bidoxylamine, O- (2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride, O- (2-trimethylsilylethyl) hydroxylamine hydrochloride, O- ( Trimethylsilyl) hydroxy Amine, O-4-nitrobenzylhydroxylamine hydrochloride, O-allylhydroxylamine hydrochloride, O-benzylhydroxylamine hydrochloride, O-isobutylhydroxylamine hydrochloride, O-methylhydroxylamine hydrochloride, N- (benzyloxy) ) Tert-butyl carbamate, [bis (4-methoxyphenyl) phosphinyloxy] carbamate tert-butyl and the like.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, laurylthiothiodithionate, ditridecyl-3,3′-thiodipropionate, and dimyristyl-3,3′-thiodipropioate. , Distearyl-3,3′-thiodipropionate, tetrakis-methylene-3-laurylthiopropionate methane, distearyl-3,3′-methyl-3,3′-thiodipropionate, laurylstearyl -3,3'-thiodipropionate, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl] sulfide, β-lauryl thiopropionate, 2-mercaptobenzo Examples include imidazole and 2-mercapto-5-methylbenzimidazole.

  Examples of phosphorus antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl. Isodecyl phosphite, diphenyl tridecyl phosphite, phosphonic acid [1,1-diphenyl-4,4′-diylbistetrakis-2,4-bis (1,1-dimethylethyl) phenyl] ester, triphenyl phosphite Phyto, Tris (nonylphenyl) phosphite, 4,4′-isopropylidenediphenol phenol phosphite, Tris (2,4-di-t-butylphenyl) phosphite, Tris (biphenyl) phosphite Phyto, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol Diphosphite (hereinafter abbreviated as “PEP-36”), di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetra (tridecyl) -4,4′-butylidenebis (3- Methyl-6-tert-butylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, 3,5-diphosphite -T-butyl-4-hydroxybenzyl phosphate Ethyl ester, sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, 1,3-bis (diphenoxy) Phosphoryl secondary antioxidants such as (phosphonyloxy) benzene.

  As addition amount of antioxidant, it is preferable that it is 0.1 mass part-10 mass parts with respect to 100 mass parts of high molecular compounds, and it is still more preferable that it is 0.1 mass part-5 mass parts. If the addition amount of the antioxidant is 0.1 parts by mass or more, the thermal oxidation is excellently suppressed, and if it is 10 parts by mass or less, the solder resistance is excellent.

  Moreover, as an antioxidant, you may use 1 type or in mixture of 2 or more types. In particular, the combined use of an antioxidant having a phenol structure and a phosphorus-based antioxidant can further prevent oxidation of the polyether structure contained in the polymer compound.

(C) Polyfunctional crosslinkable compound The polyfunctional crosslinkable compound is a compound having two or more crosslinkable functional groups. Here, the crosslinkable functional group refers to a functional group capable of forming a crosslink between the hydroxyl group or carboxyl group of the polymer compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound. Examples of the crosslinkable functional group include, but are not limited to, an isocyanate group and an oxazoline group. As the polyfunctional crosslinkable compound, a bifunctional crosslinkable compound having two crosslinkable functional groups may be used, or a crosslinkable compound having three or more crosslinkable functional groups may be used. Examples of the polyfunctional crosslinking compound include a polyfunctional isocyanate compound having two or more isocyanate groups or a polyfunctional oxazoline compound having two or more oxazoline groups.

  As the polyfunctional crosslinkable compound, it is preferable to use a polyfunctional isocyanate compound having two or more isocyanate groups. When a polyfunctional isocyanate is used, a three-dimensional network is formed via a urethane bond between the isocyanate group of the polyfunctional isocyanate compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound and / or the hydroxyl group of the polymer compound. In the polymer compound, an interaction due to hydrogen bonding occurs between a hydrogen bonding functional group (amide group, imide group, hydroxyl group, carboxyl group and the like) and a C═O group and an NH group contained in the urethane structure. Thereby, the low resilience of the resin composition can be improved, and appropriate fluidity is expressed in the resin composition by combining the plasticity of the polymer compound and the elasticity of the resin composition. As a result, for example, when using the resin composition as an interlayer insulating film of a multilayer flexible printed wiring board, two conflicting physical properties (fluidity and viscosity) can be achieved, so that the interlayer insulating film Excellent performance can be ensured. As the polyfunctional isocyanate compound, various isocyanate compounds having two or more isocyanate groups can be used.

