WO2012098734A1

WO2012098734A1 - Resin composition, cured object, resin film, and wiring board

Info

Publication number: WO2012098734A1
Application number: PCT/JP2011/071494
Authority: WO
Inventors: 足立　弘明; 透日下部; 洋朗佐々木; 山本　正樹; 康史飯塚; 華菜子水村; 下田　浩一朗
Original assignee: 旭化成イーマテリアルズ株式会社
Priority date: 2011-01-18
Filing date: 2011-09-21
Publication date: 2012-07-26
Also published as: CN103270070B; JP5820825B2; JPWO2012098734A1; CN103270070A; KR101516103B1; KR20130087589A; TWI498380B; TW201237101A

Abstract

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

Description

Resin composition, cured product, resin film and wiring board

The present invention relates to a resin composition useful as a material for a surface protective film of a semiconductor element, an interlayer insulating film, a semiconductor package substrate, a bonding sheet, and a protective insulating film for a printed wiring board, a cured product using the resin composition, and a resin composition The present invention relates to a resin film using, and a wiring board using them.

As a material for the surface protection film of semiconductor elements, interlayer insulation films, and protection insulation films for printed wiring boards, polyimide resin compositions having excellent heat resistance are being used. In particular, 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 heat resistance. A polyimide-based ink composed of an ester-terminated oligomer and an amine-terminated oligomer has been proposed as a polyimide-based resin composition that has excellent heat resistance and can reduce warping after curing (see, for example, Patent Document 1).

The polyimide-based ink described in Patent Document 1 is used after being applied onto a flexible wiring circuit and then heat-treated at a temperature of 250 ° C. or higher to be imidized. In this imidization process, the polyimide resin to be formed contracts due to the stress caused by the ring closure reaction accompanying solvent removal and oligomer imidization. For this reason, suppression of curvature is not necessarily sufficient, and a problem also arises in workability. Further, when copper foil is used as the circuit material, there is a problem that the carboxyl group and the wiring material react with each other by heat treatment at 250 ° C. or more, and the wiring material is oxidized.

Also, polyimide precursors that can be imidized at low temperatures and can reduce warping after curing have been developed. Examples of such polyimide precursors include non-silicone polyimide precursors using alkyl ether diamines (for example, see Patent Document 2), and silicone-based polyimide precursors using diaminosiloxane as a diamine component (for example, patents). Reference 3 and Patent Document 4).

JP-A-2-145664 JP 2006-321924 A JP-A-57-143328 JP 58-13631 A

However, the polyimide precursor described in Patent Document 2 has a polyamic acid structure derived from an alkyl ether diamine and a polyimide structure derived from an aromatic diamine as structural units. For this reason, when it uses for the insulating material of a flexible printed wiring board as a polyimide-type resin composition, the polyimide site | part originating in aromatic diamine shrink | contracts and there exists a problem which cannot fully suppress the curvature at the time of hardening.

Further, since the polyimide precursors described in Patent Document 3 and Patent Document 4 are silicone-based polyimide precursors, they are applied to a circuit board as a polyimide-based resin composition and imidized to form a circuit protective film. In the case of forming, the silicone part segregates on the surface in the subsequent prepreg or bonding process, and the surface of the protective film may have low surface tension and high water repellency, which may repel the adhesive component. For this reason, the adhesive force between a protective film and an adhesive sheet is insufficient, and there is a problem that sufficient performance as a protective film is not necessarily obtained.

The present invention has been made in view of the above points, and can reduce warping during curing, has excellent heat resistance, and is a surface protective film for semiconductor elements, an interlayer insulating film, a protective insulating film for printed wiring boards, and an interlayer insulating film. 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.

The resin composition of the present invention comprises (A) a polymer compound, (B) a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups, and (C) the polymer compound and / or the polyfunctional hydroxyl group-containing compound. A polyfunctional crosslinkable compound having two or more crosslinkable functional groups that form a crosslink between them, wherein the polyfunctional crosslinkable compound is the polymer compound and / or the polyfunctional hydroxyl group-containing compound. It is characterized in that a three-dimensional bridge can be formed between them.

In the resin composition of the present invention, it is preferable that the polymer compound has an imide group and / or an amide group, and the three-dimensional crosslinking includes a C═O group and / or an NH group.

In the resin composition of the present invention, the polyfunctional hydroxyl group-containing compound and / or the polyfunctional crosslinkable compound is preferably trifunctional or more.

In the resin composition of the present invention, the polymer compound preferably has a hydroxyl group and / or a carboxyl group.

In the resin composition of the present invention, it is preferable that the polyfunctional hydroxyl group-containing compound includes at least one selected from both-end phenol-modified silicone, polybutadiene polyol, hydrogenated polybutadiene polyol, and polycarbonate polyol.

In the resin composition of the present invention, the polyfunctional hydroxyl group-containing compound preferably has an aliphatic structure.

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

The resin composition of the present invention preferably contains a polyfunctional isocyanate compound having two or more isocyanate groups as the polyfunctional crosslinkable compound.

In the resin composition of the present invention, the polyfunctional crosslinkable compound preferably contains two or more blocked isocyanate groups.

In the resin composition of the present invention, the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the crosslinkable functional group contained in the polyfunctional crosslinkable compound is hydroxyl group / crosslinkable functional group = 0.5. Is preferably .about.1.

In the resin composition of the present invention, the content of the polyfunctional hydroxyl group-containing compound is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polymer compound.

In the resin composition of the present invention, 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.

In the resin composition of the present invention, the polyfunctional hydroxyl group-containing compound preferably has a number average molecular weight of 500 to 3,000.

In the resin composition of this invention, it is preferable that the said high molecular compound has a repeating structure represented by following General formula (1).

(In Formula (1), Y ₁ represents a divalent organic group, Z ₁ represents a tetravalent organic group, and a represents an integer of 1 to 50.)

In the resin composition of the present invention, the polymer compound is preferably polyimide.

In the resin composition of this invention, it is preferable that the said high molecular compound has a repeating structure represented by following General formula (2).

(In formula (2), Z ₁ and Z ₂ represent a tetravalent organic group, and Y ₁ , Y ₂ , Y ₃ , Y ₄ , and Y ₅ are each independently 1 to 5 carbon atoms. And may be branched. B, c and d each independently represents an integer of 1 to 50.)

In the resin composition of the present invention, the polymer compound may have a polyimide structure represented by the following general formula (3) and a polyamic acid structure represented by the following general formula (4) as repeating structural units, respectively. preferable.

(In Formula (3) and Formula (4), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently a hydrogen atom. Alternatively, it represents a monovalent organic group having 1 to 20 carbon atoms, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ are each independently a tetravalent organic group having 1 to 20 carbon atoms. M, n, and p each independently represents an integer of 0 to 100. R ₁₆ represents a tetravalent organic group, and R ₁₇ represents a divalent group having 1 to 90 carbon atoms. Represents an organic group of

In the resin composition of this invention, it is preferable that the diamine represented by the following general formula (5) is included as a diamine component which comprises the polyimide represented by the said General formula (3).

(In formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ 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 ₁₅ each independently represents a tetravalent organic group having 1 to 20 carbon atoms; , N and p are each independently an integer of 0 or more and 30 or less and satisfy 1 ≦ (m + n + p) ≦ 30.)

In the resin composition of the present invention, the polymer compound preferably has a structure represented by the following general formula (6) as a repeating unit.

(In formula (6), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ 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 ₁₅ represent a tetravalent organic group having 1 to 20 carbon atoms, m, n, p Each independently represents an integer of 0 to 30. R ₁₆ represents a tetravalent organic group, R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms, A, B, C represents mol% of each unit and satisfies 0.10 ≦ (A + B) / (A + B + C) ≦ 0.85.

In the resin composition of the present invention, the polymer compound preferably has a polyimide structure represented by the following general formula (7) and a polyamic acid structure represented by the following general formula (8) as structural units.

(In Formula (7) and Formula (8), Z ₃ and Z ₄ are tetravalent organic groups derived from tetracarboxylic dianhydride represented by the following General Formula (9), and are the same as each other. R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, R ₁₉ is a monovalent organic group having 1 to 30 carbon atoms, and e is 1 or more and 20 Represents the following integers.)

The resin composition of the present invention preferably contains (D) a (meth) acrylate compound having two or more unsaturated groups capable of photopolymerization and (E) a photopolymerization initiator.

In the resin composition of the present invention, the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds preferably includes a (meth) acrylate compound having three or more double bonds.

In the resin composition of this invention, it is preferable that the compound represented by following General formula (10) is included as a (meth) acrylate compound which has three or more of the said double bonds.

(In the formula (10), R ₂₀ represents a hydrogen atom or a methyl group, and a plurality of E's each independently represents an alkylene group having 2 to 5 carbon atoms, which may be the same or different. f is an integer of 1 to 10.)

In the resin composition of the present invention, the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is a (meth) acrylate compound having two double bonds and three double bonds. It is preferable to contain the (meth) acrylate compound having the above.

The resin composition of the present invention preferably contains (F) a phosphorus compound.

In the resin composition of the present invention, it is preferable that the phosphorus compound includes a phosphate ester compound and / or a phosphazene compound.

The resin composition of the present invention has an interlayer insulation resistance of 10 ⁹ Ω or more in an insulation reliability test at a temperature of 85 ° C., a humidity of 85%, and 1000 hours, and a viscosity at 120 ° C. to 220 ° C. of 5000 Pa · S to 100000 Pa · S. And having an elastic region with an elongation of less than 20% and a plastic region with an elongation of 50% or more, and the film thickness of the interlayer insulating layer is 40 μm or less.

The cured product of the present invention is obtained by heating the resin composition at 100 ° C. to 130 ° C. for 5 minutes to 60 minutes and then heating at 160 ° C. to 200 ° C. for 15 minutes to 60 minutes. .

The resin film of the present invention includes 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.

The resin film of the present invention preferably includes a cover film provided on the resin composition.

In the resin film of the present invention, the base material is preferably a copper foil.

The wiring board of the present invention is characterized by comprising a base material having wiring and the resin composition provided so as to cover the wiring.

According to the present invention, warpage during curing can be reduced, heat resistance is excellent, and it can be suitably used as a material for a surface protection film of a semiconductor element, an interlayer insulating film, a protective insulating film for a printed wiring board, an interlayer insulating film, and the like. 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.

In recent years, with the increase in functionality and weight of electronic devices such as mobile phones, the flexible printed circuit boards used in various electronic devices have been improved in functionality such as thinning and component mounting. Epoxy resins and polyimide resins are used in the manufacturing process of flexible printed circuit boards, but when using an epoxy resin as a protective film, the high insulation reliability required for thinning the flexible printed circuit board , Flexibility, low resilience, and flame retardancy are not always sufficiently obtained. Moreover, since epoxy resin has reactivity, it lacks storage stability. In addition, even when a conventional polyimide resin is used, a polyimide resin that can realize a reduction in warpage and heat resistance is expensive, and a resin composition that has a good reduction in warpage and heat resistance of a cured product accompanying imidization. Is desired.

The present inventors paid attention to a polyfunctional crosslinkable compound capable of forming a three-dimensional crosslink with a polymer compound or a polyfunctional hydroxyl group-containing compound. And the present inventors heated the resin composition containing a polymer compound and / or a polyfunctional hydroxyl group-containing compound and a polyfunctional crosslinkable compound, thereby producing a polyfunctional crosslinkable compound and a polyfunctional hydroxyl group-containing compound. The idea was to form a three-dimensional network by three-dimensional crosslinking formed between the two. Furthermore, the present inventors have found that this three-dimensional network can reduce warping during curing and can realize a resin composition having excellent heat resistance, and have completed the present invention.

That is, the resin composition according to the present invention includes (A) a polymer compound, (B) a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups, and (C) a polymer compound and / or a polyfunctional hydroxyl group-containing compound. A polyfunctional crosslinkable compound having two or more crosslinkable functional groups that form a crosslink between the polyfunctional crosslinkable compound and the polymer compound and / or the polyfunctional hydroxyl group-containing compound. A three-dimensional bridge can be formed.

In this resin composition, three-dimensional crosslinking is formed between the crosslinking functional group of the polyfunctional crosslinking compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound by heating, and a three-dimensional network is formed by this three-dimensional crosslinking. Is done. Thereby, while shrinkage | contraction of the high molecular compound at the time of hardening of a resin composition can be suppressed, the compatibility between a high molecular compound, a polyfunctional hydroxyl-containing compound, and a polyfunctional crosslinkable compound improves. As a result, it is possible to reduce warping during curing, excellent heat resistance, and a resin composition that can be suitably used as a material for semiconductor device surface protective films, interlayer insulating films, protective insulating films for printed wiring boards, interlayer insulating films, etc. Can be realized.

In the resin composition according to the present invention, the polymer compound has an imide group and / or an amide group, and the three-dimensional crosslinking formed between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is C═O. It preferably contains groups and / or NH groups. With this configuration, an interaction mainly including hydrogen bonding occurs between the C═O group and / or NH group included in the three-dimensional crosslinking and the imide group and / or amide group of the polymer compound. The compatibility between the compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is further improved. Thereby, the curvature at the time of hardening can be reduced more and heat resistance improves further.

In the resin composition according to the present invention, the polymer compound, the polyfunctional hydroxyl group-containing compound, and the polyfunctional crosslinkable compound include a polymer compound and / or a polyfunctional hydroxyl group-containing compound and a polyfunctional crosslinkable compound by heating or the like. Various compounds can be used in combination as long as they form a three-dimensional bridge between them as long as the effects of the present invention are achieved. Hereinafter, embodiments of the resin composition according to the present invention will be described in detail.

(First aspect)
In the resin composition according to the first aspect of the present invention, the polyfunctional hydroxyl group-containing compound and / or the polyfunctional crosslinkable compound is trifunctional or more. Thus, if at least one of the polyfunctional hydroxyl group-containing compound or the polyfunctional crosslinkable compound is trifunctional or more, a plurality of hydroxyl groups of the polyfunctional hydroxyl group containing compound and a plurality of crosslinkable functional groups of the polyfunctional crosslinkable compound (for example, , An isocyanate group, an oxazoline group) to form a three-dimensional network including a plurality of C═O groups and / or NH groups, thereby forming a three-dimensional network. In this case, shrinkage of the polymer compound can be suppressed by a three-dimensional network between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound formed without using the polymer compound, and sufficient warpage can be reduced. And excellent heat resistance is exhibited.

In the resin composition according to the first aspect of the present invention, the shrinkage of the polymer compound is suppressed by the three-dimensional network formed between the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound. The effects of the present invention can be achieved without being limited by the molecular structure of the polymer compound. For this reason, for example, even when an inexpensive polymer compound having no complicated molecular structure is used, warpage during curing of the resin composition can be reduced, and excellent heat resistance is exhibited.

(Second aspect)
In the resin composition according to the second aspect of the present invention, the polymer compound has a hydroxyl group and / or a carboxyl group. As described above, when the polymer compound has one of a hydroxyl group and a carboxyl group, the hydroxyl group and / or carboxyl group of the polymer compound and the crosslinkable functional group of the polyfunctional crosslinkable compound (for example, isocyanate group, oxazoline). Crosslinks are also formed between these groups. As a result, a three-dimensional network is formed between the polymer compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound via the polymer compound. The compatibility of the functional compound is improved, and the shrinkage of the polymer compound can be further suppressed. In particular, the warpage during curing of the resin composition can be reduced, and excellent heat resistance is exhibited.

In the resin composition according to the second aspect of the present invention, three-dimensional crosslinking is formed via the polymer compound, so that at least one of the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinking compound is not trifunctional or higher. In both cases, a three-dimensional network can be formed. Moreover, since a three-dimensional network is formed via the polymer compound, the compatibility between the polymer compound, the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is further improved. For this reason, even when a polymer compound having low compatibility with the polyfunctional hydroxyl group-containing compound and the polyfunctional crosslinkable compound is used, a practical resin composition that can be used in the production process of a flexible printed wiring board is obtained. . Hereinafter, each component will be described in detail.

(A) Polymer compound As the polymer compound, various polymer compounds can be used as long as the effects of the present invention are exhibited. Examples of the polymer compound include polyamide, polyamideimide, polyamic acid, polyimide obtained by imidizing polyamic acid, and the like. In the present invention, 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.

In the resin composition according to the first aspect, the polymer compound is not limited to the molecular structure, and various polymer compounds such as polyimide described above can be used. Among these, as the polymer compound, it is preferable to use polyimide from the viewpoints of heat resistance and moisture absorption resistance.

In the resin composition according to the second embodiment, a polymer compound having a hydroxyl group and / or a carboxyl group in the molecular chain is used. As such a polymer compound, polyamic acid, polyimide having a hydroxyl group or a carboxyl group in a molecular chain, or the like can be used.

Polyimide is obtained by reacting acid dianhydride and diamine. 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.

As the polymer compound, for example, a compound having a repeating structural unit represented by the following general formula (1) can be used.

Moreover, as a high molecular compound, you may use the non-silicone-type polyimide obtained by making alkyl ether diamine and acid dianhydride react, The silicone type obtained by making diaminosiloxane and acid dianhydride react. The polyimide may be used.

As the polymer compound, it is preferable to use a compound having a repeating structure represented by the following general formula (2). Since the polymer compound has an oxyalkylene group, the molecular chain is given flexibility and the solvent solubility of the polymer compound is improved.

Moreover, as a high molecular compound, it is preferable to use what has each the polyimide structure represented by following General formula (3), and the polyamic acid structure represented by following General formula (4) as a repeating structural unit. This polymer compound contains an alkyl ether structure in the polyimide structure and a polyamic acid structure, so that flexibility is imparted to the molecular chain without impairing the molecular weight stability, thereby improving development stability. To do. Further, in this polymer compound, the carboxyl group of the polyamic acid structure contained in the following general formula (4) reacts with the crosslinkable functional group (for example, isocyanate group, oxazoline group, etc.) of the polyfunctional crosslinkable compound. Further, cross-linking is also formed between the polymer compound and the polyfunctional crosslinkable compound, and the shrinkage of the polyimide during curing can be further suppressed. Moreover, since the carboxyl group in hardened | cured material reduces because a carboxyl group reacts with a crosslinkable functional group, the hardened | cured material excellent in insulation can be obtained.

Moreover, as a high molecular compound, what contains the diamine represented by the following general formula (5) as a diamine component which comprises the high molecular compound represented by the said General formula (3) is preferable.

(In Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently a hydrogen atom or a carbon atom having 1 to carbon atoms. And R ₃ , R ₆ , R ₉ , R ₁₂ and R ₁₅ each independently represents a tetravalent organic group having 1 to 20 carbon atoms, m, n , P are each independently an integer of 0-30, which satisfies 1 ≦ (m + n + p) ≦ 30.)

Moreover, as a high molecular compound, it is preferable to use what has a structure represented by following General formula (6) as a repeating unit.