  In the case where the resin composition according to the present embodiment is used as an interlayer insulating film such as a multilayer flexible wiring board, the resin composition is required to flow into the wiring part or through-hole part of the wiring board, It is required that the composition be held to some extent without flowing out of the end of the wiring board. This is because the resin composition generally flows out from the end of the wiring board when attempting to sufficiently flow into the through hole in the press process under high pressure, and the thickness of the insulating layer at the end of the wiring board It is because there exists a possibility that insulation may fall and it may become thin. Here, for example, when a polyfunctional isocyanate compound is used as the polyfunctional crosslinkable compound in the resin composition described above, the isocyanate group of the polyfunctional isocyanate compound and the hydroxyl group and / or high molecular weight of the polyfunctional hydroxyl group-containing compound are used. Due to the urethane bond formed between the hydroxyl groups of the molecular compound, the polyfunctional hydroxyl compound and / or the polymer compound and the polyfunctional isocyanate compound are bound together, and the hydrogen bond between the urethane structure and the polymer compound. Interaction occurs. This ensures the fluidity necessary for the flow of the resin composition into the opposite wiring part and the thickness of the insulating film at the end of the wiring part by combining the plasticity of the polymer compound and the elasticity of the resin composition. Therefore, it is possible to achieve both an appropriate viscosity necessary for preventing the resin composition from flowing out. As a result, the resin composition is prevented from flowing out from the end portion of the wiring board, and the resin composition is held to some extent without flowing out from the end portion of the wiring board, so that particularly good embedding can be achieved.

  Moreover, you may use a block isocyanate compound as a polyfunctional crosslinking | crosslinked compound. Here, the blocked isocyanate compound is a compound containing a blocked isocyanate group obtained by reacting a blocking agent with a polyfunctional isocyanate containing two or more isocyanate groups. As the blocked isocyanate compound, those containing two or more blocked isocyanate groups are preferred from the viewpoints of polymerization by reaction with a hydroxyl group of a polyfunctional hydroxyl group-containing compound, improvement of heat resistance by cross-linking formation, and chemical resistance. In addition, from the viewpoint of forming a plurality of crosslinks between the polyfunctional hydroxyl group-containing compound and / or the hydroxyl group of the polymer compound and the isocyanate compound, the polyfunctional crosslinkable compound is a polyfunctional isocyanate containing three or more isocyanates. It is preferable to use a compound or a blocked isocyanate.

  Examples of the isocyanate compound having two or more isocyanate groups in the molecule used in the resin composition according to the present embodiment include 1,6-hexane diisocyanate and 4,4′-diphenylmethane. Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-water Oxidized diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenyl diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene 1,4- Diisocyanate, phenylene 2,6-diisocyanate, 1,3,6-hexamethylene triisocyanate, or hexamethylene diester Isocyanate, and the like. Moreover, as a blocked isocyanate compound, the compound obtained by making a blocking agent react with the said isocyanate compound can be used. Blocking agents include alcohols, phenols, ε-caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, carbamates , Imines, sulfites and the like.

  Examples of the blocked isocyanate compound include trade names Duranate SBN-70D, TPA-B80E, TPA-B80X, 17B-60PX, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, K6000, and the like manufactured by Asahi Kasei Chemicals Corporation. Hexamethylene diisocyanate (hereinafter also referred to as “HDI”) based blocked isocyanate. Moreover, as Mitsui Chemicals Polyurethane products, trade name Takenate B-882N, trade name Takenate B-830 which is a tolylene diisocyanate block isocyanate, and 4,4'-diphenylmethane diisocyanate block isocyanate. Trade name Takenate B-815N, Takenate B-846N which is 1,3-bis (isocyanatomethyl) cyclohexane block isocyanate. In addition, trade names Coronate AP-M2503, 2515, 2507, 2513, or Millionate MS-50 manufactured by Nippon Polyurethane Industry Co., Ltd., and product numbers 7950, 7951, 7990 manufactured by Baxenden, which is an isophorone diisocyanate-based blocked isocyanate, can be used. . These blocked isocyanate compounds may be used alone or in combination of two or more.

  As the polyfunctional crosslinkable compound, it is also preferable to use a polyfunctional oxazoline compound having two or more oxazoline groups (oxazoline rings) in the molecule. In this case, the oxazoline group of the polyfunctional oxazoline compound reacts with the hydroxyl group of the polyfunctional hydroxyl group-containing compound to form an amide bond. Further, when the polymer compound has a hydroxyl group or a carboxyl group, the oxazoline group of the polyfunctional oxazoline compound reacts with the hydroxyl group or the carboxyl group to contain an amide bond and / or an amide ester (three-dimensional Cross-linking) is formed. As a result, a three-dimensional network is formed between the polymer compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound by three-dimensional crosslinking including an amide bond and / or an amide ester. The flexibility of the polyfunctional hydroxyl group-containing compound can be effectively reflected in the polymer compound by the interaction such as hydrogen bond and chemical bond with the polymer compound, and sufficient warpage reduction and excellent heat resistance can be realized.

  As the polyfunctional oxazoline compound, various polyfunctional oxazoline compounds having two or more oxazoline groups can be used. In addition, as the polyfunctional oxazoline compound, when a crosslink is formed between the polymer compound and / or the polyfunctional hydroxyl group-containing compound, the polyfunctional oxazoline compound has at least two C═O groups and / or NH groups in the crosslink. preferable.

  Specific examples of the polyfunctional oxazoline compound include 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, K-2010E, K-2020E, K-2030E, and 2,6-bis manufactured by Nippon Shokubai Co., Ltd. (4-Isopropyl-2-oxazolin-2-yl) pyridine, 2,6-bis (4-phenyl-2-oxazolin-2-yl) pyridine, 2,2′-isopropylidenebis (4-phenyl-2-) Oxazoline), 2,2′-isopropylidenebis (4-tertiarybutyl-2-oxazoline), and the like. These polyfunctional oxazoline compounds may be used alone or in combination of two or more.

  In the resin composition according to the present embodiment, the content of the polyfunctional crosslinkable compound is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polymer compound. If content of a polyfunctional crosslinking compound is 5 mass parts or more, since sufficient bridge | crosslinking can be formed between polyfunctional hydroxyl-containing compounds, the curvature at the time of hardening can be reduced. Moreover, if content of a polyfunctional crosslinking compound is 60 mass parts or less, since a high molecular compound will become a good fluidity at the time of heating-pressing, a through-hole embedding property can be improved. Furthermore, the content of the polyfunctional crosslinking compound is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polymer compound.

  In the resin composition according to the present embodiment, the molar ratio between the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound and the crosslinkable functional group contained in the polyfunctional crosslinkable compound is hydroxyl group / crosslinkable functional group = 0. It is preferable that it is 5-1. Thereby, since the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound becomes excessive with respect to the crosslinkable functional group of the polyfunctional crosslinking compound, the crosslinking bond between the multifunctional hydroxyl group-containing compound and the multifunctional crosslinking compound is reduced. Moderately formed. For this reason, the shrinkage | contraction of the polyimide accompanying hardening of a resin composition can be suppressed, and sufficient reduction of the curvature at the time of hardening and the outstanding heat resistance are realizable.

(D) Polyfunctional hydroxyl group-containing compound As the polyfunctional hydroxyl group-containing compound, various hydroxyl group-containing compounds having two or more hydroxyl groups in the molecule can be used. For example, various diols as a bifunctional hydroxyl group-containing compound containing two hydroxyl groups may be used, and various polyols containing three or more hydroxyl groups may be used. Among these, from the viewpoint of forming a plurality of crosslinks between a polyfunctional hydroxyl group-containing compound and a polyfunctional crosslinkable compound (for example, polyfunctional isocyanate or polyfunctional oxazoline compound), as the polyfunctional hydroxyl group-containing compound, It is preferable to use a polyfunctional hydroxyl group-containing compound containing three or more hydroxyl groups.

  The polyfunctional hydroxyl group-containing compound preferably contains at least one selected from both-end phenol-modified silicones, polybutadiene polyols, hydrogenated polybutadiene polyols, and polycarbonate polyols from the viewpoint of enhancing insulation. Moreover, as a polyfunctional hydroxyl-containing compound, what has an aliphatic structure is preferable. Thereby, since water resistance improves and it becomes low elasticity, curvature and insulation reliability can be improved. From the above viewpoints, among the specific examples given above, the polyfunctional hydroxyl group-containing compound is preferably a hydrogenated polybutadiene polyol or a polycarbonate polyol. In particular, from the viewpoint of reducing warpage during curing of the resin composition, the polycarbonate It is preferable to use a polyol.

  In the resin composition concerning this Embodiment, it is preferable that content of a polyfunctional hydroxyl compound is 5 mass parts-60 mass parts with respect to 100 mass parts of high molecular compounds. When the polyfunctional hydroxyl group-containing compound is 5 parts by mass or more, sufficient crosslinking can be formed with the polyfunctional crosslinkable compound, so that it is possible to reduce warpage during curing. Moreover, since the excess hydroxyl group in a resin composition reduces because a polyfunctional hydroxyl compound is 60 mass parts or less, the insulation reliability after hardening of a resin composition improves. Furthermore, the content of the polyfunctional hydroxyl group-containing compound is preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polymer compound.

  As the polyfunctional hydroxyl group-containing compound, it is preferable to use a compound having a number average molecular weight of 500 to 3,000. Here, the number average molecular weight means the number average molecular weight of styrene conversion molecular weight measured by gel permeation chromatography. If the polyfunctional hydroxyl group-containing compound has a number average molecular weight of 500 or more, the resin composition has low elasticity, and thus warpage can be reduced. Moreover, since the viscosity of a resin composition can be reduced if the number average molecular weight of a polyfunctional hydroxyl-containing compound is 3000 or less, the embedding property to the wiring part and through-hole part of a wiring board becomes favorable. Furthermore, the number average molecular weight of the polyfunctional hydroxyl group-containing compound is preferably 500 to 2000 from the viewpoint of low elasticity and viscosity reduction of the resin composition.