(In formula (6), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ 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 ₁₅ represent a tetravalent organic group having 1 to 20 carbon atoms, m, n, p Each independently represents an integer of 0 or more and 30 or less, R ₁₆ represents a tetravalent organic group, and R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms. , C represents mol% of each unit, and satisfies 0.10 ≦ (A + B) / (A + B + C) ≦ 0.85.)

In the polymer compound represented by the general formula (6), by satisfying 0.10 ≦ (A + B) / (A + B + C), the alkyl ether structure in the molecular chain is increased, and the molecular chain of the polymer compound is increased. Since the flexibility is improved, warping after curing can be reduced. Further, by satisfying (A + B) / (A + B + C) ≦ 0.85, the carboxyl group in the molecular chain increases, so that the solubility of the cured product in the alkaline developer is developed and the developability is improved.

Furthermore, as a high molecular compound, it is preferable to use what has a polyimide structure represented by the following general formula (7) and a polyamic acid structure represented by the following general formula (8) as a repeating structural unit. In this high molecular compound, since the siloxane part is contained in the polyimide structure, the polyimide structure is imparted with appropriate flexibility, so that the shrinkage of the molecular chain of the high molecular compound can be suppressed, and the warpage after curing can be suppressed. . Moreover, since an aromatic ring is contained in the polyamic acid structure, a decrease in the molecular weight of the polyamic acid structure can be suppressed, and the storage stability of the resin composition and the development time stability of the dry film obtained from the resin composition are improved. Furthermore, since the polyimide structure and the polyamic acid structure contain a tetravalent organic group derived from tetracarboxylic dianhydride, moderate rigidity is imparted to the molecular chain, heat resistance is improved, and insulation reliability is improved.

(In formula (7) and formula (8), Z ₃ and Z ₄ are tetravalent organic groups derived from tetracarboxylic dianhydride represented by the following general formula (9), and are the same as each other. R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, R ₁₉ is a monovalent organic group having 1 to 30 carbon atoms, and e is 1 or more and 20 or less. Represents an integer.)

Furthermore, when a polymer compound having a polyimide structure represented by the general formula (7) and a polyamic acid structure represented by the general formula (8) as a repeating structural unit is used, a polyamic acid structure is used. The carboxyl group contained in reacts with the crosslinkable functional group (for example, isocyanate group) of the polyfunctional crosslinkable compound. Thereby, a high molecular compound is taken in into the three-dimensional network between a polyfunctional hydroxyl-containing compound and a polyfunctional crosslinkable compound, and can suppress the segregation to the surface of the hardened | cured material of a silicone part. Thereby, since the decrease in surface tension and the expression of water repellency can be suppressed, a good adhesive force can be obtained even when a protective film is used.

(B) Polyfunctional hydroxyl group-containing compound As the polyfunctional hydroxyl group-containing compound, a common polyfunctional hydroxyl group-containing compound can be used in the resin composition according to the first and second embodiments. As the polyfunctional hydroxyl group-containing compound, various hydroxyl group-containing compounds can be used as long as they have two or more hydroxyl groups in the molecular chain within the scope of the effects of the present invention. As a polyfunctional hydroxyl group-containing compound, for example, various diols as a bifunctional hydroxyl group-containing compound containing two hydroxyl groups may be used, or various polyols containing three or more hydroxyl groups may be used. Among these, from the viewpoint of forming a plurality of cross-linking bonds 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 two or more hydroxyl groups.

The polyfunctional hydroxyl group-containing compound preferably contains at least one selected from both-ends 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 viewpoint, as the polyfunctional hydroxyl group-containing compound, among the specific examples given above, hydrogenated polybutadiene polyol and polycarbonate polyol are preferable, and polycarbonate polyol is preferably used from the viewpoint of reducing warpage.

In the resin composition according to the present invention, the content of the polyfunctional hydroxyl group-containing compound is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polyimide. 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 excessive hydroxyl group in a resin composition reduces because a polyfunctional hydroxyl-containing compound is 60 mass parts or less, the insulation reliability after hardening of a resin composition improves. Further, the content of the polyfunctional hydroxyl group-containing compound is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyimide.

As the polyfunctional hydroxyl group-containing compound, those having a number average molecular weight of 500 to 3000 are preferably used. 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 2,000 from the viewpoint of low elasticity and viscosity reduction of the resin composition.

(C) Polyfunctional crosslinkable compound As a polyfunctional crosslinkable compound, the common polyfunctional crosslinkable compound can be used in the resin composition which concerns on a 1st aspect and a 2nd aspect. As the polyfunctional crosslinkable compound, various polyfunctional crosslinkable compounds can be used as long as they have two or more crosslinkable functional groups within the scope of the effects of the present invention. 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. Moreover, as a polyfunctional crosslinkable compound, the bifunctional crosslinkable compound which has two crosslinkable functional groups may be used, and the crosslinkable compound which has 3 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 and a polyfunctional oxazoline compound having two or more oxazoline groups.

As the polyfunctional crosslinkable compound, it is preferable to use a polyfunctional isocyanate compound containing two or more isocyanate groups. With this configuration, 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 the imide group and amide group contained in the polymer compound. Alternatively, an interaction due to a hydrogen bond occurs between a hydroxyl group and a carboxyl group 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, two conflicting physical properties (fluidity and viscosity) required when the resin composition is used as an interlayer insulating film of a multilayer flexible printed wiring board can be achieved. Performance can be ensured. As the polyfunctional isocyanate compound, various isocyanate compounds can be used as long as they have two or more isocyanate groups within the scope of the effects of the present invention.

In the case where the resin composition according to the present invention is used as an interlayer insulating film such as a multilayer flexible wiring board, the resin composition is required to flow into the wiring part or through-hole part of the wiring board. Is required to 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. Therefore, for example, in the above-described resin composition, when a polyfunctional isocyanate compound is used as the polyfunctional crosslinkable compound, between the isocyanate group of the polyfunctional isocyanate compound and the hydroxyl group of the polyfunctional hydroxyl group-containing compound. By the urethane bond formed, the polyfunctional hydroxyl group-containing compound and the polyfunctional isocyanate compound are bonded to each other, and an interaction by a hydrogen bond between the urethane structure and the polymer compound 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 very good embedding can be achieved. .

Further, as the polyfunctional crosslinkable compound, a blocked isocyanate containing a blocked isocyanate group obtained by reacting a blocking agent with a polyfunctional isocyanate compound containing two or more isocyanate groups may be used. In this case, the polyfunctional crosslinkable compound contains two or more blocked isocyanate groups from the viewpoints of polymerization by reaction with a hydroxyl group of the polyfunctional hydroxyl group-containing compound, heat resistance improvement by crosslink formation, and chemical resistance. Those that do are preferred. Furthermore, from the viewpoint of forming a cross-linking bond between the polyfunctional hydroxyl group-containing compound and the isocyanate compound, it is preferable to use a polyfunctional isocyanate compound or a blocked isocyanate containing two or more isocyanates as the polyfunctional hydroxyl group-containing compound.

In addition, it is also preferable to use a polyfunctional oxazoline compound having two or more oxazoline groups as the polyfunctional crosslinkable compound. With this configuration, 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 oxazoline compounds can be used as long as they have two or more oxazoline groups as long as the effects of the present invention are achieved.

In the resin composition according to the present invention, 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. Further, the content of the polyfunctional crosslinkable 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 invention, the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the crosslinkable functional group contained in the polyfunctional crosslinkable compound is hydroxyl group / crosslinkable functional group = 0.5 to 1 is preferable. 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) Photosensitizer The resin composition according to the present invention can be used as a photosensitive resin composition by containing a photosensitizer. As the photosensitizer, a common photosensitizer can be used in the resin composition according to the first aspect and the second aspect. The photosensitizer is not particularly limited as long as it is a compound having a property that the structure is changed by light irradiation and the solubility in a solvent is changed, and various compounds can be used. As the photosensitive agent, for example, a (meth) acrylate compound having two or more unsaturated double bonds capable of photopolymerization can be preferably used.

Moreover, in the resin composition which concerns on this invention, from a viewpoint of improving resolution and insulation, 3 double bonds are used as a (meth) acrylate compound which has two or more unsaturated double bonds which can be photopolymerized. It is preferable to include at least one (meth) acrylate compound.

Furthermore, in the resin composition of the present invention, from the viewpoint of reducing the insulation resistance value and warpage, the (meth) acrylate compound having three or more double bonds is a compound represented by the following general formula (10). Is preferred. The compound represented by the following general formula (10) is not incorporated into the skeleton of the polymer compound and forms a crosslinked product as the second component, so that the polymer compound can be prevented from shrinking during curing and curving is suppressed. can do. In addition, since the compound represented by the following general formula (10) does not have a functional group such as a hydroxyl group that reduces electrical insulation, a rigid cross-linked body is formed, and the glass transition point (Tg) of the cured film is formed. ) And the elastic modulus is increased, and the insulation resistance value is estimated to be improved.

(In the formula (10), R ₂₀ represents a hydrogen atom or a methyl group, and a plurality of E's each independently represents an alkylene group having 2 to 5 carbon atoms, which may be the same or different. F is an integer from 1 to 10.)

The resin composition of the present invention has two (meth) double bonds as a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds from the viewpoint of developability and insulation reliability. It is preferable to include an acrylate compound and a (meth) acrylate compound having three or more double bonds. Since the (meth) acrylate compound having three or more double bonds forms a rigid cross-linked body with the polyfunctional hydroxyl group-containing compound, the elastic modulus and glass transition point (Tg) of the cured film are increased, and the insulation It is estimated that reliability is improved.

(E) Photopolymerization initiator In the resin composition according to the present invention, when the above-described photosensitive agent is used, it is preferably used in combination with a photopolymerization initiator. As a photoinitiator, the common photoinitiator can be used in the resin composition which concerns on a 1st aspect and a 2nd aspect. As the photopolymerization initiator, various compounds can be used as long as they are compounds activated by various actinic rays, ultraviolet rays and the like to start polymerization. As the photopolymerization initiator, for example, oxime esters can be suitably used.

The resin composition according to the present invention preferably contains a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds and a photopolymerization initiator. Thereby, it can use suitably as a photosensitive resin composition.

(F) Flame retardant The resin composition according to the present invention preferably contains a flame retardant. As the flame retardant, a common flame retardant can be used in the resin composition according to the first aspect and the second aspect. Although it does not specifically limit as a kind of flame retardant, A halogen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, an inorganic flame retardant, etc. are mentioned. Moreover, as a phosphorus compound, if it is a compound which contains a phosphorus atom in a structure as a phosphorus compound, it will not specifically limit. 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.

The resin composition according to the present invention preferably contains a phosphorus compound. Thereby, the flame retardance of a resin composition improves.

In the resin composition according to the present invention, it is preferable that a phosphoric acid ester compound and / or a phosphazene compound is included as the phosphorus compound. Thereby, especially the flame retardance of a resin composition improves.

In the resin composition according to the present invention, 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 invention on a base material, and drying. Moreover, the photosensitive resin composition containing the photosensitive agent can also be used as a photosensitive film. These resin films and photosensitive films can be suitably used, for example, as an interlayer insulating film / wiring protective film of a flexible printed board.

The cured product according to the present invention can be obtained by heating the resin composition at 100 ° C. to 130 ° C. for 5 minutes to 60 minutes and then heating at 160 ° C. to 200 ° C. for 15 minutes to 60 minutes.

The resin film according to the present invention 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 invention, 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 invention, a copper foil is used as a 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 invention 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 the wiring pattern of the wiring board.

In the resin composition according to the present invention, since it contains a low molecular weight polyfunctional hydroxyl group-containing compound and a polyfunctional crosslinkable compound that are well compatible with the polymer compound, the viscosity of the resin composition is reduced and the fluidity is reduced. improves. Thereby, 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, the outline of the manufacturing process of the wiring board according to the present invention will be described with reference to FIG. As shown in FIG. 1A, a double-sided flexible substrate 10 including an insulating substrate 11 and copper foils 12a and 12b provided on both main surfaces of the insulating substrate layer 11 is used for manufacturing a multilayer flexible wiring board. . 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 invention is filled in the through holes 13 and insulated. Here, as described above, in the resin composition according to the present invention, when a polyfunctional isocyanate compound is used as the polyfunctional crosslinkable compound and a hydroxyl group and / or a carboxyl group is used as the polymer compound, the resin composition Appropriate fluidity and viscosity are developed in the object. Thereby, even if the minute through hole 13 is provided, the through hole 13 can be filled.

Next, as shown to FIG. 1D, the laminated body 15 provided with the copper foil 15a and the protective layer 15b obtained by apply | coating the resin composition which concerns on this copper foil 15a to

copper foil

12a, 12b Laminate each on top. Here, in the resin composition according to the present invention, 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 invention on the copper foil 15a having the wiring pattern processed. Here, as described above, in the resin composition according to the present invention, when a polyfunctional isocyanate compound is used as the polyfunctional crosslinkable compound and a hydroxyl group and / or a carboxyl group is used as the polymer compound, the resin composition Appropriate fluidity and viscosity are developed in the object. Thereby, even when a fine wiring pattern is formed, the resin composition is filled between the wiring patterns, and insulation protection can be performed.

In addition, the resin film according to the present invention has an interlayer insulation resistance of 10 ⁹ Ω or more in an insulation reliability test at a temperature of 85 ° C., a humidity of 85%, and 1000 hours, and a viscosity of 120 ° C. to 220 ° C. is 5000 Pa · S to 100000 Pa. -It is S, it is desirable to have an elastic region with an elongation of less than 20% and a plastic region with an elongation of 50% or more, and the thickness of the interlayer insulating layer is 40 μm or less. Thereby, when laminating the resin film and the resin film formed on the copper foil on the wiring board, the through-hole portion can be satisfactorily filled and used suitably without the resin flow at the end of the wiring board. When used as an interlayer insulating film, it is required that the resin flow into the wiring portion and through-hole portion of the wiring board, while the resin composition is required to be held to some extent without flowing out from the end portion 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. In the case of the above configuration, by controlling the viscosity of the resin film at 120 ° C. to 220 ° C. and the elastic region and the plastic region of the resin film, the flow into the mutually opposing through holes and the end of the wiring board, which were difficult in the prior art, are controlled. It is possible to achieve both prevention of outflow of the resin composition from the part and achieve very good embedding properties.

That is, when the viscosity of the resin film is 120 ° C. to 220 ° C. and the viscosity is 5000 Pa · S or more between 120 ° C. and 220 ° C. used for lamination, the resin composition flows out from the end of the wiring board. If prevention and good embedding property are obtained and the viscosity is 100000 Pa · S or less, the film can be well laminated by a general-purpose laminating apparatus such as a vacuum press. In addition, the resin composition can be prevented from flowing out from the end of the wiring board in an elastic region of less than 20% elongation of the resin film, and good embedding can be achieved by the plastic region of the resin film having an elongation of 50% or more. it can. Furthermore, when the film thickness of the interlayer insulating layer is 40 μm or less, it exhibits very good low resilience, so that it can be easily incorporated into a small portable electronic device, and the insulation reliability test at a temperature of 85 ° C., a humidity of 85%, and 1000 hours. When the interlayer insulation resistance at 10 is ^{9 9} Ω or more, good insulation reliability can be obtained even when the thickness of the interlayer insulation layer is 40 μm or less.

Hereinafter, the above-described embodiment of the present invention will be described in detail. In the following first to fourth embodiments, the resin composition according to the second aspect will be mainly described. However, the following first to fourth embodiments will be described. In this form, it is also possible to use the resin composition according to the first aspect by appropriately selecting the polymer compound to be used.

(First embodiment)
As a material used for manufacturing a flexible printed circuit board, a resin composition including a polyimide precursor obtained by imidizing a part of polyamic acid has been proposed. In this resin composition, by using a polyimide precursor obtained by imidizing a part of the polyamic acid, the warpage accompanying the shrinkage of the polyimide is reduced, and the polyimide precursor accompanying the imidization can be achieved by enabling imidization at a low temperature. In addition to suppressing the reaction between the wiring material and the wiring material, development with an aqueous alkali solution is facilitated. However, due to the recent increase in functionality and weight of flexible printed circuit boards, even when a resin containing a conventional polyimide precursor is used, it is not always possible to sufficiently reduce warpage, and improvement in heat resistance is desired. Yes.

The present inventors have focused on (A) using a polyimide containing a polyamic acid structure and a polyimide structure as structural units as a polymer compound. The inventors of the present invention contain (A) a polyimide as a polymer compound, (B) a polyfunctional hydroxyl group-containing compound, and (C) an isocyanate compound (block isocyanate compound) as a polyfunctional crosslinkable compound. By setting the molar ratio of the hydroxyl group contained in the functional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate compound within a predetermined range, it is possible to reduce warpage during curing and to achieve excellent heat resistance. It has been found that a resin composition that can be suitably used as a material such as a surface protective film of an element, an interlayer insulating film, a protective insulating film for a printed wiring board, and an interlayer insulating film can be obtained.

In this resin composition, the polyfunctional hydroxyl group-containing compound is not incorporated into the polyimide skeleton and is present as the second component, and three-dimensional crosslinking is formed between the polyfunctional hydroxyl group-containing compound and the blocked isocyanate compound. The shrinkage of the molecular chain of the polyimide during curing can be suppressed, the warpage can be suppressed, and the melt viscosity of the resin composition before curing can be reduced to improve the through-hole embedding property. Moreover, since a polyimide has the polyamic acid structure which has a heat crosslinkable functional group as a structural unit, the three-dimensional network through a polyimide is formed between a polyfunctional hydroxyl-containing compound and a block isocyanate compound. By these, the curvature at the time of hardening can be reduced. Furthermore, since polyimide has good compatibility with other components and has a polyimide structure as a structural unit that forms a three-dimensional structure or an interpenetrating network structure [InterPenetration Network (IPN)], high heat resistance (for example, High solder heat resistance). Further, since the blocked isocyanate compound is contained, the carboxyl group is inactivated at a low temperature and can be cured at a low temperature. Therefore, shrinkage of the polyimide skeleton at the time of curing can be prevented and warpage can be suppressed. Hereinafter, the first embodiment of the present invention will be described in detail.

The resin composition according to the first embodiment of the present invention contains (a) a polyimide, (B) a polyfunctional hydroxyl group-containing compound, and (c-1) an isocyanate compound (block isocyanate compound). It has a polyimide structure and a polyamic acid structure as constituent units, and the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate compound is hydroxyl group / isocyanate group = 0.5 to 1. .

In this resin composition, the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate is hydroxyl group / isocyanate group = 0.5 to 1, and The amount is excessive. With this configuration, it is presumed that heat resistance is exhibited by the following mechanism. The isocyanate group reacts with a hydroxyl group to form a urethane structure, but the isocyanate group remains because the amount of the isocyanate group is excessive with respect to the hydroxyl group. The surplus isocyanate group reacts with the carboxyl group of the polyamic acid structure contained in the polyimide remaining after the imidation reaction to form an amide structure, a urea structure, or the like. That is, it is considered that chemical crosslinking between the polyimide and the blocked isocyanate compound and chemical crosslinking between the polyfunctional hydroxyl group-containing compound and the blocked isocyanate compound are formed by thermosetting. Thus, further heat resistance is expressed by forming a three-dimensional network by a plurality of types of crosslinking such as reaction between isocyanates.

Next, each component constituting the resin composition will be described in detail.

(A) Polyimide The polyimide used for the resin composition according to the present embodiment can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine. There is no restriction | limiting in the tetracarboxylic dianhydride to be used, A conventionally well-known tetracarboxylic dianhydride can be used. As tetracarboxylic dianhydride, aromatic tetracarboxylic acid, aliphatic tetracarboxylic dianhydride, etc. are applicable. Moreover, there is no restriction | limiting in the diamine to be used, A conventionally well-known diamine can be used.

Specific examples of the aromatic tetracarboxylic acid include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-Zika Ruboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2- Bis (4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4- (2,5-dioxotetrahydrofuran) -3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4 Dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4- And dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, and the like.

Specific examples of the aliphatic tetracarboxylic dianhydride include cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic Acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] oct-7 -Ene-2,3,5,6 tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride and the like.

The above-described tetracarboxylic dianhydrides may be used alone or in combination of two or more. Of the tetracarboxylic dianhydrides described above, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic acid, from the viewpoint of heat resistance and polymerization rate of polyimide. Particularly preferred are dianhydrides, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and bis (3,4-dicarboxyphenyl) sulfone dianhydride.

Specific examples of diamines include, for example, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,3-bis (3-amino Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, bis (3- (3-aminophenoxy) phenyl) ether, bis (4- (4-aminophenoxy) phenyl) ether, 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,4-bis (4- (4-aminophenoxy) phenoxy) benzene, bis (3- (3- (3-aminophenoxy) phenoxy) phenyl) ether, Bis (4- (4- (4-aminophenoxy) phenoxy) phenyl) ether, 1,3-bis ( -(3- (3-aminophenoxy) phenoxy) phenoxy) benzene, 1,4-bis (4- (4- (4-aminophenoxy) phenoxy) phenoxy) benzene, 4,4'-bis (3-aminophenoxy) ) Biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (3-aminophenoxy) 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-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, bis (3-amino Enyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 2 , 2-bis [4- (3-aminophenoxy) phenyl] butane, α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω -Bis (4-aminobutyl) polydimethylsiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, and the like. Not. Preferably, 4,4′-bis (3-aminophenoxy) biphenyl, 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, polyoxy Alkylene diamine.

Examples of the diamine include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, and α, ω-bis (4-aminobutyl) polydimethylsiloxane. Α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, and the like are also preferable.

In the diamine described above, it is preferable to use polyoxyethylene diamine, polyoxypropylene diamine, and other polyoxyalkylene diamines containing oxyalkylene groups having different numbers of carbon chains from the viewpoint of reducing the warpage of the cured product of the resin composition. . Examples of polyoxyalkylenediamines include polyoxyethylenediamines such as Jeffamine ED-600, ED-900, ED-2003, EDR-148, and HK-511 manufactured by Huntsman, Inc., and Jeffamine D-230 and D-400. , D-2000, D-4000, polyoxypropylene diamines such as polyetheramines D-230, D-400, and D-2000 manufactured by BASF, Germany, and polytetramethylenes such as Jeffamine XTJ-542, XTJ533, and XTJ536 Examples thereof include those having an ethylene group.

Among them, EDR-148, D-230, D-400, HK-511, etc. having a relatively low molecular weight can be polymers having a relatively high glass transition temperature, and thus are preferable in applications requiring heat resistance and chemical resistance. Used. On the other hand, D-2000 having a relatively high molecular weight is excellent in flexibility. From the viewpoint of balance between heat resistance, chemical resistance and flexibility, and solvent solubility, the weight average molecular weight of polyoxyalkylene diamine is preferably 400 to 3000, particularly preferably 400 to 2000, D-400, D- 2000, ED-600, ED-900, and XTJ-542 are preferably used.

The polyimide used in the resin composition according to the present embodiment has a polyimide structure and a polyamic acid structure as structural units. Thus, by having both a polyimide structure part having good compatibility with other components and a polyamic acid structure part having a heat-crosslinkable functional group, the remaining carboxyl group at the time of low-temperature curing can be reacted with a blocked isocyanate. It can be inactivated and warpage can be suppressed by the blocked isocyanate and the polyfunctional hydroxyl group-containing compound.

Moreover, it is preferable that the polyimide used in the resin composition according to the present embodiment includes a polyimide having a polyether structure. This is because by having the polyether structure in the skeleton, the glass transition temperature and the elastic modulus of the cured product after thermosetting can be controlled, and warpage can be further reduced. In addition, after thermosetting, chemical crosslinking is formed between the polyimide having a polyether structure and the compound having a thermally crosslinkable functional group, and the polyimide having a polyether structure has a polyoxyalkylene chain. This is because a three-dimensional network is formed by local interaction between polymer chains, and heat resistance can be expressed.

Further, as the polyimide, it is preferable to use a polyimide including a polyimide part having a structure of the following general formula (2). This is for improving the solvent solubility of polyimide.

(In Formula (2), Z ₁ and Z ₂ represent a tetravalent organic group. Y ₁ , Y ₂ , Y ₃ , Y ₄ , and Y ₅ represent an alkylene group having 1 to 5 carbon atoms. And may have a side chain. B, c, and d represent an integer of 1 to 50.)

Moreover, as the polyimide, it is also preferable to use a polyimide including a polyimide portion having a structure of the following general formula (11). The solvent solubility of polyimide is also improved by including a polyimide part having the structure of the following general formula (11). As the polyimide, it is preferable to use a polyimide containing a polyimide part having the structure of the above general formula (2) or the following general formula (11).

(In the formula (11), _{Z 5} and _{Z 6,} it is _{_{_{_{.Y 6, Y 7, Y 8}}}} , Y 9, Y 10, Y 11, Y 12 and _{Y 13} which represents a tetravalent organic group, a hydrocarbon group (G represents an integer of 3 to 100)

In the general formula (2), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ are alkylene groups having 1 to 5 carbon atoms, such as methylene group, ethylene group, propylene group, isopropylene. Group, butylene group and isobutylene group. b, c, and d represent an integer of 1 to 50, preferably 3 to 40, and more preferably 5 to 30.

In the general formula (11), Z ₅ and Z ₆ represent a tetravalent organic group, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a benzophenone group, a diphenyl sulfone group, and a naphthalene group. Among these, a biphenyl group, a diphenyl ether group, a benzophenone group, and a diphenyl sulfone group are preferable, and a diphenyl ether group is more preferable.

In the general formula (11), Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ and Y ₁₃ represent a hydrocarbon group. Examples of Y ₆ and Y ₇ include alkylene groups having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Examples of Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ and Y ₁₃ include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group, an ethyl group, and a propyl group are more preferable. g represents an integer of 3 to 100, preferably 5 to 70, and more preferably 10 to 50.

Furthermore, in all diamines in the polyimide, it is preferable that the content of diamine having the structure of the following general formula (12) is 15 mol% or more and 85 mol% or less. This is for improving the solvent solubility and lowering the elastic modulus of polyimide.

(In Formula (12), Y ₁ , Y ₂ , Y ₃ , Y ₄ , and Y ₅ represent an alkylene group having 1 to 5 carbon atoms and may have a side chain. B, c, and d represents an integer of 1 to 50.)

In the general formula (12), Y ₂ , Y ₃ , Y ₄ and Y ₅ preferably have two or more types of alkylene groups from the viewpoint of adhesion to the substrate.

Furthermore, it is preferable that the content rate of the diamine which has the structure of following General formula (13) is 15 mol% or more and 95 mol% or less in all the diamines in a polyimide. This is for improving the solvent solubility and lowering the elastic modulus of polyimide.

(In Formula (13), Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ and Y ₁₃ represent a hydrocarbon group. G represents an integer of 3 to 100)

The imidation ratio of the polyimide is preferably 25% or more and less than 100% from the viewpoint of forming a crosslink between the polyimide and an isocyanate compound as a polyfunctional crosslinkable compound having a crosslinkable functional group. % To 98% is more preferable. If the imidization ratio of the polyimide is 98% or less, the carboxyl group in the polyimide precursor that crosslinks with the compound having a thermally crosslinkable functional group remains sufficiently, and thus exhibits chemical resistance and heat resistance after curing. Moreover, if the imidation ratio of polyimide is 25% or more, the carboxyl residue soluble in the alkaline solution decreases after curing, and chemical resistance and heat resistance can be exhibited.

In the above-described embodiment, the resin composition according to the second aspect using a polyimide containing a polyimide structure and a polyamic acid structure has been described. However, the polyamic acid structure is within the scope of the effects of the present invention. It is also possible to use the resin composition according to the first aspect by using a polyimide that does not substantially contain. In this case, since the imidization ratio of the polyimide is 100%, there is no need for an imidization reaction, and deterioration of the wiring layer is suppressed and good insulation reliability and heat resistance are exhibited.

Next, a method for producing polyimide will be described. As a method for producing polyimide according to the present embodiment, all methods capable of producing polyimide, including known methods, can be applied. Among them, it is preferable to use a method of performing the reaction in an organic solvent. Examples of the solvent used in such a reaction include 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. The concentration of the reaction raw material in this reaction is usually 2% by mass to 80% by mass, preferably 30% by mass to 70% by mass.

The molar ratio of tetracarboxylic dianhydride to be reacted and 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 to 1.1, more preferably 0.95 to 1.05.

The weight average molecular weight of the polyimide is preferably 5000 or more and 100,000 or less. Here, the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The weight average molecular weight is more preferably from 10,000 to 60,000, and most preferably from 20,000 to 50,000. When the weight average molecular weight is 5,000 or more and 100,000 or less, the warp of the protective film obtained using the resin composition is improved, and the low resilience and heat resistance are excellent. Furthermore, printing can be performed without bleeding at a desired film thickness during coating printing, and mechanical properties such as elongation of the obtained protective film are excellent.

Polyimide can be 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. for imidization or chemically imidized using an imidizing agent such as acetic anhydride to have 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.

It is also preferable to obtain a polyimide having a polyimide structure and a polyamic acid structure by carrying out a reaction at 80 ° C. to 220 ° C. to advance both the production of a polyimide having a polyamic acid structure and a thermal imidization reaction. That is, by suspending or dissolving a diamine component and an acid dianhydride component in an organic solvent and reacting them under heating at 80 ° C. to 220 ° C., both generation of polyimide and dehydration imidization are performed. It is also preferable to obtain a polyimide.

Also, the end 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 terminal blocking 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-aminobenz Tolyl, 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-a Aromatic monoamines such as no-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene and 9-aminoanthracene; Can be mentioned. Among these, aniline derivatives are preferably used. These may be used alone or in combination of two or more.

Examples of the end-capping agent comprising 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 addition, without further solvent removal.

In the above-described embodiment, (A) the resin composition according to the second aspect using a polyimide structure containing an aliphatic diamine component as a polymer compound and a polyimide having a polyamic acid structure as a structural unit is described. However, it is also possible to use the resin composition according to the first aspect by using a polyimide that does not substantially contain a polyamic acid structure within the range where the effects of the present invention are exhibited.

(B) Polyfunctional hydroxyl group-containing compound The polyfunctional hydroxyl group-containing compound used in the resin composition according to the present embodiment refers to a compound containing two or more hydroxyl groups per molecular chain. Examples of the skeleton include those containing hydrocarbon groups such as aliphatic, aromatic, and alicyclic groups, and those having a structure represented by the following formula (14) in the skeleton from the viewpoint of enhancing the insulating properties. It is preferable that it is an aliphatic compound from the viewpoint of warpage suppression. This is because by having an aliphatic skeleton, hygroscopicity can be suppressed without impairing the effect of suppressing warpage, and high insulating properties can be expressed even during moisture absorption. In addition, it is preferable to include a long-chain aliphatic group because the effect of suppressing warpage is enhanced.

(In the formula (14), X is an aromatic, Y is an aliphatic having 1 to 10 carbon atoms, and Z is a functional group selected from an ether group, an ester group, a carbonate group, a urethane group, and a urea group. H represents an integer from 0 to 2, i represents an integer from 0 to 1, and j represents an integer from 1 to 1000.)

In particular, for electronic materials, those not containing halogen such as fluorine and chlorine are preferable.

Specific examples of the polyfunctional hydroxyl group-containing compound include polytetramethylene diol such as PTMG1000 (manufactured by Mitsubishi Chemical Corporation), polybutadiene diol such as G-1000 (manufactured by Nippon Soda Co., Ltd.), and GI-1000 (manufactured by Nippon Soda Co., Ltd.). Hydrogenated polybutadiene diol, polycarbonate diols such as Duranol T5651, Duranol T5652, Duranol T4671 (Asahi Kasei Chemicals) and Plaxel CD (Daicel Chemical), polycaprolactone diols such as Plaxel 200 (Daicel Chemical), bisphenol A ( Bisphenols such as Daicel Chemical Industries, Ltd., and hydrogenated bisphenols such as Ricabinol HB (Shin Nihon Rika Co., Ltd.).

Of these, polybutadiene diol, hydrogenated polybutadiene diol, and polycarbonate diol are preferable from the viewpoint of enhancing the insulating properties, and polycarbonate diol is preferable from the viewpoint of reducing warpage.

In addition, the polyfunctional hydroxyl group-containing compound is preferably a liquid compound at room temperature in terms of warpage reduction and solubility in an organic solvent. The molecular weight is preferably 500 to 3000, and particularly preferably 500 to 2000.

The polyfunctional hydroxyl group-containing compound is preferably contained in an amount of 3 parts by mass to 70 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of achieving both reduction in warpage, solder heat resistance and chemical resistance. More preferably, it is contained in parts by mass.

In addition, in this Embodiment, although the polyfunctional hydroxyl-containing compound containing two hydroxyl groups was demonstrated as (B) polyfunctional hydroxyl-containing compound, it contains two or more hydroxyl groups in the range with the effect of this invention. Polyols can also be used.

(C-1) Blocked isocyanate compound The blocked isocyanate compound used in the resin composition according to this embodiment is obtained by reacting a blocking agent with an isocyanate having two or more isocyanate groups in the molecule. The resulting compound. Examples of isocyanate compounds having two or more isocyanate groups in the molecule include 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate. Nate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-hydroxylated diisocyanate, isophorone diisocyanate, 1 , 5-naphthalene diisocyanate, 4,4-diphenyl diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, phenylene 1,4-diisocyanate, phenylene 2,6-diisocyanate, Examples thereof include 1,3,6-hexamethylene triisocyanate and hexamethylene diisocyanate. Blocking agents include alcohols, phenols, ε-caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, carbamates , Imines, or sulfites.

Specific 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 manufactured by Asahi Kasei Chemicals Corporation. And hexamethylene diisocyanate (hereinafter also referred to as “HDI”) block isocyanate. The Mitsui Chemicals Polyurethane products include the product name Takenate B-882N, the product name Takenate B-830, which is a tolylene diisocyanate block isocyanate, and the 4,4′-diphenylmethane diisocyanate block isocyanate. Trade name Takenate B-815N, Takenate B-846N which is a 1,3-bis (isocyanatemethyl) cyclohexane block isocyanate. Moreover, the product name Coronate AP-M2503, 2515, 2507, 2513, or Millionate MS-50 manufactured by Nippon Polyurethane Industry Co., Ltd., or the product number 7950, 7951, 7990 manufactured by Baxenden, which is an isophorone diisocyanate block isocyanate, can be used. . These blocked isocyanate compounds may be used alone or in combination of two or more.

In addition, in this Embodiment, although the example using a block isocyanate compound was demonstrated as (C) polyfunctional crosslinking | crosslinked compound, it replaced with the block isocyanate compound and the polyfunctional isocyanate compound which has two or more isocyanate groups mentioned above is used. It is also possible to use it. Furthermore, a polyfunctional oxazoline compound can also be used in place of the polyfunctional isocyanate compound within the range where the effects of the present invention are exhibited.

In addition, the resin composition may contain an organic solvent in addition to the polyimide, the polyfunctional hydroxyl group-containing compound, and the blocked isocyanate compound. It is because it can use preferably as a varnish by setting it as the state melt | dissolved in the organic solvent.

Examples of such organic solvents include amide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, γ- Lactone solvents such as butyrolactone and γ-valerolactone, sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide and hexamethyl sulfoxide, phenol solvents such as cresol and phenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), Examples include ether solvents such as tetraglyme, dioxane, tetrahydrofuran, butyl benzoate, ethyl benzoate, and methyl benzoate. These organic solvents may be used alone or in combination. In particular, from the viewpoint of high boiling point and low water absorption, it is preferable to use γ-butyrolactone, triglyme, butyl benzoate, and ethyl benzoate.

(F) Flame retardant The resin composition may further contain a flame retardant. The kind of flame retardant is not particularly limited, and examples thereof include halogen-containing compounds, phosphorus-containing compounds, and inorganic flame retardants. 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. For example, it can be used in the range of 5% by mass to 50% based on the polyimide content.

Examples of halogen-containing compounds include organic compounds containing chlorine and compounds containing bromine. Specific examples include pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane tetrabromobisphenol A, and the like.

As the phosphorus-containing compound, phosphorus compounds such as phosphazene, phosphine, phosphine oxide, phosphate ester, and phosphite ester are fried. In particular, from the viewpoint of compatibility with the polyimide composition, it is preferable to use phosphazene, phosphioxide, or phosphate ester.

Specific examples of phosphorus-containing compounds include phosphazene derivatives FP100, FP110, FP300, and FP400 manufactured by Fushimi Pharmaceutical Co., Ltd.

Inorganic flame retardants include antimony compounds and metal hydroxides. Antimony compounds include antimony trioxide and antimony pentoxide. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide. By using an antimony compound in combination with the above halogen-containing compound, antimony oxide is extracted from the flame retardant to produce antimony halide in the thermal decomposition temperature range of the plastic. Can be increased.

Since the inorganic flame retardant does not dissolve in the organic solvent, the particle size of the powder is preferably 100 μm or less. If the particle size is 100 μm or less, it is easy to be mixed into the polyimide composition, and the transparency of the cured resin is not impaired. In order to sufficiently increase the flame retardancy, the particle size of the powder is preferably 50 μm or less, particularly preferably 10 μm or less.

Further, a nitrogen-containing compound may be used as the flame retardant. One of the nitrogen-containing compounds may be used as a flame retardant, or two or more of the above-described halogen-containing compounds, phosphorus-containing compounds, and indefinite flame retardants and nitrogen-containing compounds may be mixed and used as a flame retardant. The amount of the nitrogen-containing compound added is not particularly limited and can be changed according to the type of flame retardant used. As addition amount of a nitrogen-containing compound, it can use in the range of 5 mass% to 50 mass% on the basis of content of a polyimide like the flame retardant mentioned above, for example. Examples of the nitrogen-containing compound include melamine cyanurate manufactured by Nissan Chemical Co., Ltd. and Sakai Chemical Industry Co., Ltd.