(E) Flame retardant In the resin composition which concerns on this Embodiment, it is preferable to contain a flame retardant. Thereby, the flame retardance of a resin composition improves. Although it does not specifically limit as a kind of flame retardant, A halogen-containing compound, a nitrogen-containing compound, a phosphorus compound, an inorganic flame retardant, etc. are mentioned. The phosphorus compound is not particularly limited as long as it is a compound containing a phosphorus atom in the molecule. Examples of phosphorus compounds include phosphate ester compounds and phosphazene compounds. One kind of these flame retardants may be used, or two or more kinds may be mixed and used. The addition amount of the flame retardant is not particularly limited and can be appropriately changed according to the type of the flame retardant used.

  Moreover, in the resin composition which concerns on this Embodiment, it is preferable as a phosphorus compound that a phosphate ester compound and / or a phosphazene compound are included. Thereby, especially the flame retardance of a resin composition improves.

  In the resin composition according to the present embodiment, a cured product (cured film) can be obtained by heating or drying at a predetermined temperature. This hardened | cured material can be used as a resin film, for example by apply | coating the resin composition which concerns on this Embodiment on a base material, and drying. The resin film can be suitably used, for example, as an interlayer insulating film / wiring protective film of a flexible printed board.

  The resin film according to the present embodiment includes a base material and a resin composition provided on the base material. In this case, copper foil, a carrier film, etc. can be used as a base material. Moreover, in the resin film which concerns on this Embodiment, it is preferable to comprise the carrier film, the resin composition provided on this carrier film, and the cover film provided on this resin composition. Thereby, the surface of the resin film can be protected.

  In the resin film according to the present embodiment, a copper foil is used as the base material, and the resin composition can be provided on the copper foil. Thus, it can use suitably as interlayer insulation films, such as a multilayer flexible wiring board, by providing and drying a resin composition on copper foil.

  The wiring board according to the present embodiment includes a base material having wiring and the resin composition provided so as to cover the wiring. Thus, by providing the resin composition so as to cover the wiring, it can be suitably used as a protective film for wiring patterns of various wiring boards such as a flexible printed wiring board.

  In the resin composition according to the present embodiment, when a low molecular weight polyfunctional hydroxyl group-containing compound and a polyfunctional crosslinkable compound that are well compatible with the polymer compound are included, the viscosity of the resin composition is reduced. Fluidity is improved. As a result, in the manufacturing process of the flexible printed wiring board, the through hole provided in the insulating substrate of the wiring board and the embedding property in the wiring pattern are improved, so it is suitable as an interlayer insulating film for multilayer flexible wiring boards and a wiring protective film. Can be used.

  Here, an outline of the manufacturing process of the wiring board according to the present embodiment will be described with reference to FIG. As shown in FIG. 1A, a double-sided flexible substrate 10 is used for manufacturing a multilayer flexible wiring board. The double-sided flexible substrate 10 includes an insulating substrate 11 and copper foils 12 a and 12 b provided on both main surfaces of the insulating substrate 11. First, after laminating a dry film on the copper foils 12 and 12b, a part of the copper foils 12a and 12b is removed by exposure / development of the dry film and etching of the copper foils 12a and 12b. Hole 13 is formed. Next, copper plating 14 is formed on the surface of the through hole 13 to electrically connect the copper foils 12a and 12b on both sides (see FIG. 1B).

  Next, as shown in FIG. 1C, the copper foil 12b in the region to be the flexible portion 16 is removed by etching. Next, the resin composition according to the present embodiment is filled in the through holes 13 and insulated. Here, as described above, in the resin composition according to the present embodiment, a polyfunctional isocyanate compound and / or a polyfunctional oxazoline compound is used as the polyfunctional crosslinkable compound, and a hydroxyl group and / or a carboxyl group is formed as the polymer compound. When the polymer compound is used, appropriate fluidity and viscosity are expressed in the resin composition. Thereby, even if it is a case where the minute through hole 13 is provided, it becomes possible to fill the resin composition in the through hole 13.

  Next, as shown to FIG. 1D, the copper foil 15a and the laminated body 15 provided with the protective layer 15b obtained by apply | coating the resin composition which concerns on this Embodiment on this copper foil 15a are made into copper foil. Laminate on 12a and 12b, respectively. Here, in the resin composition according to the present embodiment, when polyimide is used as the polymer compound, imidization after coating becomes unnecessary. Thereby, the post-curing process after lamination | stacking is not required but lamination | stacking by a quick press is attained.