When forming a coating film, the viscosity and thixotropy are adjusted according to the coating method. If necessary, a filler or a thixotropic agent can be added and used. It is also possible to add additives such as known antifoaming agents, leveling agents and pigments.

Also, when forming a coating film, a urethanization catalyst may be added and used. U-CAT SA (registered trademark) 102, 603, 506, U-CAT (registered trademark) 1102 manufactured by San Apro, an organozirconium compound manufactured by Matsumoto Fine Chemical Co., and zirconium K-KAT manufactured by Enomoto Kasei Co., Ltd. Etc.

The resin composition may further contain a compound having a thermally crosslinkable functional group. Examples of the compound having a thermally crosslinkable functional group include triazine compounds, benzoxazine compounds, and epoxy compounds.

As the triazine compound, melamines and melamine cyanurates are preferable. Examples of melamines include melamine derivatives, condensates of compounds having a structure similar to melamine and melamine, and the like. Specific examples of melamines include, for example, methylolated melamine, ammelide, ammelin, formoguanamine, guanylmelamine, cyanomelamine, arylguanamine, melam, melem, melon and the like. Examples of melamine cyanurates include molar reactants such as cyanuric acid and melamines. Moreover, some of the amino groups or hydroxyl groups in melamine cyanurate may be substituted with other substituents. The benzoxazine compound may be composed only of monomers, or several molecules may be polymerized into an oligomer state. Moreover, you may use the benzoxazine compound which has a different structure simultaneously. Among these, bisphenol benzoxazine is preferably used.

In addition, the resin composition can be used as a negative photosensitive resin composition by further adding an acrylic monomer and a photo radical generator. Moreover, it can be used as a positive photosensitive resin composition by adding a photoacid generator.

A cured product can be obtained by heating the resin composition described above. The mode of heating is not particularly limited, but it is preferable to heat for 5 minutes to 60 minutes in a two-step temperature range. After heating at 100 ° C. to 130 ° C. for 5 minutes to 60 minutes, 15 ° C. at 160 ° C. to 200 ° C. It is more preferable to heat for 60 minutes. Thus, by making it harden | cure in two types of temperature ranges, the reaction between the compounds contained in a resin composition can be controlled, and a three-dimensional network can be formed. And thereby, the heat resistance and chemical resistance of hardened | cured material can be improved. More specifically, it is as follows. First, in the low temperature range (for example, 100 ° C. to 130 ° C.), a polyfunctional hydroxyl group-containing compound and a blocked isocyanate compound react to produce a urethane structure. Thereby, the chemical bridge | crosslinking I between a polyfunctional hydroxyl-containing compound and a block isocyanate compound is formed (henceforth "process (I)"). Thereafter, an imidization reaction of polyimide mainly occurs in a high temperature region (for example, 160 ° C. to 200 ° C.). Then, a reaction between the carboxylic acid of the polyamic acid in the polyimide remaining without being imidized and an isocyanate group occurs to form an amide structure or a urea structure. Thereby, the chemical bridge | crosslinking II between a polyamic acid and isocyanate is formed (henceforth "process (II)"). A cured product having excellent heat resistance can be obtained by the three-dimensional network formed by the crosslinks I and II. In addition, the isocyanate group remaining after the formation of the bridge II reacts with the remaining isocyanate groups. This eliminates the active species and enhances the insulation of the cured product.

In the above step (II), depending on the thickness of the resin composition film to be formed, the maximum temperature is set in the range of 150 ° C. to 220 ° C. with an oven or a hot plate, for 5 to 100 minutes, air or nitrogen, etc. The solvent is removed by heating in an inert atmosphere. The heating temperature may be constant over the entire processing time or may be gradually raised. The resin composition film can be formed by printing on the surface of a flexible printed circuit board or a semiconductor wafer by known screen printing or a precision dispensing method.

Since the resin composition exhibits excellent heat resistance when thermally cured, it is useful as a surface cured film for semiconductor elements, interlayer insulating films, bonding sheets, protective insulating films for printed wiring boards, surface protective films for printed circuit boards, etc. And is applied to various electronic components. For example, Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (insulating layer thickness: 25 μm, conductor layer: copper foil F2-WS (18 μm)) is used as a flexible printed circuit board. The composition is applied and cured. The part not coated can be used as an external terminal by applying electrolytic nickel-gold plating. The surface protective film thus formed exhibits good insulating properties. In addition, since the thermosetting of the resin composition in the present embodiment is performed under relatively low temperature conditions (for example, 160 ° C. to 200 ° C.), copper oxidation does not occur. Such low-temperature curing is possible because carboxylic acid reacts with a blocked isocyanate compound (more precisely, an isocyanate compound that has been unblocked by heating), so complete imidization is unnecessary and high-temperature heating as high as 250 ° C is not required. Because it becomes.

Also, the resin composition according to the present embodiment can be used as a resin film by coating on a substrate and drying.

In addition, using a double-sided copper-clad board of Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (insulating layer thickness 25 μm, conductor layer copper foil F2-WS (18 μm)), a double-sided component-mounted circuit board was created. Even if the resin composition is applied and cured in addition to the component mounting portion of the circuit board, good insulating properties are exhibited even if the resin composition is used as a surface protective film. Here, the thickness of the surface protective film is preferably 1 μm to 50 μm. When the film thickness is 1 μm or more, the handling becomes easy, and when the film thickness is 50 μm or less, it is easy to bend and incorporate easily.

In addition, the resin composition which concerns on this Embodiment can also be used as a photosensitive resin composition by containing the (D) photosensitive agent. Moreover, the photosensitive film can also be obtained by apply | coating the photosensitive resin composition on a base material.

Furthermore, the resin composition according to the present embodiment can be suitably used as an interlayer insulating film such as a multilayer flexible wiring board by providing a resin composition on a copper foil and drying it. Moreover, the resin composition according to the present embodiment can be suitably used as a protective film for a wiring pattern on a wiring board by providing the resin composition so as to cover the wiring pattern formed on the substrate.

(Second Embodiment)
In the manufacturing process of a flexible printed circuit board, a cover lay excellent in electrical insulation reliability, bending resistance, heat resistance, and flame retardancy is required. In order to realize such a coverlay, a resin composition containing a polyamic acid using an aliphatic diamine as a diamine component has been proposed. In this resin composition, since the aliphatic diamine is contained in the polyamic acid, the molecular weight of the varnish in which the resin composition is dissolved in the solvent is greatly reduced. The developability may deteriorate due to distortion or the like.

The present inventors have focused on (A) using a polyimide having a polyimide structure containing an aliphatic diamine component and a polyamic acid structure as a structural unit as a polymer compound. The present inventors then (A) a polyimide having a polyimide structure and a polyamic acid structure containing an aliphatic diamine component as a polymer compound as structural units, and (B) a bifunctional hydroxyl group as a polyfunctional hydroxyl group-containing compound. Photosensitive composition having good developability and warpage and having excellent insulating properties by containing a containing compound, (C) a blocked isocyanate compound as a polyfunctional crosslinkable compound, and (D) a photosensitive agent. I found out that things can be realized.

In this photosensitive resin composition, the hydroxyl group of the bifunctional hydroxyl group-containing compound and the isocyanate group of the blocked isocyanate compound react to form a urethane structure, and the bifunctional hydroxyl group-containing compound is not taken into the polyimide skeleton, Present as the second component in the photosensitive resin composition. Thereby, the shrinkage | contraction of the polyimide frame | skeleton at the time of hardening can be prevented, and reduction of curvature can be achieved. Moreover, since an aliphatic diamine component is contained in the polyimide structure of polyimide, it is possible to suppress a decrease in molecular weight due to depolymerization of the polyamic acid structure. Thereby, since molecular weight is stabilized, the fall of the remaining film rate at the time of the pattern by lithography and distortion of a pattern shape can be suppressed, and the fall of developability can be suppressed. Hereinafter, the second embodiment of the present invention will be described in detail.

The photosensitive resin composition according to the second embodiment of the present invention includes (a) a polyimide, (b) a bifunctional hydroxyl group-containing compound, (c-1) an isocyanate compound (block isocyanate compound), and a photosensitive agent. The molar ratio of the hydroxyl group contained in the bifunctional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate compound is hydroxyl group / isocyanate group = 0.5-1.

In this resin composition, when the molar ratio of the hydroxyl group contained in the bifunctional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate compound is hydroxyl group / isocyanate group = 0.5 to 1, excess isocyanate The group reacts with a carboxylic acid having a polyamic acid structure contained in polyimide. Thereby, a three-dimensional network is formed, and excellent insulation reliability can be achieved. Hereinafter, each component will be described in detail.

(A) Polyimide First, the polyimide in the photosensitive resin composition according to the present embodiment will be described. In the photosensitive resin composition according to the present embodiment, polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine. There is no restriction | limiting in the tetracarboxylic dianhydride to be used, A conventionally well-known tetracarboxylic dianhydride can be used. As tetracarboxylic dianhydride, aromatic tetracarboxylic acid, aliphatic tetracarboxylic dianhydride, etc. are applicable. Moreover, there is no restriction | limiting in the diamine to be used, A conventionally well-known diamine can be used.

In the photosensitive resin composition according to the present embodiment, the polyimide is represented by the polyimide structure represented by the following general formula (3) and the following general formula (4) from the viewpoint of developability and molecular weight stability. It is preferable that each has a polyamic acid structure as a repeating structural unit.

(In Formula (3) and Formula (4), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently a hydrogen atom. Or a monovalent organic group having 1 to 20 carbon atoms, which may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R _{15 each} have 1 to carbon atoms 20 represents a tetravalent organic group, and m, n, and p each independently represent an integer of 0 to 100. R ₁₆ represents a tetravalent organic group, and R ₁₇ represents 1 carbon atom. Represents a divalent organic group having 90 carbon atoms.

In addition, the polyimide preferably contains a diamine represented by the following general formula (15) as a diamine component constituting the polyimide structure represented by the general formula (3).

(In formula (15), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, and may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ are tetravalent having 1 to 20 carbon atoms. M, n, and p are each independently an integer of 0 to 30, and satisfy 1 ≦ (m + n + p) ≦ 30.)

As a method for synthesizing polyimide, tetracarboxylic dianhydride and aliphatic diamine represented by the general formula (15) are polymerized and cyclized to obtain a polyimide, and then tetracarboxylic dianhydride and the following: Examples include a synthesis method in which the diamine represented by the general formula (16) is polymerized.

(In the formula (16), R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms.)

Examples of the tetracarboxylic dianhydride 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”), diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic acid dianhydride Anhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as “TMEG”), p-phenylene bis (trimellitic acid monoester acid anhydride), p-biphenylene bis (trimellitic acid) Monoester acid anhydride), m-phenylenebis (trimellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride) ), Pentanediol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as “5-BTA”), decanediol bis (trimellitic acid monoester acid anhydride), pyromellitic anhydride, bis (3 , 4-Dicarboxyphenyl) ether dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3 ′, 4,4′-tetracarboxylic Acid 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-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4- (2, 5- Oxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic acid anhydride, and the like. The tetracarboxylic dianhydrides described above may be used alone or in combination of two or more. From the viewpoint of polyimide developability, BPDA, ODPA, BTDA, TMEG, 5-BTA, and decanediol bis (trimellitic acid monoester acid anhydride) are more preferable.

The diamine represented by the general formula (15) is not limited as long as it has the structure represented by the general formula (15), but may be 1,8-diamino-3,6-dioxyoctane or the like. Polyoxyethylenediamine compounds, polyoxyalkylenediamine compounds such as Huntsman's Jeffamine EDR-148 and EDR-176, Jeffamine D-230, D-400, D-2000, D-4000, polyether amine manufactured by BASF Examples include polyoxypropylenediamine compounds such as D-230, D-400, and D-2000, and compounds having different oxyalkylene groups such as HK-511, ED-600, ED-900, ED-2003, and XTJ-542. It is done. By using these compounds having an oxyalkylene group, warpage of FPC after baking of the polyimide can be reduced.

In the diamine represented by the general formula (15), m, n, and p are each independently an integer of 0 or more and 30 or less. From the viewpoint of insulation reliability, 1 ≦ (m + n + p) ≦ 30 is preferable, and 3 ≦ (m + n + p) ≦ 10 is more preferable. Since the skeleton having an oxyalkylene group is short as 1 ≦ (m + n + p) ≦ 30, it can be estimated that the elastic modulus of polyimide is increased and the insulation reliability is improved. In addition, usually when such an oxyalkylene group skeleton is short, warping tends to occur. In this embodiment, warpage is in a good state by using a bifunctional hydroxyl group-containing compound and blocked isocyanate in combination. It is estimated that the insulation reliability can be further improved while maintaining the above.

Although the polyimide which concerns on this Embodiment has a polyimide structure and a polyamic-acid structure as a repeating structural unit, respectively, by introduce | transducing the diamine represented by the said General formula (15) in a polyimide structure, a polyimide varnish and a film of The molecular weight is stable. When the diamine of the above general formula (15) is introduced into the polyamic acid structure, the aliphatic diamine has a high basicity, and the depolymerization of the polyamic acid proceeds and the molecular weight decreases remarkably as compared with the conventional polyamic acid. By introducing into the polyimide structure, the molecular weight is stabilized without being affected by the basicity of the aliphatic diamine.

Examples of the diamine represented by the general formula (16) include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy). ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3, 3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3, 7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminoben Phenone, 4,4′-bis (4-aminophenyl) sulfide, 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) Trimethylene-bis (4-aminobenzoate) (hereinafter abbreviated as TMAB), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, bis [4- (4 -Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 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) and the like. Among these, APB, BAPP, and TMAB are preferable from the viewpoint of low Tg of polyimide and developability. Some of these diamines can also be used as diamines used in polyimide.

Furthermore, in the present embodiment, it is preferable that the polyimide has a structure represented by the following general formula (6) as a repeating unit.

(In formula (6), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently a hydrogen atom or a carbon number of 1 to Represents a monovalent organic group having 20 carbon atoms, and may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ are tetravalent having 1 to 20 carbon atoms. M, n, and p each independently represents an integer of 0 or more and 30 or less, R ₁₆ represents a tetravalent organic group, and R ₁₇ represents a divalent having 1 to 90 carbon atoms. A, B, and C represent mol% of each unit, and satisfy 0.10 ≦ (A + B) / (A + B + C) ≦ 0.85.

Among the structures represented by the general formula (6), from the viewpoints of developability, warpage, and insulation reliability, 0.10 ≦ (A + B) / (A + B + C) ≦ 0.85 is preferable. 15 ≦ (A + B) / (A + B + C) ≦ 0.8 is more preferable, and 0.2 ≦ (A + B) / (A + B + C) ≦ 0.7 is more preferable. When (A + B) which is a structure containing the diamine represented by the general formula (15) is 0.10 or more based on the whole, warpage can be reduced. Moreover, since the (A + B) which is a structure containing the diamine represented by the general formula (15) is 0.85 or less with respect to the whole, a decrease in elastic modulus and glass transition point (Tg) is suppressed, Insulation reliability is maintained. Furthermore, when (A + B) which is a polyimide structure is 0.85 or less with respect to the whole, the solubility with respect to the alkaline developer is developed, and the developability is improved.

The main chain terminal of the polyimide is not particularly limited as long as it does not affect the performance. A terminal derived from an acid dianhydride or a diamine used for producing polyimide may be used, or the terminal may be sealed with another acid anhydride or an amine compound.

The weight average molecular weight of the polyimide is preferably from 1,000 to 1,000,000. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight average molecular weight as a standard. The weight average molecular weight is preferably 1000 or more from the viewpoint of the strength of the polyimide film. Moreover, it is preferable that it is 1000000 or less from a viewpoint of the viscosity of a polyimide containing resin composition and a moldability. The weight average molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000, and most preferably from 20,000 to 50,000.

A polyimide having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a process of synthesizing a first-stage polyimide site by reacting acid dianhydride and diamine in an unequal molar amount (process 1), followed by a second stage. It can be produced by the step of synthesizing the polyamic acid moiety (step 2). Hereinafter, each process will be described.

(Process 1)
The process of synthesizing the first stage polyimide site will be described. The step of synthesizing the first-stage polyimide site is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto. Then, a solvent that is azeotroped with water is added, and the mixture is heated and stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours, while removing by-product water azeotropically using a mechanical stirrer. In this case, the monomer concentration is 0.5% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less.

When synthesizing the polyimide part, the polyimide part can be obtained by adding a known imidation catalyst or by using no catalyst. The imidization catalyst is not particularly limited, but an acid anhydride such as acetic anhydride, a lactone compound such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalido acid, Examples thereof include tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of γ-valerolactone and pyridine and a non-catalyst are particularly preferable from the viewpoint of high reactivity and influence on the next reaction.

The amount of the imidization catalyst added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less when the polyamic acid is 100 parts by mass.

The reaction solvent used in the synthesis of the polyimide moiety is an ether having 2 to 9 carbon atoms, such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether. Compound; ketone compound having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene, Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as toluene, xylene, mesitylene, tetralin; methyl acetate, ethyl acetate, γ-butyrolactone Ester compounds having 3 to 12 carbon atoms such as methyl benzoate; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing compounds having 2 to 10 carbon atoms; sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as required. Particularly preferred solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

In the synthesis of the polyimide part, the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower. If the reaction temperature is 15 ° C. or higher, the reaction starts, and if it is 250 ° C. or lower, there is no deactivation of the catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.

The time required for the reaction varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

(Process 2)
Next, the process for synthesizing the second stage polyamic acid moiety will be described. The synthesis of the polyamic acid moiety in the second stage can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and adding diamine and / or acid dianhydride for polymerization. The polymerization temperature in the synthesis of the second stage polyamic acid moiety is preferably 0 ° C. or higher and 250 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 0 ° C. or higher and 80 ° C. or lower.

The time required for the reaction during the synthesis of the polyamic acid varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

As the reaction solvent, the same solvent used for the synthesis of the polyimide moiety in Step 1 can be used. In that case, the polyamic acid moiety can be synthesized using the reaction solution of Step 1 as it is. Moreover, you may use the solvent different from what was used for the synthesis | combination of a polyimide site | part.

Examples of such a solvent include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. Ketone compounds having 2 to 6 carbon atoms; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms, such as methyl acetate, ethyl acetate, γ-butyrolactone, methyl benzoate More than 12 ester compounds; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Nitrogen-containing compounds having 2 to 10 carbon atoms such as -2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide.

These may be one kind or a mixture of two or more kinds as required. Particularly preferred solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

After completion of production, the polyimide may be used as it is dissolved in the reaction solvent, or may be recovered and purified by the following method. Moreover, the collection | recovery of the polyimide after completion | finish of manufacture can be performed by depressurizingly distilling the solvent in a reaction solution.

Examples of the polyimide purification method include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like. Moreover, the purification method by what is called reprecipitation which adds a reaction solution to a poor solvent and precipitates can be implemented. Furthermore, when a particularly high-purity polyimide is required, a purification method by extraction using supercritical carbon dioxide is also possible.