  Next, as shown in FIG. 1E, after the copper foil 15a and the protective layer 15b are removed by etching or the like, the copper plating 14 is applied to the copper foil 15a as the external conductive layer and the copper foils 12a and 12b as the internal conductive layers. And electrically connect. Next, the copper foil 15a is patterned by a subtractive method or the like to form a wiring pattern. Finally, as shown in FIG. 1F, the protective film 17 is formed by applying the resin composition according to the present embodiment on the copper foil 15a having the wiring pattern processed. Here, as described above, in the resin composition according to the present embodiment, a polyfunctional isocyanate compound and / or a polyfunctional oxazoline compound is used as the polyfunctional crosslinkable compound, and a hydroxyl group and / or a carboxyl group is formed as the polymer compound. When the polymer compound is used, appropriate fluidity and viscosity are expressed in the resin composition. Thereby, even when a fine wiring pattern is formed, the resin composition is filled between the wiring patterns, and insulation protection can be performed.

(F) Other compounds The resin composition according to the present embodiment may contain other compounds as long as the performance is not adversely affected. Examples of other compounds include thermosetting resins used for improving the toughness, solvent resistance, and heat resistance (thermal stability) of the fired film, and compounds having reactivity with polyimide. Moreover, the heterocyclic compound used for adhesiveness improvement, the pigment, dye, etc. which are used for coloring of a film are mentioned.

  The heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom. Hetero atoms include oxygen, sulfur, nitrogen, and phosphorus. Examples of the hetero atom include N-alkyl group substitution such as 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, imidazole such as 2-phenylimidazole, and 1,2-dimethylimidazole. Aromatic group-containing imidazole such as imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, cyano group-containing imidazole such as 1-cyanoethyl-2-phenylimidazole, imidazole compounds such as silicon-containing imidazole such as imidazolesilane, 5-methylbenzotriazole, 1- (1 ' 2'-di-carboxyethyl benzotriazole), triazole compounds such as 1- (2-ethyl-F carboxymethyl aminomethyl benzotriazole), 2-methyl-5-phenyl-benzoxazole such as oxazole compounds.

  Examples carried out to clarify the effects of the present invention will be described below. In addition, this invention is not limited at all by the following examples.

<Reagent>
In the examples and comparative examples, the reagents used are shown below.

(A) Polymer compound Tetracarboxylic acid dianhydride component: BPDA (manufactured by Mitsui Chemicals), ethylene glycol bis (trimellitic acid monoester acid anhydride) (hereinafter simply referred to as “TMEG”), Shin Nippon Rika ), APB (trade name: APB-N, manufactured by Mitsui Chemicals), BAPP (manufactured by Wakayama Seika Kogyo Co., Ltd.), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (New Japan) (Rika Co., Ltd., hereinafter simply referred to as “DSDA”)
Diamine component: Jeffamine (trade name: Jeffamine XTJ-542 (hereinafter simply referred to as “XJT-542”), manufactured by Huntsman Co., Ltd., in the above general formula (2), R ¹ , R ⁴ , R ⁷ , R ⁸ , R ¹¹ , R ¹³ = H, R ² , R ⁵ , R ¹⁰ , R ¹⁵ = CH ₃ , R ³ , R ⁶ , R ¹² , R ¹⁴ = C ₂ H ₂ , R ⁹ = C ₄ H ₆ , m + n + p = 15), polyetheramine (trade name: polyetheramine D-400 (hereinafter simply referred to as “D-400”), manufactured by BASF, in the above general formula (2), R ¹ , R ⁴ , R ⁷ , R ¹⁰ , R ¹³ = H, R ² , R ⁵ , R ⁸ , R ¹¹ , R ¹⁵ = CH ₃ , R ³ , R ⁶ , R ⁹ , R ¹² , R ¹⁴ = C ₂ H ₂ , m + n + p = 6.1)

(B) Antioxidant Antioxidant having a phenol structure: IRGANOX245 (manufactured by BASF), IRGANOX1010 (manufactured by BASF)
Phosphorus antioxidant: ADK STAB PEP-36 (manufactured by ADEKA)

(C) Polyfunctional crosslinkable compound Polyfunctional isocyanate compound: Block isocyanate (trade name: Duranate SBN-70D (hereinafter simply referred to as “SBN-70D”), manufactured by Asahi Kasei Chemicals), isocyanate (trade name: Duranate TPA) -100 (hereinafter simply referred to as “TPA-100”), manufactured by Asahi Kasei Chemicals)
Polyfunctional oxazoline compound: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene (trade name: 1,3-PBO (hereinafter simply referred to as “1,3-PBO”) Mikuni Pharmaceutical Co., Ltd. Made)

(D) Polyfunctional hydroxyl group-containing compound Bifunctional hydroxyl group-containing oil-containing compound: Polycarbonate diol (trade name: DURANOL T5651 (number average molecular weight Mn: 1000, hereinafter simply referred to as “T5651”), manufactured by Asahi Kasei Chemicals), (trade name) : Duranol T5650E (number average molecular weight Mn: 500, hereinafter simply referred to as “T5650E”), manufactured by Asahi Kasei Chemicals)

(E) Flame retardant:
Phosphazene compound (trade name: FP-300, manufactured by Fushimi Pharmaceutical)

  Others: Toluene (manufactured by Wako Pure Chemical Industries, Ltd., for organic synthesis), γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.)

<Weight average molecular weight measurement>
The weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) was used as a solvent, and 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement). 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)
A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

<Preparation of cured film>
The resin composition is applied to the substrate with a bar coater, leveled at room temperature for 5 to 10 minutes, and heated and dried in a hot air oven at 140 ° C for 12 minutes, then 250 ° C for 5 minutes to prepare a sample. did. As the substrate, copper foil (F2-WS, manufactured by Furukawa Electric Co., Ltd.) was used. The resin composition was applied to one side of the substrate. The film thickness was adjusted to 30 μm.

<Lamination conditions>
Lamination was performed using a vacuum press (made by Kitagawa Seiki). The press temperature was 180 ° C., the press pressure was 0.5 MPa, and the press time was 120 seconds.

<Insulation reliability (IM resistance) evaluation>
The insulation reliability evaluation was performed as follows. After laminating the cured film on the comb substrate having a line and space of 20 μm / 20 μm under the above laminating conditions, the copper foil portion of the cured film is removed with an etching solution (ferric chloride), and a migration tester is applied to the film. The cable was soldered and an insulation reliability test was performed under the following conditions.
Insulation degradation evaluation system: SIR-12 (Enomoto Kasei Co., Ltd.)
IM chamber: EHS-211M (Espec Corp.)
Temperature: 85 ° C
Humidity: 85%
Applied voltage: 20V
Application time: 1000 hours

The standard of insulation reliability evaluation is shown below.
Insulation resistance: 1.0 × a × less than 10 ⁶ Omega, less than ^{1.0 × 10 6 Ω~1.0 × 10 8} Ω △ and then, was ○ over 1.0 × 10 ⁸ Ω.
Appearance (swelling and discoloration): The comb substrate after the insulation reliability test was observed with an optical microscope (ECLIPS LV100, manufactured by Nikon Corp.) under the condition of 100 times bright field. The case where blistering and discoloration of the insulating film was observed was rated as x, the case where only blistering of the insulating film was observed was marked as Δ, and the case where blistering and discoloration was not observed was marked as ◯.

<Evaluation of warpage>
The warpage was evaluated by lifting from the center of the sample at the four corners of the sample. The cured film was laminated on a polyimide film (Kapton (registered trademark) 25 μm) under the above laminating conditions, then cut to 5 cm × 5 cm, and sampled at four corners with respect to the center of the sample in an environment of 23 ° C. and humidity of 50%. Was measured as the warp. Those having a warp of 10 mm or less were evaluated as “good”, those having a warp of 5 mm or less were evaluated as “good”, も の were determined as 15 mm or less, and those exceeding 15 mm were evaluated as “poor”.

<Evaluation of through-hole embedding>
The through-hole embedding property was evaluated with an optical microscope after embedding, cutting, and polishing a four-layer wiring board in which the cured film was produced under the above-described lamination conditions. A through hole having a diameter of 100 μm was used. The case where the resin composition was embedded in the through hole without a gap was marked with ◯, and the case where a gap was observed in the through hole was marked with x.

<Evaluation of spill prevention>
The outflow prevention property evaluated visually the protrusion of the resin composition of a sample edge part, after laminating | stacking the said cured film on copper foil F2-WS (12 micrometers) on the said lamination conditions. The case where the protrusion of the resin composition was 1 mm or less was evaluated as ◯, the case where it was 1 mm or more and less than 2 mm was evaluated as Δ, and the case where it was 2 mm or more was evaluated as ×.

<Evaluation of solder resistance>
Solder resistance was evaluated by laminating the cured film on copper foil F2-WS (12 μm) under the above laminating conditions, cutting it to 3 cm × 3 cm, and immersing the sample in a solder bath at 260 ° C. for 60 seconds. The appearance is inspected visually to confirm the presence or absence of changes such as deformation and dissolution traces. The time from the immersion until the appearance of the change is 60 seconds or longer is marked as ◯, and 20 seconds to 60 seconds. The case where it was less than Δ was marked with Δ, and the case where it was less than 20 seconds was marked with ×.

<Polymer compound (1)>
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (161.0 g), toluene (45.0 g), XTJ-542 (23.5 g), BPDA (24.0 g), BAPP (21.5 g) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. Toluene, which is an azeotropic solvent, was removed to obtain a solution of the polymer compound (1). The weight average molecular weight of the obtained polymer compound (1) is shown in Table 1 below.

<Polymer compound (2)>
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (200.0 g), toluene (45.0 g), XTJ-542 (24.5 g), BPDA (24.1 g), BAPP (23.5 g) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. Toluene, which is an azeotropic solvent, was removed to obtain a solution of the polymer compound (2). The weight average molecular weight of the obtained polymer compound (2) is shown in Table 1 below.