In the photosensitive resin composition according to the present embodiment, insulation reliability is improved and warpage can be suppressed by containing a bifunctional hydroxyl group-containing compound and blocked isocyanate. It is presumed that the insulation reliability is improved by the formation of a crosslinked body by the reaction between the hydroxyl group contained in the bifunctional hydroxyl group-containing compound and the isocyanate group contained in the blocked isocyanate. In addition, since the bifunctional hydroxyl group-containing compound is present as the second component without being taken into the polyimide skeleton, shrinkage of the polyimide skeleton during curing can be prevented and warpage can be suppressed. Furthermore, the inclusion of the blocked isocyanate inactivates the carboxyl group at a low temperature and enables low-temperature curing. Therefore, it is considered that the shrinkage of the polyimide skeleton during curing can be prevented and the warpage can be suppressed.

In the above-described embodiment, the example in which polyimide is used as the polymer compound (A) has been described. However, as the polymer compound, polyimide that does not include a polyamic acid structure, polyamide that does not include a polyimide structure, It is also possible to use a polyamideimide containing both a polyamic acid structure and a polyimide structure.

In the resin composition according to the present embodiment, from the viewpoint of heat resistance, the molar ratio of the hydroxyl group contained in the bifunctional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate is hydroxyl group / isocyanate group = 0. It is preferably 5 to 1.

(B) Bifunctional hydroxyl group-containing compound The bifunctional hydroxyl group-containing compound is the same as the polyfunctional hydroxyl group-containing compound used in the resin composition according to the first embodiment as long as the effects of the present invention are achieved. Can be used.

(C-1) Blocked isocyanate compound As the blocked isocyanate compound, the same compounds as those used for the resin composition according to the first embodiment can be used. Moreover, similarly to the resin composition according to the first embodiment, other polyfunctional isocyanate compounds and polyfunctional oxazoline compounds can also be used within the range where the effects of the present invention are exhibited.

(D) Photosensitive agent The photosensitive resin composition according to the present embodiment includes a (meth) acrylate compound having at least two or more photopolymerizable unsaturated double bonds as a photosensitive agent, and further includes (E) light. It preferably contains a polymerization initiator. The photosensitive agent in the photosensitive resin composition according to the present embodiment represents a compound having a property that the structure is changed by light irradiation and the solubility in a solvent is changed. In the photosensitive resin composition which concerns on this Embodiment, two or more light is contained by including the (meth) acrylate compound and photoinitiator which have two or more photopolymerizable unsaturated double bonds. Since a crosslinked body is formed also by the (meth) acrylate compound having a polymerizable unsaturated double bond, developability and insulation reliability are improved.

Examples of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds include tricyclodecane dimethylol diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi ( (Meth) acrylate, tris (2-acryloxyethyl) isocyanurate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, glycerol tri (meth) acrylate, trimethylolprop Tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether (meth) acrylate, Bisphenol A diglycidyl ether di (meth) acrylate, β-hydroxypropyl-β '-(acryloyloxy) -propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri / tetra (meth) acrylate, etc. And the like. Among them, EO-modified bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A diacrylate, and pentaerythritol tri / tetra (meth) acrylate are preferable from the viewpoint of developability and warpage after firing.

In addition, from the viewpoint of developability and insulation reliability, a combination of a compound having two double bonds and a compound having three or more double bonds is preferable. It is estimated that the compound having three or more double bonds forms a rigid cross-linked body, whereby the elastic modulus and glass transition point (Tg) of the cured film are increased, and the insulation reliability is improved.

In general, when a compound having three or more double bonds is included, warping tends to occur because the number of crosslinking points increases. However, in this embodiment, the bifunctional hydroxyl group-containing compound is present as a second component in the photosensitive resin composition without forming a crosslinked structure with the compound having a double bond, thereby reducing warpage. can do.

Examples of the compound having three or more double bonds include pentaerythritol tri / tetraacrylate (trade name: Aronix (registered trademark) M-306, manufactured by Toagosei Co., Ltd.), trimethylolpropane PO-modified triacrylate (trade name: Aronix M). -310, manufactured by Toagosei Co., Ltd., pentaerythritol tetraacrylate (trade name: A-TMMT, Shin-Nakamura Chemical Co., Ltd.), EO-modified glycerol tri (meth) acrylate (trade name: A-GLY-9E (EO-modified 9 mol) ), Shin-Nakamura Chemical Co., Ltd.), ditrimethylolpropane tetraacrylate (trade name: Aronix M-408, manufactured by Toagosei Co., Ltd.), dipentaerythritol pentaacrylate and hexaacrylate (trade name: Aronix M-403, manufactured by Toagosei Co., Ltd.) ) And the like.

The amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is preferably 5 parts by mass or more and 60 parts by mass or less from the viewpoint of developability when the amount of polyimide is 100 parts by mass. 10 parts by mass or more and 40 parts by mass or less are more preferable.

In the resin composition according to the present embodiment, when not used as a photosensitive resin, it is not always necessary to use (D) a photosensitive agent.

(E) Photopolymerization initiator Photopolymerization initiators include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyl dipropyl ketals, benzyl diphenyl ketals, benzoin Methyl ethers, benzoin ethyl ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-isopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4′-bis (dimethylamino) benzophenone [Michler's ketone], 4,4′- Aromatic ketone compounds such as su (diethylamino) benzophenone, 2,2-dimethoxy-2-phenylacetophenone, triarylimidazole dimers such as lophine dimer, acridine compounds such as 9-phenylacridine, α, α-dimethoxy Oxime ester compounds such as -α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, N-aryl-α-amino acid, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid, p- Diethylaminobenzoic acid, p-diisopropylaminobenzoic acid, p-benzoic acid ester, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-Hydro Xyloxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[(2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2 Α-hydroxyalkylphenones such as methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (dimethylamino) -2- [ Α-aminoalkylphenones such as (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis Acylphosphine oxides such as (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octyl Tandione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O And oxime esters such as -acetyloxime). Among these, oxime esters are preferable from the viewpoint of sensitivity.

The amount of the photopolymerization initiator is preferably 0.01 parts by mass or more and 40 parts by mass or less from the viewpoint of sensitivity and resolution when the amount of polyimide is 100 parts by mass. 0.5 parts by mass or more and 35 parts by mass or less are more preferable.

(F) Phosphorus compound It is preferable that the photosensitive resin composition contains a phosphorus compound. A phosphorus compound will not be limited if it is a phosphorus atom containing compound which contains a phosphorus atom in a structure. Examples of such phosphorus compounds include phosphate ester compounds having a phosphate ester structure and phosphazene compounds having a phosphazene structure.

Phosphoric acid ester compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, etc., phosphoric acid ester substituted with an aliphatic hydrocarbon group, tris (butoxyethyl) phosphate, etc. Phosphorus ester, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, resorcinol bis (diphenyl phosphate) and other aromatic organic groups as substituents Examples include acid ester compounds. Among these, tris (butoxyethyl) phosphate and triisobutyl phosphate are preferable from the viewpoint of developability.

Examples of the phosphazene compound include structures represented by the following general formula (17) and the following general formula (18).

R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ in the phosphazene compound represented by the general formula (17) and the general formula (18) are not limited as long as they are organic groups having 1 to 20 carbon atoms. A carbon number of 1 or more is preferable because flame retardancy tends to be exhibited. A carbon number of 20 or less is preferred because it tends to be compatible with polyimide. Among these, a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable from the viewpoint of flame retardancy. Such functional groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-cyanophenyl. Groups, functional groups having a phenyl group such as 3-cyanophenyl group, 4-cyanophenyl group, functional groups having a naphthyl group such as 1-naphthyl group, 2-naphthyl group, pyridine, imidazole, triazole, tetrazole, etc. Examples include functional groups derived from nitrogen heterocyclic compounds. These compounds may be used alone or in combination of two or more as required. Of these, compounds having a phenyl group, a 3-methylphenyl group, a 4-hydroxyphenyl group, and a 4-cyanophenyl group are preferred because of their availability.

V in the phosphazene compound represented by the general formula (17) is not limited as long as it is 3 or more and 25 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, it is preferable that v is 3 or more and 10 or less because of availability.

W in the phosphazene compound represented by the general formula (18) is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.

G and J in the phosphazene compound represented by the general formula (18) are not limited as long as they are organic groups having 3 to 30 carbon atoms. In this, as G, —N═P (OC ₆ H ₅ ) ₃ , —N═P (OC ₆ H ₅ ) ₂ (OC ₆ H ₄ OH), —N═P (OC ₆ H ₅ ) ( OC ₆ H ₄ OH) ₂ , —N═P (OC ₆ H ₄ OH) ₃ , —N═P (O) (OC ₆ H ₅ ), —N═P (O) (OC ₆ H ₄ OH) preferable. J includes -P (OC ₆ H ₅ ) ₄ , -P (OC ₆ H ₅ ) ₃ (OC ₆ H ₄ OH), -P (OC ₆ H ₅ ) ₂ (OC ₆ H ₄ OH) ₂ ,- P (OC ₆ H ₅ ) (OC ₆ H ₄ OH) ₃ , —P (OC ₆ H ₄ OH) ₄ , —P (O) (OC ₆ H ₅ ) ₂ , —P (O) (OC ₆ H ₄ OH) ₂ , —P (O) (OC ₆ H ₅ ) (OC ₆ H ₄ OH) and the like are preferable.

As the phosphorus compound, one type of phosphorus compound may be used, or two or more types of phosphorus compounds may be used in combination.

The addition amount of the phosphorus compound in the photosensitive resin composition is preferably 50 parts by mass or less from the viewpoint of developability and the like when the amount of polyimide is 100 parts by mass. From the viewpoint of flame retardancy of the cured product, 45 parts by mass or less is more preferable. Moreover, if it is 5 mass parts or more, an effect is exhibited.

(G) Other compounds The photosensitive resin composition may contain other compounds as long as the performance is not adversely affected. Specific examples 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.

Examples of the thermosetting resin include epoxy resins, cyanate ester resins, unsaturated polyester resins, benzoxazine resins, benzoxazolines, phenol resins, melamine resins, and maleimide compounds.

Examples of the compound having reactivity with polyimide include a compound capable of reacting with a carboxyl group, amino group or terminal acid anhydride in a polymer to form a three-dimensional crosslinked structure. Among them, a so-called thermal base generator compound that generates an amino group as a base by heating is preferable. For example, there is a compound obtained by protecting the amino group of a base compound such as an amine with an acid chloride compound, which forms a salt structure with an acid such as sulfonic acid, is protected with a dicarbonate compound. Thereby, it is stable without exhibiting basicity at room temperature, and can be a thermal base generator that generates a base by deprotection by heating.

The heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom. Here, the hetero atoms in this embodiment include oxygen, sulfur, nitrogen, and phosphorus. Specific examples include 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, imidazole such as 2-phenylimidazole, N-alkyl group-substituted imidazole such as 1,2-dimethylimidazole, Aromatic group-containing imidazole such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl Cyano group-containing imidazoles such as -2-undecylimidazole and 1-cyanoethyl-2-phenylimidazole, imidazole compounds such as silicon-containing imidazoles such as imidazole silane, 5-methylbenzotriazole, 1- (1 ′, 2′-dica Bo carboxyethyl benzotriazole), triazole compounds such as 1- (2-ethyl-F carboxymethyl aminomethyl benzotriazole), etc. oxazole compounds 2-methyl-5-phenyl-benzoxazole and the like.

Examples of pigments and dyes include phthalocyanine compounds.

The addition amount of other compounds is not limited as long as it is 0.01 parts by mass or more and 30 parts by mass or less. If it is 0.01 mass part or more, there exists a tendency for adhesiveness and the coloring property to a film to fully improve, and if it is 30 mass parts or less, there will be no bad influence on photosensitivity. The photosensitive resin composition may optionally contain an organic solvent.

The organic solvent is not limited as long as it can uniformly dissolve and / or disperse the polyimide. Examples of such organic solvents include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. Ketone compounds having 2 to 6 carbon atoms; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as: carbons such as methyl acetate, ethyl acetate, γ-butyrolactone, methyl benzoate 3 to 9 ester compounds; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N- Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as methyl-2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide.

These may be one kind or a mixture of two or more kinds as required. Particularly preferable organic solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Or a mixture of two or more of them. From the viewpoint of polyimide solubility, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

The concentration of polyimide in the resin composition composed of polyimide and an organic solvent is not particularly limited as long as it is a concentration capable of forming a resin molded body. The polyimide concentration is preferably 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the polyimide concentration is preferably 90% by mass or less from the uniformity of the film thickness of the resin molded body. From the viewpoint of the film thickness of the obtained resin molding, it is more preferably 2% by mass or more and 80% by mass or less.

(H) Photosensitive film The photosensitive resin composition which concerns on this Embodiment can be used suitably for formation of a photosensitive film. The photosensitive film which concerns on this Embodiment is obtained by apply | coating the photosensitive resin composition on a base material. The photosensitive film according to the present embodiment includes a carrier film, the photosensitive resin composition provided on the carrier film, and a cover film formed on the photosensitive resin. Is preferred.

From the viewpoint of producing a photosensitive film, the polyimide concentration in the photosensitive resin composition is preferably 1% by mass or more and 90% by mass or less. As a density | concentration of a polyimide, 1 mass% or more is preferable from a viewpoint of the film thickness of a photosensitive film, and 90 mass% or less is preferable from a viewpoint of the viscosity of the photosensitive resin composition, and the uniformity of a film thickness. From a viewpoint of the film thickness of the obtained photosensitive film, 2 mass% or more and 80 mass% or less are more preferable.

Next, a method for producing a photosensitive film will be described. First, the substrate is coated with the photosensitive resin composition. As a base material, if it is a base material which is not damaged in the case of photosensitive film formation, it will not be limited. Examples of such a substrate include a silicon wafer, glass, ceramic, heat resistant resin, and carrier film. Examples of the carrier film include a polyethylene terephthalate film and a metal film. A heat-resistant resin and a carrier film are preferable from the viewpoint of easy handling, and a polyethylene terephthalate film is particularly preferable from the viewpoint of peelability after pressure bonding to the substrate.

Examples of coating methods include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating. After the coating, if necessary, a heat treatment called pre-baking may be performed with a hot plate or the like.

When manufacturing the photosensitive film comprised with the photosensitive resin composition, the solution of the photosensitive resin composition is apply | coated on arbitrary base materials (carrier film) by arbitrary methods. Next, after drying the photosensitive resin composition into a dry film, for example, a laminated film having a carrier film and a photosensitive film is obtained.

In addition, a laminate film may be formed by providing at least one layer of an optional antifouling or protective cover film on the photosensitive film. In the laminated film according to the present embodiment, the cover film is not limited as long as it is a film that protects a photosensitive film such as low-density polyethylene.

(I) Flexible printed wiring board The photosensitive film which concerns on this Embodiment can be used suitably for a flexible printed wiring board. The flexible printed wiring board according to the present embodiment includes a base material having wiring and the photosensitive film provided so as to cover the wiring on the base material. This flexible wiring board can be obtained by pressure-bonding a photosensitive film on a substrate having wiring, alkali-developing, and then baking.

Examples of the substrate having wiring in the flexible printed wiring board include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a copper clad laminate. Among these, a flexible substrate is preferable from the viewpoint of bendability.

The formation method of the flexible printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring. As such a forming method, hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating, or the like is performed in a state where the wiring side of the substrate having wiring and the photosensitive film according to the present embodiment are in contact with each other. The method etc. are mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a heat vacuum press or a heat vacuum laminate is preferable.

The heating temperature when laminating the photosensitive film on the substrate having wiring is not limited as long as the photosensitive film can be in close contact with the substrate. From the viewpoint of adhesion to the substrate and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or more and 400 ° C. or less are preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.

The surface treatment of the substrate having wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.

The photosensitive film can be subjected to negative photolithography by irradiating with light and then dissolving the portion other than the light irradiated portion by alkali development. In this case, examples of the light source used for light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.

The aqueous alkali solution used for development is not limited as long as it is a solution that can dissolve other than the light irradiation site. Examples of such a solution include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred. Examples of the development method include spray development, immersion development, and paddle development.

Next, a printed wiring board is formed by firing the printed wiring board to which the photosensitive film is pressure-bonded. Firing is preferably carried out at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoints of solvent removal, side reactions and decomposition. More preferably, it is 100 degreeC or more and 300 degrees C or less.

The reaction atmosphere in the firing can be performed in an air atmosphere or an inert gas atmosphere. In the production of a printed wiring board, the time required for the firing varies depending on the reaction conditions, but is usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.

The polyimide and the photosensitive resin composition according to the present embodiment have good warpage after curing, good developability, and chemical resistance when used as a cured product. Formation of protective layers for printed wiring boards and circuit boards used for operation panels of electronic devices, insulation layers for laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, peripheral members of semiconductor devices, semiconductor mounting substrates It is used for film formation on electronic parts for protection, insulation and adhesion of heat sinks, lead pins, semiconductors, etc. A protective film that protects wiring formed on a silicon wafer, a copper clad laminate, a printed wiring board, or the like is called a coverlay.

Moreover, the polyimide and the photosensitive resin composition according to the present embodiment include a flexible printed circuit (FPC) substrate, a tape automation bonding (TAB) substrate, an electrical insulating film and a liquid crystal display substrate in various electronic devices, It can be suitably used for an organic electroluminescence (EL) display substrate, an electronic paper substrate, a solar cell substrate, particularly a coverlay for a flexible printed circuit.

(Third embodiment)
A resin composition containing a polyimide having a polyamic acid structure having a siloxane moiety using silicone diamine as a diamine component and a polyimide structure has been proposed as a material used in the manufacturing process of the flexible printed circuit board. In these resin compositions, the siloxane moiety exists only in the polyamic acid structure. For this reason, there is a problem that the polyimide structure shrinks and warps during curing, the molecular weight of the polyamic acid structure is remarkably lowered, and the development time of the dry film (resin film) becomes unstable. In recent years, as a component mounting reliability of a flexible printed circuit board, a high acceleration test (HAST) has been carried out, and a material with high insulation reliability having HAST resistance and warpage suppressed for improving connection reliability. Is required.

The inventors of the present invention have focused on (A) using a polyimide structure having a siloxane moiety and a polyamic acid structure as a structural unit as a polymer compound. (A) a polyimide having a siloxane moiety as a polymer compound and a polyimide having a polyamic acid structure as a structural unit, (D) a (meth) acrylate compound having a specific structure as a photosensitizer, and (E) light It has been found that a photosensitive resin composition having excellent HAST resistance can be realized by a photosensitive resin composition containing a polymerization initiator.