<Polymer compound (3)>
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (106.0 g), toluene (45.0 g), D-400 (20.2 g), BPDA (24.0 g), BAPP (12.8 g) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. Toluene, which is an azeotropic solvent, was removed to obtain a solution of the polymer compound (3). The weight average molecular weight of the obtained polymer compound (3) is shown in Table 1 below.

<Polymer compound (4)>
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (170.0 g), toluene (45.0 g), XTJ-542 (23.5 g), BPDA (24.0 g), 6FAP (20.0 g) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. Toluene, which is an azeotropic solvent, was removed to obtain a solution of the polymer compound (4). The weight average molecular weight of the obtained polymer compound (4) is shown in Table 1 below.

<Polymer compound (5)>
Under a nitrogen atmosphere, in a separable flask equipped with a Dean Stark apparatus and a refluxer, γ-butyrolactone (170.0 g), toluene (45.0 g), D-400 (17.0 g), BPDA (24.0 g), 6FAP (14.0 g) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. Toluene, which is an azeotropic solvent, was removed to obtain a solution of the polymer compound (5). The weight average molecular weight of the obtained polymer compound (5) is shown in Table 1 below.

<Polymer compound (6)>
Under a nitrogen atmosphere, in a separable flask equipped with a Dean Stark apparatus and a refluxer, γ-butyrolactone (170.0 g), toluene (45.0 g), XTJ-542 (20.0 g), TMEG (30.0 g), APB (14.0 g) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. Toluene, which is an azeotropic solvent, was removed to obtain a solution of the polymer compound (6). The weight average molecular weight of the obtained polymer compound (6) is shown in Table 1 below.

<Polymer compound (7)>
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (170.0 g), toluene (45.0 g), XTJ-542 (18.0 g), DSDA (26.4 g), APB (12.0 g) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. Toluene, which is an azeotropic solvent, was removed to obtain a solution of the polymer compound (7). The weight average molecular weight of the obtained polymer compound (7) is shown in Table 1 below.

[Example 1]
IRGANOX245 (1 part by mass) was mixed with 100 parts by mass of the polymer compound (1) to prepare a resin composition. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 2]
IRGANOX245 (9 mass parts) was mixed with respect to 100 mass parts of high molecular compounds (2), and the resin composition was prepared. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 3]
IRGANOX 1010 (3 parts by mass) was mixed with 100 parts by mass of the polymer compound (3) to prepare a resin composition. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 4]
IRGANOX245 (4 mass parts) and SBN-70D (10 mass parts) were mixed with respect to 100 mass parts of high molecular compounds (4), and the resin composition was prepared. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 5]
IRGANOX245 (2 parts by mass) and 1,3-PBO (10 parts by mass) were mixed with 100 parts by mass of the polymer compound (5) to prepare a resin composition. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 6]
IRGANOX245 (5 mass parts), SBN-70D (8 mass parts), and T5651 (8 mass parts) were mixed with respect to 100 mass parts of the high molecular compound (1), and the resin composition was prepared. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 7]
IRGANOX245 (13 mass parts), SBN-70D (8 mass parts), and T5651 (8 mass parts) were mixed with respect to 100 mass parts of the high molecular compound (1), and the resin composition was prepared. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 8]
PEP-36 (10 parts by mass) was mixed with 100 parts by mass of the polymer compound (1) to prepare a resin composition. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 9]
IRGANOX245 (5 mass parts), TPA-100 (4 mass parts), and T5651 (8 mass parts) were mixed with respect to 100 mass parts of high molecular compounds (1), and the resin composition was prepared. The obtained resin composition was made into a dry film by the method described above to obtain a cured film. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 10]
IRGANOX245 (5 mass parts), TPA-100 (4 mass parts), and T5650E (5 mass parts) were mixed with respect to 100 mass parts of high molecular compounds (1), and the resin composition was prepared. A cured film was obtained from the obtained resin composition by the method described above. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Example 11]
IRGANOX245 (5 parts by mass), TPA-100 (4 parts by mass), T5650E (5 parts by mass), and FP-300 (35 parts by mass) are mixed with 100 parts by mass of the polymer compound (1) to obtain a resin composition. A product was prepared. A cured film was obtained from the obtained resin composition by the method described above. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Comparative Example 1]
A cured film was obtained from the polymer compound (1) by the method described above. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Comparative Example 2]
IRGANOX245 (2 mass parts) was mixed with respect to 100 mass parts of high molecular compounds (6), and the resin composition was prepared. A cured film was obtained from the obtained resin composition by the method described above. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. The results are shown in Table 2 and Table 3 below.

[Comparative Example 3]
IRGANOX 1010 (2 parts by mass) was mixed with 100 parts by mass of the polymer compound (7) to prepare a resin composition. A cured film was obtained from the obtained resin composition by the method described above. The cured film was evaluated for insulation reliability (IM resistance), warpage, through-hole embedding, outflow prevention, and solder resistance by the above-described methods. Warpage, insulation reliability (IM resistance), embedding property, outflow prevention property, and solder resistance were evaluated. The results are shown in Table 2 and Table 3 below.