In this photosensitive resin composition, since the siloxane portion is contained in the polyimide structure, it is possible to suppress a decrease in the molecular weight of the polyamic acid structure, and thus it is possible to suppress a decrease in developability. Moreover, since moderate softness | flexibility is provided to the polyimide site | part of a molecular chain, the curvature of the resin film at the time of hardening can be reduced. Furthermore, by including a bifunctional hydroxyl group-containing compound and a blocked isocyanate compound, shrinkage and segregation of the polyimide having a silicone moiety can be suppressed, and the reduction in warpage and the heat resistance during curing are improved, and the adhesiveness to the substrate is improved. Reduction can be suppressed. Hereinafter, the third embodiment of the present invention will be described in detail.

The photosensitive resin composition according to the third embodiment of the present invention includes (a) a polyimide having a polyimide structure and a polyamic acid structure as constituent units, and (D) two unsaturated double bonds capable of photopolymerization. The (meth) acrylate compound having the above and (E) a photopolymerization initiator are contained. Hereinafter, each component will be described in detail.

(A) Polyimide The polyimide according to the present embodiment is a block copolymer having a polyimide structure represented by the following general formula (7) and a polyamic acid structure represented by the following general formula (8) as repeating structural units. It is a coalescence. The polyimide according to the present embodiment is synthesized using an acid dianhydride and a diamine.

(In the formulas (7) and (8), Z ₃ and Z ₄ are tetravalent organic groups derived from tetracarboxylic dianhydride represented by the following general formula (9), and are the same. R ₁₈ represents a divalent organic group having 1 to 30 carbon atoms, R ₁₉ represents a monovalent organic group having 1 to 30 carbon atoms, and e is 1 represents an integer of 1 to 20.)

In the present embodiment, since the polyimide includes a polyimide structure represented by the general formula (7), a siloxane site is included in the polyimide structure. Thereby, since moderate softness | flexibility is provided to the polyimide site | part of a molecular chain, the curvature of the film after baking can be reduced. Moreover, since a polyimide contains the polyamic acid structure represented by the said General formula (8), an aromatic ring is introduce | transduced into a molecular chain. Thereby, since the fall of the molecular weight of a polyamic acid structure can be suppressed, the storage stability of the photosensitive resin composition and the development time stability of a dry film improve. Furthermore, since the polyamic acid structure and polyimide structure of polyimide contain a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the general formula (9), moderate rigidity is imparted to the molecular chain, Heat resistance is improved and insulation reliability (HAST resistance) is improved.

Examples of the acid dianhydride used in this embodiment include pyromellitic anhydride (hereinafter also abbreviated as “PMDA”), oxydiphthalic dianhydride (hereinafter also abbreviated as “ODPA”), biphenyltetracarboxylic dianhydride. Product (hereinafter also abbreviated as “BPDA”). For oxydiphthalic dianhydride and biphenyltetracarboxylic dianhydride, there are structural isomers, but the structure is not particularly limited. These acid dianhydrides may be used alone or in combination.

As the aromatic diamine used in this embodiment, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene Is mentioned. From the viewpoint of warping, 1,3-bis (3-aminophenoxy) benzene having flexibility is preferable.

Further, the silicone diamine used in the present embodiment is not particularly limited as long as it is a structure represented by the following general formula (19).

In the general formula (7) and the general formula (19), e is an integer that satisfies 1 ≦ e ≦ 20. If e is 20 or less, alkali solubility and HAST resistance will become favorable. The e in the general formula (19) is preferably 1 or more and 15 or less, more preferably 1 or more and 12 or less, from the viewpoint of Tg of the polyimide to be produced and flame retardancy.

In the general formula (7) and the general formula (19), R ₁₈ is not limited as long as it is a divalent organic group having 1 to 30 carbon atoms. The divalent organic group (R ₁₉ ) having 1 to 30 carbon atoms is represented by CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , etc. from the viewpoint of flame retardancy. A divalent organic group derived from an aliphatic saturated hydrocarbon having 10 or less carbon atoms is preferred.

In the general formula (7) and the general formula (19), R ₁₉ represents an organic group having 1 to 30 carbon atoms, which may be the same or different. Examples of the organic group (R ₁₉ ) having 1 to 30 carbon atoms include an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, an organic group containing a cyclic structure, and a group obtained by combining them.

Examples of the aliphatic saturated hydrocarbon group include primary hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group, secondary hydrocarbon groups such as isobutyl group and isopentyl group, and tertiary hydrocarbon groups such as a t-butyl group.

Examples of the aliphatic unsaturated hydrocarbon group include a hydrocarbon group containing a double bond such as a vinyl group and an allyl group, and a hydrocarbon group containing a triple bond such as an ethynyl group.

Examples of the functional group containing a cyclic structure include a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, and a cyclooctyl group; a polycyclic functional group such as a norbornyl group and an adamantyl group; pyrrole, furan, A heterocyclic functional group having a thiophene, imidazole, oxazole, thiazole, tetrahydrofuran, dioxane structure; an aromatic hydrocarbon group containing a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring structure.

The organic group (R ₁₉ ) having 1 to 30 carbon atoms may contain a halogen atom, a hetero atom and a metal atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Moreover, oxygen, sulfur, nitrogen, and phosphorus are mentioned as a hetero atom. Examples of the metal atom include silicon and titanium.

Further, when the organic group (R ₁₉ ) having 1 to 30 carbon atoms contains a hetero atom and / or a metal atom, R ₁₉ may be directly bonded to the bonded hetero atom and / or metal atom. And / or may be bonded via a metal atom.

The number of carbon atoms of R ₁₉ in the general formula (7) and the general formula (19), taking into account the flame retardant, 1 to 20 are preferred. Furthermore, from the viewpoint of solvent solubility of the polyimide to be produced, the number of carbon atoms is particularly preferably 1 or more and 10 or less.

As the compound represented by the general formula (19), compounds represented by R ₁₈ : propylene group and R ₁₉ : methyl group include PAM-E (n≈2), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.). n≈10), X-22-161A (n≈20), BY16-871 (n≈2), and BY16-853U (n≈10) manufactured by Toray Dow Corning. Examples of the compound represented by R ₁₈ : propylene group and R ₁₉ : phenyl group include X-22-1660B-3 (n≈20) manufactured by Shin-Etsu Chemical Co., Ltd.

The main chain terminal of the polyimide is not particularly limited as long as it does not affect the performance. The main chain terminal derived from the acid dianhydride and diamine used when producing polyimide may be used, or the main chain terminal may be sealed with another acid anhydride or an amine compound.

The weight average molecular weight of the polyimide is preferably 1,000 or more and 1,000,000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight average molecular weight as a standard. The weight average molecular weight is preferably 1000 or more from the viewpoint of the strength of the polyimide film. Moreover, it is preferable that it is 1000000 or less from a viewpoint of the viscosity of a polyimide containing resin composition and a moldability. The weight average molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000, and most preferably from 25,000 to 50,000.

As a method for producing a polyimi having a polyimide structure and a polyamic acid structure as repeating units, the production method shown in the second embodiment can be used.

In the above-described embodiment, the resin composition according to the second embodiment using (A) a polyimide structure having a siloxane moiety as a polymer compound and a polyimide having a polyamic acid structure as a structural unit has been described. It is also possible to use the resin composition according to the first aspect by using a polyimide that does not substantially contain a polyamic acid structure as long as the effects of the present invention are achieved.

(B) Bifunctional hydroxyl group-containing compound The photosensitive resin composition according to the present embodiment preferably contains a bifunctional hydroxyl group-containing compound and a blocked isocyanate compound. Since the bifunctional hydroxyl group-containing compound does not have a direct bond with polyimide, it is not taken into the skeleton and exists as the second component. Thereby, shrinkage | contraction of the polyimide frame | skeleton at the time of hardening can be prevented, and curvature can be suppressed. Further, the inclusion of the blocked isocyanate compound inactivates the carboxyl group of the polyimide at low temperature and enables low temperature curing, thereby preventing shrinkage of the polyimide skeleton during curing and suppressing warpage.

In the photosensitive resin composition according to the present embodiment, from the viewpoint of heat resistance, the molar ratio of the hydroxyl group contained in the bifunctional hydroxyl group-containing compound to the isocyanate group contained in the blocked isocyanate is hydroxyl group / isocyanate group. = 0.5 to 1 is preferable.

As the bifunctional hydroxyl group-containing compound, the same compounds as those used in the resin composition according to the first embodiment can be used. In addition, as a bifunctional hydroxyl-containing compound, the polyfunctional hydroxyl-containing compound containing a 2 or more hydroxyl group can also be used in the range with the effect of this invention.

In the present embodiment, the bifunctional hydroxyl group-containing compound is contained in an amount of 1 part by mass to 70 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of achieving both reduction in warpage, solder heat resistance and chemical resistance. The content is preferably 1 part by mass to 60 parts by mass.

(C-1) Blocked isocyanate compound As the blocked isocyanate compound, the same compounds as those used for the resin composition according to the first embodiment can be used. In addition, in this Embodiment, although the example using a blocked isocyanate compound was demonstrated as (C) polyfunctional crosslinking | crosslinked compound, in the range with the effect of this invention, the polyfunctional isocyanate compound which has two or more isocyanate groups, It is also possible to use a polyfunctional crosslinkable compound having two or more crosslinkable functional groups or a polyfunctional oxazoline compound.

(D) (Meth) acrylate compound As the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, tricyclodecane dimethylol diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, EO modified Hydrogenated bisphenol A diacrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-di ( p-hydroxyphenyl) propane di (meth) acrylate, tris (2-acryloxyethyl) isocyanurate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, glycerol tri (meth) acrylic , Trimethylolpropane tri (meth) acrylate, polyoxyethylenetrimethylolpropane tri (meth) acrylate, polyoxypropylenetrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl Ether (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) -propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol And re / tetra (meth) acrylate.

The photosensitive resin composition according to the present embodiment contains a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds. From the viewpoint of resolution and HAST resistance, it is preferable to include a (meth) acrylate compound having three or more double bonds.

Examples of (meth) acrylate compounds having three or more double bonds include pentaerythritol tri / tetraacrylate (Toagosei Co., Ltd., Aronix M-306), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., A-TMMT) , EO-modified glycerol tri (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-GLY-9E (EO-modified 9 mol)), ditrimethylolpropane tetraacrylate (manufactured by Toagosei Co., Ltd., Aronix M-408), dipentaerythritol penta And hexaacrylate (Aronix M-403, manufactured by Toagosei Co., Ltd.).

In the present embodiment, the (meth) acrylate compound having three or more double bonds may be a compound represented by the following general formula (10) from the viewpoint of insulation resistance (HAST resistance) and warpage. More preferred. This is because the compound represented by the following general formula (10) is not taken into the skeleton of the polyimide and forms a crosslinked body as the second component, thereby preventing the polyimide skeleton from shrinking at the time of curing and suppressing warpage. It is. In addition, since it does not have a functional group such as a hydroxyl group that reduces electrical insulation, a rigid cross-linked body is formed in the polyimide matrix according to this embodiment, and the Tg and elastic modulus of the cured film are high. Therefore, it is estimated that HAST resistance is improved.

(In the formula (10), R ₂₀ represents a hydrogen atom or a methyl group. A plurality of E each independently represents an alkylene group having 2 to 5 carbon atoms, which may be the same or different. F is an integer from 1 to 10.)

In the above formula (10), examples of the alkylene group having 2 to 6 carbon atoms (E) include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, and a neopentyl group. . From the viewpoint of resolution, E is more preferably 2 or 3 alkylene groups. In the above formula (10), from the viewpoint of flame retardancy, f is particularly preferably 1 or more and 5 or less.

Examples of the compound represented by the general formula (10) include Aronix M-350 (E: ethylene group, f: 1), M-360 (E: ethylene group, f: 2), M-310 manufactured by Toagosei Co., Ltd. (E: propylene group, f: 1), M-321 (E: propylene group, f: 2), SR502 (E: ethylene group, f: 3), SR9035 (E: ethylene group, f: manufactured by SARTOMER) 5). These may be used alone or in combination.

Moreover, in the photosensitive resin composition which concerns on this Embodiment, it has the (meth) acrylate compound which has two double bonds, and three or more double bonds from the viewpoint of the curvature after baking and resolution ( It is preferable to use together with a (meth) acrylate compound.

(Meth) acrylate compounds having two double bonds are classified into aliphatic di (meth) acrylates and aromatic di (meth) acrylates having a bisphenol structure. Examples of the aliphatic di (meth) acrylate include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and polyethylene / polypropylene glycol di (meth) acrylate. Specifically, nonaethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., 9G), heptapropylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., 9PG) and the like are preferable from the viewpoint of suppressing warpage.

Further, examples of the aromatic di (meth) acrylate include compounds represented by the following general formula (20).

(In the formula (20), R ₂₅ and R ₂₆ each represent a hydrogen atom or a methyl group. A plurality of E's each independently represents an alkylene group having 2 to 6 carbon atoms, which may be the same or different. May be.)

In the general formula (20), examples of the alkylene group having 2 to 6 carbon atoms (E) include ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentyl group, and the like. It is done.

In the general formula (20), l and k are each an integer of 1 to 10, and 2 ≦ l + k ≦ 20. If l and k are 10 or less, flame retardancy and HAST resistance are improved. Further, from the viewpoint of warpage and resolution, l and k in the general formula (20) are more preferably 3 or more and 6 or less and 6 ≦ l + k ≦ 12, respectively.

Specific examples of the general formula (20) include Aronix M-208 (R ₂₅ , R ₂₆ : hydrogen atom, E: ethylene group, l, k≈2) manufactured by Toagosei Co., Ltd., Shin-Nakamura Chemical Co., Ltd. Made in _{_{BPE-500 (R 25, R}} 26: methyl group, E: ethylene, l + k = 10), BPE-900 (R 25, R 26: methyl group, E: ethylene, l + k = 17), A- BPE-500 (R ₂₅ , R ₂₆ : hydrogen atom, E: ethylene group, l + k = 10), AB1206PE (the following general formula (21), R ₂₅ : hydrogen atom, R ₂₆ : methyl group, E ₁ : ethylene) Group, E ₂ : propylene group, l1 + k1 = 6, l2 + k2 = 12) and the like.

The amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is 5 parts by mass or more and 60 parts by mass or less from the viewpoint of resolution when the amount of polyimide is 100 parts by mass. Preferably, 10 parts by mass or more and 40 parts by mass or less are more preferable.

In addition, in the resin composition which concerns on this Embodiment, when not using as a photosensitive resin, it is not necessarily required to contain the (D) (meth) acrylate compound as a photosensitive agent.

(E) Photopolymerization initiator As the photopolymerization initiator, those similar to those shown in the second embodiment can be used.

(F) Phosphorus compound As the phosphorus compound, the same compounds as those described in the second embodiment can be used. Specific examples of the phosphazene compound represented by the general formula (17) include Rabitle (registered trademark) FP-300, FP-390 (abbreviated as FP-300 (R ₂₁ = R ₂₂ = 4-cyanophenyl group) and abbreviation FP-390 (R ₂₁ = R ₂₂ = 3-methylphenyl group).

(G) Other compounds Moreover, in the photosensitive resin composition which concerns on this Embodiment, another compound can be included in the range which does not have a bad influence on the performance. Examples of other compounds include the same compounds as those described in the second embodiment.

(H) Photosensitive film Moreover, the photosensitive resin composition which concerns on this Embodiment can be used for formation of a photosensitive film similarly to the photosensitive resin composition which concerns on the said 2nd Embodiment.

(I) Flexible printed wiring board Moreover, the photosensitive resin composition which concerns on this Embodiment should be used suitably for a flexible printed wiring board similarly to the photosensitive resin composition which concerns on the said 2nd Embodiment. Is possible.

(Fourth embodiment)
As a material used for the production of a flexible printed circuit board, a resin composition containing an arikari aqueous solution-soluble / solvent-soluble polyimide containing all of the polyamic acid and imidized with a hydroxyl group and / or a carboxyl group has been proposed. In this resin composition, the laser via processing used in the production of a flexible printed wiring board is not required, and it can be used as an interlayer insulating material for via processing using an antkari aqueous solution or a solvent. However, since the resistance to the solvent and alkaline aqueous solution used in the manufacturing process of the flexible printed wiring board is poor, improvement is required. In addition, when an insulating material in the form of a film that has been desolvated is laminated on a wiring board by a heat and pressure press method and used as an interlayer insulating film, since it is a polymer compound, resin fluidity is poor and through-hole embedding is poor, improving It is desired.

The present inventors have focused on using a solvent-soluble polyimide having a hydroxyl group and / or a carboxyl group and a siloxane moiety as the polymer compound (A). And, the present inventors have (A) a solvent-soluble polyimide as a polymer compound, (B) a bifunctional hydroxyl group-containing compound as a polyfunctional hydroxyl group-containing compound, and (C) an oxazoline compound as a polyfunctional crosslinkable compound. Can be processed with a solvent or an aqueous alkali solution before the crosslinking reaction, exhibits good through-hole embedding properties, and has an excellent resistance to an aqueous solvent and an aqueous alkali solution after the crosslinking reaction. It was found that can be realized. Hereinafter, the fourth embodiment of the present invention will be specifically described.

The resin composition according to the fourth embodiment of the present invention includes (a) a polyimide having a hydroxyl group and / or a carboxyl group, (b) a bifunctional hydroxyl group-containing compound, and (c-2) an oxazoline compound. The content of the bifunctional hydroxyl group-containing compound and the oxazoline compound is from 2 parts by mass to 45 parts by mass with respect to 100 parts by mass of the polyimide.

In this resin composition, since the polyimide has a hydroxyl group and / or a carboxyl group, and the content of the bifunctional hydroxyl group-containing compound and the oxazoline compound is within a predetermined range, the through-hole embedding property is excellent before crosslinking. It is soluble in an ant potassium solution and becomes insoluble in an alkaline solution after crosslinking. Moreover, when a polyimide has a hydroxyl group and / or a carboxyl group, it can react with an oxazoline compound and suppress warpage. In addition, since the bifunctional hydroxyl group-containing compound is present as the second component without being taken into the polyimide skeleton, shrinkage of the polyimide skeleton during curing can be prevented and warpage can be suppressed. In addition, the inclusion of the oxazoline compound inactivates the carboxyl group at a low temperature and enables low-temperature curing, thus preventing shrinkage of the polyimide skeleton during curing and suppressing warpage.

In this resin composition, since the polyimide has a hydroxyl group and / or a carboxyl group, it becomes soluble in an alkaline aqueous solution before curing, becomes insoluble in an alkaline aqueous solution after curing, and has high heat resistance (for example, high solder heat resistance). Is expressed. Moreover, the curvature at the time of hardening can be suppressed by the said structure.

In addition, although the polyimide structure has a hydroxyl group and / or a carboxyl group, the presence of a bifunctional hydroxyl group-containing compound in the resin composition can prevent the polyimide skeleton from shrinking during curing. That is, the curvature of the hardened | cured material obtained from a resin composition can further be reduced by containing a bifunctional hydroxyl-containing compound as a 2nd component, without being taken in in frame | skeleton. Further, by containing an oxazoline compound, insolubility in an alkaline aqueous solution and higher heat resistance can be realized by polymerizing and crosslinking by reaction with a hydroxyl group.