  From the results shown in Table 3, in the resin compositions according to Examples 1 to 11 containing the polymer compound having no ester structure and sulfonic acid group in the molecule and the antioxidant, Comparative Example 1 From the results, it can be seen that, compared with the resin composition according to Comparative Example 3, it is possible to reduce warpage during curing and to have good insulation reliability.

  On the other hand, in the resin composition not containing the antioxidant, the insulation resistance value was low and appearance abnormality occurred (see Comparative Example 1). This is presumably because the polymer was subjected to thermal oxidation at the time of forming a cured film and laminating, and the polymer was subjected to thermal oxidation, the molecular weight was lowered, the insulation resistance value was lowered, and the appearance was deteriorated. Moreover, also in the resin composition containing an ester group, the insulation resistance value decreased and the appearance abnormality occurred (Comparative Example 2). This is thought to have occurred because the ester group has undergone hydrolysis. Furthermore, the resin composition containing a sulfonyl group also exhibited a decrease in insulation resistance and abnormal appearance (Comparative Example 3). As a result, the DSDA which is a raw material of the polymer compound (7) contains a sulfonic acid component (a sulfonic acid or a byproduct containing a sulfonic acid group), and the sulfonic acid component is mixed into the resin composition. It is thought that the resistance value deteriorated.

  The present invention is particularly suitably used as a surface protective film for semiconductor elements, an interlayer insulating film, a bonding sheet, a semiconductor package substrate, a protective layer for circuit boards, a protective insulating film for printed wiring boards, and a protective insulating film for flexible printed boards. be able to.

DESCRIPTION OF SYMBOLS 10 ... Double-sided flexible substrate 11 ... Insulating substrate 12a, 12b ... Copper foil 13 ... Through-hole 14 ... Copper plating 15 ... Laminated body 15a ... Copper foil 15b ... Protective layer 16 ... Flexible part 17 ... Protective film

Claims (17)

  (A) a polymer compound obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component having a polyether structure and at least two terminal amine structures, and (B) an antioxidant, The polymer composition has no ester structure and no sulfonyl group in the molecule.   (C) a polyfunctional crosslinkable compound having two or more crosslinkable functional groups that react with a hydroxyl group and / or a carboxyl group to form a crosslink, and the polymer compound has a hydroxyl group and / or a carboxyl group The resin composition according to claim 1.   3. The polymer compound and / or the polyfunctional crosslinkable compound is trifunctional or more, and can form a three-dimensional crosslink between the polymer compound and the polyfunctional crosslinkable compound. The resin composition as described.   (C) a polyfunctional crosslinkable compound having two or more crosslinkable functional groups that react with a hydroxyl group and / or a carboxyl group to form a crosslink; and (D) a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups; The resin composition according to claim 1, comprising:   The polyfunctional crosslinkable compound and / or the polyfunctional hydroxyl group-containing compound is trifunctional or more, and a three-dimensional crosslink can be formed between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound. The resin composition according to claim 4.   The resin composition according to any one of claims 2 to 5, comprising a polyfunctional isocyanate compound having two or more isocyanate groups as the polyfunctional crosslinkable compound.   The resin composition according to any one of claims 2 to 5, comprising a polyfunctional oxazoline compound having two or more oxazoline groups as the polyfunctional crosslinkable compound.   The resin composition according to any one of claims 2 to 7, wherein the polyfunctional hydroxyl group-containing compound is a polycarbonate polyol. The resin composition according to any one of claims 1 to 8, wherein the polymer compound has a repeating structure represented by the following general formula (1).

(In formula (1), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹³ , and R ¹⁵ are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, R ³ , R ⁶ , R ⁹ , R ¹² , and R ¹⁴ each independently represents a tetravalent organic group having 1 to 20 carbon atoms; , N and p each independently represents an integer of 0 to 100. R ¹⁶ represents a tetravalent organic group.)   The resin composition according to any one of claims 1 to 8, wherein the polymer compound has a weight average molecular weight of 20,000 to 200,000.   The resin composition according to any one of claims 1 to 10, comprising 0.1 to 10 parts by mass of the antioxidant with respect to 100 parts by mass of the polymer compound.   The resin composition according to any one of claims 1 to 11, wherein the antioxidant is an antioxidant having a hindered phenol structure.   A resin film comprising: a base material; and the resin composition according to any one of claims 1 to 12 provided on the base material.   The resin film according to claim 13, wherein the substrate is a carrier film.   The resin film according to claim 13 or 14, further comprising a cover film provided on the resin composition.   The resin film according to claim 13, wherein the base material is a copper foil.   A wiring board comprising: a base material having wiring; and the resin composition according to any one of claims 1 to 12 provided so as to cover the wiring.

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