Further, the content of the bifunctional hydroxyl group-containing compound and the oxazoline compound is 2 to 45 parts by mass with respect to 100 parts by mass of the polyimide, and the polyimide is excessive with respect to other components. With this configuration, it is presumed that heat resistance is exhibited by the following mechanism. The oxazoline group reacts with a hydroxyl group to form a structure containing a C═O group or an NH group, but the oxazoline group further reacts with a hydroxyl group and / or carboxylic acid contained in the polyimide remaining after the imidization reaction, An amide structure or a urea structure containing a C═O group or an NH group is formed. That is, it is considered that chemical crosslinking between the polyimide and the oxazoline compound and chemical crosslinking between the bifunctional hydroxyl group-containing compound and the oxazoline compound are formed by thermosetting. As described above, by forming a three-dimensional cross-link by a plurality of types of cross-links, the heat resistance is further increased by making the polyimide excellent in heat resistance excessive.

Next, details of each composition constituting the resin composition will be described.

(A) Polyimide The polyimide used for the resin composition according to the present embodiment has a hydroxyl group and / or a carboxyl group as a structural unit. Thus, when the polyimide structure part reacts with the crosslinkable functional group of the polyfunctional crosslinkable compound and cures, it shows insolubility in the alkaline aqueous solution after curing. In addition, it is possible to inactivate a carboxyl group remaining during low-temperature curing by a reaction with an oxazoline compound and / or a blocked isocyanate compound, and to suppress warping by the oxazoline compound and / or the blocked isocyanate compound and a bifunctional hydroxyl group-containing compound. it can.

The polyimide used in the resin composition according to the present embodiment has a hydroxyl group and / or a carboxyl group as a structural unit. A hydroxyl group and / or a carboxyl group can be introduced into polyimide by using a diamine having a hydroxyl group and / or a carboxyl group. Such diamines include 2,5-diaminophenol, 3,5-diaminophenol, 4,4 ′-(3,3′-dihydroxy) diaminobiphenyl, 4,4 ′-(2,2 '-Dihydroxy) diaminobiphenyl, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3-hydroxy-4-aminobiphenyl (HAB), 4,4'-(3,3'- Dicarboxy) diphenylamine, methylenebisaminobenzoic acid (MBAA), 2,5-diaminobenzoic acid (DABA), 3,3′-dicarboxy-4,4′-diaminodiphenyl ether, and the like.

As for other configurations of the polyimide, those similar to those in the first embodiment can be used. In the above-described embodiment, the resin composition according to the second aspect using the solvent-soluble polyimide having a hydroxyl group and / or a carboxyl group and a siloxane moiety as the polymer compound (A) has been described. It is also possible to use the resin composition according to the first aspect by using a polyimide that does not substantially contain a polyamic acid structure as long as the effects of the present invention are achieved.

As a method for manufacturing polyimide according to the present embodiment, the same method as the method for manufacturing polyimide described in the first embodiment described above can be used.

(B) Bifunctional hydroxyl group-containing compound The bifunctional hydroxyl group-containing compound used in the resin composition according to the present embodiment refers to a compound containing two hydroxyl groups per molecular chain. Examples of the skeleton include those containing hydrocarbon groups such as aliphatic, aromatic, and alicyclic groups. When crosslinked with an oxazoline compound, the skeleton is represented by the following formula (14) from the viewpoint of enhancing insulation. Those having a structure in the skeleton are preferred, and compounds containing aliphatic groups are preferred from the viewpoint of warpage suppression. This is because by having an aliphatic skeleton, hygroscopicity can be suppressed without impairing the effect of suppressing warpage, and high insulating properties can be expressed even during moisture absorption. In addition, it is preferable to include a long-chain aliphatic group because the effect of suppressing warpage is enhanced.

(In the formula (14), X is aromatic, Y is aliphatic having 1 to 10 carbon atoms, Z is a functional group selected from an ether group, an ester group, a carbonate group, a urethane group, and a urea group, h = 0 represents an integer of 0 to 2, i represents an integer of 0 to 1, and j represents an integer of 1 to 1000.)

Also, a polyphenol-terminated compound is preferable for crosslinking with the oxazoline compound. In particular, for electronic materials, those not containing halogen such as fluorine and chlorine are preferable.

Specific examples of the bifunctional hydroxyl group-containing compound include polytetramethylene diol such as PTMG1000 manufactured by Mitsubishi Chemical Corporation, polybutadiene diol such as G-1000 manufactured by Nippon Soda Co., Ltd., hydrogenated polybutadiene diol such as GI-1000, Asahi Kasei Chemicals Corporation DURANOL T5651, DURANOL T5652, DURANOL T4671, and polycarbonate diols such as Placel CD manufactured by Daicel Chemical Co., Ltd. Hydrogenated bisphenols such as HB, phenol-modified silicones at both ends such as X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd., BY16-752 manufactured by Dow Corning, and BY16-799 are listed. It is.

Among these, a both-ends phenol-modified silicone, polybutadiene diol, hydrogenated polybutadiene diol, and polycarbonate diol are preferable from the viewpoint of improving insulation, and a both-end phenol-modified silicone and polycarbonate diol are preferable from the viewpoint of reducing warpage.

In addition, the bifunctional hydroxyl group-containing compound is preferably a liquid compound at room temperature from the viewpoint of warpage reduction and solubility in an organic solvent. The number average molecular weight is preferably 500 to 3000, and particularly preferably the number average molecular weight is 500 to 2000.

The bifunctional hydroxyl group-containing compound is preferably contained in an amount of 3 parts by mass to 70 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of achieving both warpage reduction, solder heat resistance and chemical resistance. More preferably, it is contained in parts by mass.

In addition, in this Embodiment, although the bifunctional hydroxyl-containing compound containing two hydroxyl groups was demonstrated as (B) polyfunctional hydroxyl-containing compound, it contains two or more hydroxyl groups in the range with the effect of this invention. Polyols can also be used.

(C-2) Oxazoline Compound The oxazoline compound used in the resin composition according to the present embodiment is a compound having two or more oxazoline groups in the molecule. As the oxazoline compound, one having at least two C═O groups and / or NH groups in the cross-linking when the cross-linking is formed between the polyimide (polymer compound) and / or the bifunctional hydroxyl group-containing compound is preferable. .

Specific examples of the oxazoline compound include 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, K-2010E, K-2020E, K-2030E, and 2,6-bis (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 oxazoline compounds may be used alone or in combination of two or more.

A cured product can be obtained by heating the resin composition described above. The mode of heating is not particularly limited, but it is preferable to heat at 50 ° C. to 140 ° C. for 1 minute to 60 minutes in order to make it soluble in an antkari aqueous solution. Furthermore, a crosslinking reaction mainly occurs by heating in a high temperature region (for example, 160 ° C. to 200 ° C.), and becomes insoluble in an alkaline aqueous solution.

In the above high temperature region, depending on the thickness of the resin composition film to be formed, the maximum temperature is set in the range of 150 ° C. to 220 ° C. with an oven or a hot plate, and air or nitrogen is not used for 5 to 100 minutes. It crosslinks by heating in an active atmosphere. The heating temperature may be constant over the entire processing time or may be gradually raised. The resin composition film can be formed by printing on the surface of a flexible printed circuit board or a semiconductor wafer by known screen printing or a precision dispensing method.

Since the resin composition exhibits excellent heat resistance by thermosetting, the surface cured film of the semiconductor element, the interlayer insulating film, the bonding sheet, the protective insulating film for the printed wiring board, the surface protective film / interlayer insulating of the printed circuit board It is useful as a film and is applied to various electronic components. For example, the resin composition can be applied to copper foil F2-WS (12 μm) and dried at 95 ° C. for 12 minutes to produce a copper foil with resin having an insulating layer thickness of 15 μm. As a flexible printed circuit board, Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (insulating layer thickness 25 μm, conductor layer copper foil F2-WS (18 μm)) is used. After laminating at 4 MPa at 100 ° C. for 1 minute in a vacuum press, forming a photosensitive etching resist layer on the copper foil, dissolving the etching resist and the resin composition with an alkaline aqueous solution to form vias, and then peeling the resist, An interlayer insulating film is obtained by curing at 180 ° C. for 1 hour. The interlayer insulating film formed in this way exhibits good insulating properties. In addition, since the thermosetting of the resin composition in the present embodiment is performed under relatively low temperature conditions (for example, 160 ° C. to 200 ° C.), copper oxidation does not occur.

In addition, a circuit board on which double-sided components were mounted was prepared using a double-sided copper-clad board of ESPANEX M (manufactured by Nippon Steel Chemical Co., Ltd., insulation layer thickness 25 μm, conductor layer copper foil F2-WS (18 μm)). Even if the resin composition is coated and dried on the substrate, cured after being processed with an alkaline aqueous solution, and the resin composition is used as a surface protective film, good insulating properties are exhibited. Here, the thickness of the surface protective film is preferably 1 μm to 50 μm. When the film thickness is 1 μm or more, the handling becomes easy, and when the film thickness is 50 μm or less, it is easy to bend and incorporate easily.

Also, the resin composition according to the present embodiment can be used by containing (F) a phosphorus compound from the viewpoint of improving flame retardancy. (F) As a phosphorus compound, a phosphate ester compound or a phosphazene compound can be used.

The resin composition may contain an organic solvent in addition to polyimide, a bifunctional hydroxyl group-containing compound, an oxazoline compound, and the like. It is because it can use preferably as a varnish by setting it as the state melt | dissolved in the organic solvent.

Hereinafter, examples performed to clarify the effects of the present invention will be described. In addition, this invention is not limited at all by the following examples.

The resin composition according to the first embodiment of the present invention will be described with reference to the following Example 1 and Comparative Example 1. In Example 1 below, Sample 1 to Sample 32 are the resin composition according to the second aspect, and Sample 33 to Sample 35 are the resin composition according to the first aspect.

Example 1
Sample 1 including a cured film of the resin composition was prepared, and its characteristics were confirmed. In this example, as a resin composition, a polyimide varnish having an imidization ratio of 88% (hereinafter referred to as polyimide A), a polycarbonate diol, DURANOL T5651 manufactured by Asahi Kasei Chemicals Co., Ltd. (molecular weight 1000; hereinafter, polyfunctional hydroxyl group-containing compound A) And Duranate SBN-70D (NCO content: 10.2 wt%; hereinafter referred to as isocyanate compound A) manufactured by Asahi Kasei Chemicals, which is a hexamethylene diisocyanate block isocyanate, was used. Polyfunctional hydroxyl group-containing compound A was 5 parts by mass and isocyanate compound A was 5 parts by mass with respect to 100 parts by mass of polyimide A. Moreover, it prepared so that the polyimide A might be 30 mass% with respect to the resin composition. In this case, the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the isocyanate group contained in the isocyanate compound A was hydroxyl group / isocyanate group = 0.9. Hereinafter, a method for synthesizing polyimide A, a method for producing a cured film, and a method for evaluating each property will be described.

[Polyimide A]
A method for synthesizing polyimide A will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. In an ice water bath at 0 ° C., 40 g of Jeffermine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000), 23.519 g of 1,3-bis (3-aminophenoxy) benzene (APB), 2.027 g of phthalic anhydride, γ -60 g of butyrolactone (GBL), 60 g of ethyl benzoate (BAEE), 20 g of toluene, 12 g of γ-valerolactone and 18 g of pyridine were added and stirred until uniform. Furthermore, 18.966 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA) and 19,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA) 19. 616 g was added in small portions. After stirring for 0.5 hour, the temperature was raised to 170 ° C. and heated for 4 hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. After the system was cooled to 60 ° C., 5.293 g of BTDA and 4.780 g of APB were added. After 5 hours, it was cooled to room temperature. Next, the product was pressure filtered through a 5 μm filter to obtain a polyimide A varnish having an imidization ratio of 88%.

In addition, the imidation ratio mentioned above was calculated | required by IR method. Specifically, the imidation rate was determined from the ratio of the peak based on the imide ring formation near 1380 cm ⁻¹ to the peak based on the benzene ring near 1480 cm ⁻¹ as a reference. The imidation ratio C at an arbitrary temperature is expressed by C = ((B3 / A3-B1 / A1) / (B2 / A2-B1) where A3 is an absorbance at 1480 cm ^-1 and B3 is an absorbance at 1380 cm ^{-1 at} an arbitrary temperature. / A1)) × 100 (%). Here, the absorbance at 1480 cm ⁻¹ of the resin synthesized at 50 ° C. and dried at 80 ° C. was A1, and the absorbance at 1380 cm ⁻¹ was B1. Further, the absorbance at 1480 cm ⁻¹ of the resin heat-treated at 220 ° C. for 60 minutes in the air atmosphere was A2, and the absorbance at 1380 cm ⁻¹ was B2. Also, for each peak, draw a baseline so that the valleys of the peaks are connected before and after the peak, and the height of each peak from the baseline (that is, each peak point and a line that descends from each peak to the baseline). And the distance to the intersection with the baseline) was defined as the respective absorbance. The imidation rate C calculated in the above formula is a value that makes the imidization rate during heat treatment at 220 ° C. for 60 minutes 100%.

[Preparation of cured film]
The above resin composition is applied to a substrate with a bar coater, leveled at room temperature for 5 to 10 minutes, dried and cured by heating in a hot air oven at 120 ° C. for 60 minutes, then at 180 ° C. for 30 minutes. 1 was produced. As the substrate, Kapton (registered trademark) 100EN manufactured by Toray DuPont was used. The resin composition was applied to one side of the substrate. The film thickness after drying and curing was about 20 μm.

[Evaluation of warpage]
The warpage was evaluated by lifting the four corners of the sample. Specifically, the sample 1 described above was cut into 5 cm × 5 cm in an environment of 23 ° C. and a humidity of 50%, and the distance at which the corner was raised relative to the central portion was measured as a 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 being 15 mm or less, “Δ”, and those exceeding 15 mm were evaluated as “poor”.

[Evaluation of solder resistance (heat resistance)]
The solder resistance was evaluated by immersing Sample 1 cut to 3 cm × 3 cm in a solder bath at 260 ° C. for 60 seconds in accordance with the JPCA-BM02 standard. Visually inspect the external appearance to confirm the presence or absence of changes such as deformation and dissolution traces. If no change is observed in 90% or more of the total area, the circle is marked as ○, and the area is 50% to 90%. The case where no change was observed was indicated by Δ, and the case where the region where no change was observed was less than 50% was indicated by ×.

[Evaluation of chemical resistance]
Sample 1 described above was immersed in methyl ethyl ketone for 10 minutes at room temperature, and the appearance of the coating film was visually inspected to confirm the presence or absence of changes such as deformation and dissolution traces. The case where no change is observed in 90% or more of the entire area is marked as ◯, the case where no change is seen in 50% to 90% of the total area is marked as △, and the region where no change is seen is less than 50% Was set as x.

[Evaluation of insulation resistance at 85 ° C and 85% humidity]
Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (insulating layer thickness 25 μm, conductor layer copper foil F2-WS (18 μm)) is used as the base material of the flexible printed circuit board. Line / space: 50 μm / 50 μm A comb-shaped wiring board was produced. A resin composition was applied to a part of the circuit board so as to have a film thickness after curing of 15 μm and cured to obtain Sample 1B. The curing conditions are the same as those of sample 1A. Thereafter, the resistance was measured while standing for 8 hours under the conditions of DC 50 V, 85 ° C., and humidity 85%. The case where the insulation resistance exceeded 10 ⁹ Ω was rated as “◯”, and the case where it did not reach 10 ⁹ Ω was marked as “X”.

[Evaluation of viscosity from 100 ° C. to 220 ° C.]
The viscosity of 100 ° C. to 220 ° C. was obtained by laminating 27 resin films obtained by etching and removing copper foil from a resin film having a copper foil as a base material using a measuring instrument AR-G2 manufactured by TA Instruments. Using the sample, evaluation was made with a rotor: 8 mm diameter parallel plate, strain: 0.1%, frequency: 1 Hz, and normal stress: 0.1 N (100 g). A case where the viscosity at 100 ° C. to 220 ° C. is in the range of 5000 Pa · s to 100000 Pa · s was marked with “◯”, and a case where there was a region less than 5000 Pa · s or exceeded 100,000 Pa · s was marked with “X”.

[Evaluation of elastic region and plastic region]
In accordance with JIS-C-2151 standard, the elastic region and plastic region are subjected to a tensile test with a sample of 5 mm in width and 100 mm in length at a distance between chucks of 50 mm and 100 mm / min, and the elongation to the yield point is determined as the elastic region and yield. The elongation from the point to the breaking point was evaluated as a plastic region. A case where the elastic region was a plastic region having an elongation of less than 20% and an elongation of 50% or more was rated as ○, and a case of a plastic region having an elastic region of 20% or more or an elongation of less than 50% was evaluated as x.

[Evaluation of interlayer insulation resistance]
Interlayer insulation resistance uses Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (insulation layer thickness 25 μm, conductor layer copper foil F2-WS (18 μm)) as the base material for flexible printed circuit boards. When a resin film as a base material is laminated, and then the resistance is measured for 1000 hours under conditions of DC 50 V, 85 ° C. and humidity 85%, the insulation resistance between the resin films is 10 ⁹ Ω or more. And the case where it did not reach 10 ⁹ Ω was marked as x.

[Evaluation of through hole embedding]
The through-hole embedding property was evaluated by an optical microscope after embedding the produced four-layer wiring board with an epoxy resin, cutting and polishing the wiring board. The case where resin 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 thermal shock test]
In the thermal shock test, the produced four-layer wiring board was evaluated at −40 ° C., 120 ° C. and 1000 cycles according to the JPCA-HD01-2003 standard. The case where the fluctuation of the connection resistance during the cycle was within 10% was marked as ◯, and the case where it exceeded 10% was marked as x.

[Evaluation of resin flow]
The resin flowability was determined by visually checking the resin protrusion at the end of the sample after laminating a 20 cm square resin sheet based on copper foil with copper foil F2-WS (12 μm) and vacuum press (180 ° C., 20 minutes, 4 MPa). And evaluated. The case where the protrusion of the resin was 1 mm or less was evaluated as “◯”, and the case where the resin exceeded 1 mm was evaluated as “X”.

The evaluation results of Sample 1 (Sample 1A, Sample 1B) are shown in Table 1 below. As can be seen from Table 1 below, the cured product using the resin composition according to Sample 1 is sufficiently suppressed in warping during curing and is excellent in solder resistance (that is, heat resistance). Moreover, it turns out that it is excellent also in chemical resistance and the insulation of high temperature, high humidity conditions.

Moreover, the cured product using the resin composition according to Sample 1 has good evaluation results in any of the evaluation of the elastic region and the plastic region, interlayer insulation resistance, through-hole embedding property, thermal shock test, and resin flow property. It was.

Next, a cured film was prepared using a resin composition prepared under conditions different from those of Sample 1, and the characteristics of Sample 2 to Sample 21 were confirmed.

[Sample 2 to Sample 5]
Samples 2 to 5 were prepared using a resin composition containing polyimide A, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A in the same manner as sample 1. The main difference between Sample 2 to Sample 5 is the content of the polyfunctional hydroxyl group-containing compound A and the isocyanate compound A. Specifically, Sample 2 was prepared using a resin composition obtained by adding 7.5 parts by mass of polyfunctional hydroxyl group-containing compound A and 7.5 parts by mass of isocyanate compound A to 100 parts by mass of polyimide A. Sample 3 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. Sample 4 was prepared using a resin composition in which 15 parts by mass of polyfunctional hydroxyl group-containing compound A and 15 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. Sample 5 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 15 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. The preparation method and evaluation method of Sample 2 to Sample 5 are the same as Sample 1.

[Sample 6 to Sample 9]
Samples 6 to 9 were prepared using a resin composition containing polyimide (hereinafter referred to as polyimide B) having an imidization rate of 28%, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A, which will be described later. The main difference between Samples 6 to 9 is the content of the polyfunctional hydroxyl group-containing compound A and the blocked isocyanate A. Specifically, Sample 6 was prepared using a resin composition in which polyfunctional hydroxyl group-containing compound A was added by 7.5 parts by mass and isocyanate compound A was added by 7.5 parts by mass with respect to 100 parts by mass of polyimide B. Sample 7 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B. Sample 8 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound A and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B. Sample 9 was prepared using a resin composition in which 60 parts by mass of polyfunctional hydroxyl group-containing compound A and 60 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B. The production method and evaluation method of Sample 6 to Sample 9 are the same as those of Sample 1.

[Polyimide B]
A method for synthesizing polyimide B is as follows. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. In an ice-water bath at 0 ° C., Jeffamine XTJ-542 (manufactured by Huntsman, weight average molecular weight 1000) 40 g, γ-butyrolactone (GBL) 60 g, ethyl benzoate (BAEE) 60 g, toluene 20 g, γ-valerolactone 12 g, pyridine 18 g And stirred until uniform. Further, 11.760 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added little by little. After stirring for 0.5 hour, the temperature was raised to 170 ° C. and heated for 4 hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. After cooling the system to 60 ° C., 35.6 g of BPDA and 29.738 g of APB were added. After 5 hours, it was cooled to room temperature. Next, the product was pressure filtered through a 5 μm filter to obtain a polyimide B varnish having an imidization rate of 28%.

[Sample 10 to Sample 15]
Samples 10 to 15 were prepared using a resin composition containing polyimide A and isocyanate compound A. The main difference between samples 10 to 15 is that any one of polyfunctional hydroxyl group-containing compounds B to F is used as the polyfunctional hydroxyl group-containing compound. As the polyfunctional hydroxyl group-containing compound B, polycarbonate diol Duranol T5652 (molecular weight 2000) manufactured by Asahi Kasei Chemicals Corporation was used. As the polyfunctional hydroxyl group-containing compound C, polycarbonate diol Duranol T4671 (molecular weight 1000) manufactured by Asahi Kasei Chemicals Corporation was used. As polyfunctional hydroxyl group-containing compound D, polybutadienediol G-1000 (molecular weight 1000) manufactured by Nippon Soda Co., Ltd. was used. As the polyfunctional hydroxyl group-containing compound E, GI-1000 (molecular weight 1000) manufactured by Nippon Soda Co., Ltd., which is a hydrogenated polybutadiene diol, was used. As the polyfunctional hydroxyl group-containing compound F, PTMG1000 (molecular weight 1000) manufactured by Mitsubishi Chemical Corporation, which is polytetramethylene diol, was used.

Sample 10 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound B and 5 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. Sample 11 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound C and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. Sample 12 was prepared using a resin composition obtained by adding 30 parts by mass of polyfunctional hydroxyl group-containing compound D and 30 parts by mass of isocyanate compound A to 100 parts by mass of polyimide A. Sample 13 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound E and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. Sample 14 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound F and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. Sample 15 was prepared using a resin composition in which 7.5 parts by mass of polyfunctional hydroxyl group-containing compound B and 7.5 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. The production method and evaluation method of Sample 10 to Sample 15 are the same as those of Sample 1.

[Sample 16, Sample 17]

Samples

16 and 17 were prepared using a resin composition containing polyimide A and polyfunctional hydroxyl group-containing compound A. The main difference between Sample 16 and Sample 17 is that any of isocyanate compounds B and C is used as the isocyanate compound. As the isocyanate compound B, hexamethylene diisocyanate block isocyanate, Duranate TPA-B80E (NCO content = 12.5 wt%) manufactured by Asahi Kasei Chemicals Corporation was used. As isocyanate compound C, product number 7951 (NCO content = 7.80 wt%) manufactured by Baxenden, which is an isophorone diisocyanate-based blocked isocyanate, was used.

Sample 16 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 9 parts by mass of isocyanate compound B were added to 100 parts by mass of polyimide A. Sample 17 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 14 parts by mass of isocyanate compound C were added to 100 parts by mass of polyimide A. The production method and evaluation method of Sample 16 and Sample 17 are the same as Sample 1.

[Sample 18, Sample 19]
Samples 18 and 19 were prepared using a resin composition containing polyimide B, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A. The main differences between Sample 18 and Sample 19 are the content of polyfunctional hydroxyl group-containing compound A and isocyanate compound A, and the heating conditions during curing. Specifically, Sample 18 was prepared using a resin composition in which 10 parts by mass of polyfunctional hydroxyl group-containing compound A and 10 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B. Sample 19 was prepared using a resin composition in which 30 parts by mass of polyfunctional hydroxyl group-containing compound A and 30 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide B. The heating conditions for curing were 180 ° C. for 60 minutes, then 180 ° C. for 60 minutes (that is, 180 ° C., 60 minutes × 2). The production method and evaluation method of Sample 18 and Sample 19 excluding the heating conditions are the same as those of Sample 1.

[Sample 20, Sample 21]
Sample 20 and Sample 21 were prepared using a resin composition containing polyimide A, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A in the same manner as Sample 1. The main difference between Sample 20 and Sample 21 is the content of polyfunctional hydroxyl group-containing compound A and isocyanate compound A. Specifically, Sample 20 was prepared using a resin composition in which 3 parts by mass of polyfunctional hydroxyl group-containing compound A and 3 parts by mass of isocyanate compound A were added to 100 parts by mass of polyimide A. Sample 21 was prepared using a resin composition obtained by adding 70 parts by mass of polyfunctional hydroxyl group-containing compound A and 70 parts by mass of isocyanate compound A to 100 parts by mass of polyimide A. The preparation method and evaluation method of the sample 20 and the sample 21 are the same as those of the sample 1.

The evaluation results of Sample 2 to Sample 21 are shown in Table 1 below. As can be seen from Table 1 below, the cured product using the resin composition in this example has sufficiently suppressed warpage during curing, and is excellent in solder resistance (ie, heat resistance). It also has excellent chemical resistance and insulation under high temperature and high humidity conditions. From the evaluation results of Sample 10 to Sample 15 and the like, it can be seen that polybutadiene diol, hydrogenated polybutadiene diol, and polycarbonate diol are preferably used as the polyfunctional hydroxyl group-containing compound from the viewpoint of enhancing the insulation. From the viewpoint of reducing warpage, it is preferable to contain at least 3 parts by mass to 70 parts by mass of polyimide, more preferably 5 parts by mass to 70 parts by mass with respect to 100 parts by mass of the resin composition. It can be seen that the content is more preferably 60 parts by mass to 60 parts by mass. From the evaluation results of Sample 18 and Sample 19, the heat treatment in the low temperature region (100 to 130 ° C) and the heat treatment in the high temperature region (160 to 200 ° C) are combined from the viewpoint of improving heat resistance and chemical resistance. It can be seen that it is preferable to use them. However, the heat treatment conditions are not limited to this.

Next, a cured film was prepared using a resin composition prepared under conditions different from those of Sample 1 to Sample 21, and the characteristics of Sample 22 to Sample 29 were confirmed.

[Sample 22 to Sample 25]
Samples 22 to 25 were prepared in the same manner as Sample 1 using a resin composition containing polyimides C to F, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A. The main difference between sample 22 to sample 25 is the imidization ratio of polyimide. Specifically, Samples 22 to 25 were prepared using a resin composition in which 15 parts by mass of the polyfunctional hydroxyl group-containing compound A and 15 parts by mass of the isocyanate compound A were added to 100 parts by mass of polyimides C to F. . The preparation method and evaluation method of Samples 22 to 25 are the same as Sample 1.

[Polyimide C]
A method for synthesizing polyimide C will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of γ-butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of 4,4′-oxydiphthalic dianhydride (manac, ODPA) Stir until uniform. Thereafter, the temperature was raised to 80 ° C., 11.30 g (13.78 mmol) of silicone diamine (manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation KF-8010) was added, and the mixture was further stirred for 0.5 hour, and then heated to 170 ° C. Heated for hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. After cooling the system to 100 ° C., 0.14 g of maleic anhydride was added and stirred for 0.5 hour. After standing at room temperature for 25 hours and cooling, 6.00 g (20.52 mmol) of 1,3-bis (3-aminophenoxy) benzene (Mitsui Chemicals, abbreviated as APB-N) was added. Stir for 5 hours at room temperature 25 ° C. Next, the product was pressure filtered through a 5 μm filter to obtain a polyimide C varnish having an imidization ratio of 40%.

[Polyimide D]
A method for synthesizing polyimide D will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature of 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of γ-butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of ODPA were added and stirred until uniform. Thereafter, the temperature was raised to 80 ° C., 11.30 g (13.78 mmol) of KF-8010 was added, and the mixture was further stirred for 2 hours. Then, 2.17 g (7.42 mmol) of APB-N for the first time was added to 0.5%. After stirring for an hour, the temperature was raised to 170 ° C. and heated for 4 hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. After cooling the system to 100 ° C., 0.14 g of maleic anhydride was added and stirred for 0.5 hour. After allowing to stand at room temperature for 25 hours and cooling, 3.83 g (13.10 mmol) of the second APB-N was added. Stir for 5 hours at room temperature 25 ° C. Next, the product was pressure filtered through a 5 μm filter to obtain a polyimide D varnish having an imidization ratio of 60%.

[Polyimide E]
A method for synthesizing polyimide E will be described. The polyimide F synthesis method except that the first APB-N is 4.03 g (13.78 mmol) and the second APB-N is 1.97 g (6.73 mmol). Similarly, a polyimide E varnish having an imidization ratio of 80% was obtained.

[Polyimide F]
A method for synthesizing polyimide F will be described. The polyimide D synthesis method except that the first APB-N is 4.86 g (16.62 mmol) and the second APB-N is 1.03 g (3.52 mmol). Similarly, a polyimide F varnish having an imidization ratio of 90% was obtained.

[Sample 26]
Sample 26 was prepared in the same manner as Sample 1 using a resin composition containing polyimide C, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A. The main difference between sample 26 and sample 22 is the addition of flame retardant components. Specifically, for sample 26, 15 parts by mass of polyfunctional hydroxyl group-containing compound A and 15 parts by mass of isocyanate compound A with respect to 100 parts by mass of polyimide C, phosphazene derivative FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd. ) Was added using 23 parts by mass of the resin composition. The preparation method and evaluation method of the sample 26 are the same as those of the sample 1.

[Sample 27]
Sample 27 was prepared using the same resin composition as Sample 26. The main difference between the sample 27 and the sample 26 is the substrate used in [Preparation of cured film]. Specifically, in Sample 27, a 12 μm-thick copper foil F2-WS film manufactured by Furukawa Circuit Foil Co., Ltd. was used as the substrate, and a cured film was formed on the mat surface of the copper foil. The film thickness after drying and curing was about 30 μm. Other manufacturing methods and evaluation methods of the sample 27 are the same as those of the sample 1.

[Sample 28]
Sample 28 was prepared in the same manner as Sample 1 using a resin composition containing polyimide C, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A. The main difference between the sample 28 and the sample 22 is the addition of a flame retardant component and the addition of a catalyst. Sample 28 is 18 parts by mass of polyfunctional hydroxyl group-containing compound A, 18 parts by mass of isocyanate compound A, and 27 parts by mass of phosphazene derivative FP-300 (flame retardant A) manufactured by Fushimi Pharmaceutical Co., Ltd. with respect to 100 parts by mass of polyimide C. 18 parts by mass of melamine cyanurate MC-20NJ pulverized product (flame retardant B: average particle size 1.1 μm, maximum particle size 3 μm) manufactured by Sakai Chemical Industry Co., Ltd., U-CAT SA (registered trademark) 102 manufactured by San Apro It was prepared using a resin composition to which (Catalyst A) was added at 0.18 parts by mass. For the preparation method and evaluation method of the sample 28, a 12 μm-thick copper foil F2-WS film manufactured by Furukawa Circuit Foil Co., Ltd. was used as a substrate, and a cured film was formed on the mat surface of the copper foil. It is the same as Sample 1 except that it is dried and cured by heating for 10 minutes and 200 ° C. for 15 minutes, and the cured film thickness is about 30 μm.

[Sample 29]
Sample 29 was prepared using the same resin composition as Sample 28. The main difference between sample 29 and sample 29 is only the catalyst species. Specifically, 0.18 parts by mass of U-CAT (registered trademark) 1102 (catalyst B) manufactured by San Apro was used. Other manufacturing methods and evaluation methods of the sample 29 are the same as those of the sample 28.

The evaluation results of Sample 22 to Sample 29 are shown in Table 2 below. As can be seen from Table 2 below, the cured products using the resin compositions according to Samples 22 to 29 are sufficiently suppressed in warping during curing and have excellent solder resistance (ie, heat resistance). Further, it was excellent in chemical resistance and insulation under high temperature and high humidity conditions, and the same effects as those of the resin compositions according to Sample 1 to Sample 21 shown in Table 1 below were obtained.

Next, Sample 30 to Sample 32 were prepared using the resin films prepared from Sample 27 to Sample 29, and their characteristics were confirmed.

[Sample 30]
Sample 30 was produced using the resin film obtained in Sample 27. The main difference between the sample 30 and the sample 30 is that a resin film is laminated on a wiring board. Specifically, Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.) (insulating layer thickness 25 μm, conductor layer copper foil F2-WS (18 μm)) is used as the base material of the flexible printed wiring board, and the diameter is 0.1 mm. Drill holes at 4 mm intervals, copper plating, and then laminate a resin film on both sides of the patterned wiring board by vacuum press (180 ° C, 20 minutes, 4 MPa), and after patterning, laser via processing in the center between the through holes A four-layer wiring board was prepared by copper plating and connecting 25 vias in a daisy chain.

[Sample 31, Sample 32]
Sample 31 was sample 28 and sample 32 was sample 29. A wiring board was prepared by the same method as sample 30 and evaluated by the same method as sample 30.

Next, a resin film was prepared using a resin composition prepared under conditions different from those of Sample 1 to Sample 32, and the characteristics of the prepared Sample 33 to Sample 35 were confirmed.

[Sample 33]
Sample 33 is a varnish of polyimide G having an imidization ratio of 100%, polyfunctional hydroxyl group-containing compound A, and Duranate TPA-100 manufactured by Asahi Kasei Chemicals, which is a hexamethylene diisocyanate-based isocyanate (NCO content: 23.1 wt%; What added the isocyanate compound C) was used. Polyfunctional hydroxyl-containing compound A was 10 parts by mass and isocyanate compound C was 4.4 parts by mass with respect to 100 parts by mass of polyimide G. Moreover, it prepared so that polyimide G might be 30 mass% with respect to the resin composition. In this case, the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the isocyanate group contained in the isocyanate compound D was hydroxyl group / isocyanate group = 0.9. Using this resin composition, a wiring board was produced in the same manner as in Sample 30 and evaluated in the same manner as in Sample 30.

[Polyimide G]
A method for synthesizing polyimide G will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of γ-butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of 4,4′-oxydiphthalic dianhydride (manac, ODPA) Stir until uniform. Thereafter, the temperature was raised to 80 ° C., 11.30 g (13.78 mmol) of silicone diamine (manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation KF-8010) was added, and the mixture was further stirred for 0.5 hour, and then heated to 170 ° C. Heated for hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. After cooling the system to 100 ° C., 0.14 g of maleic anhydride was added and stirred for 0.5 hour. After standing at room temperature for 25 hours and cooling, 1,3-bis (3-aminophenoxy) benzene (Mitsui Chemicals, abbreviation APB-N) 6.00 g (20.52 mmol), γ-butyrolactone 35 g, 20.0 g of toluene was added. After stirring for 0.5 hour, the temperature was raised to 170 ° C. and heated for 4 hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. Next, the product was pressure filtered through a 5 μm filter to obtain a polyimide G varnish having an imidization rate of 100%.

[Sample 34]
Sample 34 was obtained by adding Polyurethane G varnish to polycarbonate diol, Duranol T5650E (molecular weight 500) manufactured by Asahi Kasei Chemicals, and isocyanate compound D. T5650E was 5 parts by mass and isocyanate compound D was 4.4 parts by mass with respect to 100 parts by mass of polyimide G. Moreover, it prepared so that the polyimide H might be 30 mass% with respect to the resin composition. In this case, the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the isocyanate group contained in the isocyanate compound D was hydroxyl group / isocyanate group = 0.9. Using this resin composition, a wiring board was produced in the same manner as in Sample 30 and evaluated in the same manner as in Sample 30.

[Sample 35]
Sample 35 was obtained by adding polycarbonate polyol A having an average hydroxyl number of 3.6 as polycarbonate polyol and hexamethylene diisocyanate (hereinafter referred to as isocyanate compound E) to the varnish of polyimide G. The polycarbonate polyol A was 6.2 parts by mass and the hexamethylene diisocyanate was 2 parts by mass with respect to 100 parts by mass of the polyimide G. Moreover, it prepared so that polyimide G might be 30 mass% with respect to the resin composition. In this case, the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the isocyanate group contained in the isocyanate compound E was hydroxyl group / isocyanate group = 0.9. Using this resin composition, a wiring board was produced in the same manner as in Sample 30 and evaluated in the same manner as in Sample 30. The evaluation results of Sample 30 to Sample 35 are shown in Table 3 below.

[Polycarbonate polyol A]
A method for synthesizing the polycarbonate polyol A will be described. In a 2 liter flask equipped with a 10 mm diameter, 300 mm long distillation column and a thermometer and a stirrer packed with Dickson packing, ethylene carbonate: EC 871.6 g (9.9 mol) trimethylolpropane: TMP 530.8 g (3. 96 mol), 1.61.6 hexanediol: HDL (351.6 g, 2.98 mol) and 1.5-pentanediol: PDL (310 g, 2.98 mol) were added, and the mixture was heated and stirred under a reduced pressure of 20 torr. Was controlled to be 120 ° C to 130 ° C. The reaction was carried out for 18 hours while distilling EC and ethylene glycol having an azeotropic composition from the top of the distillation column. Next, the distillation column was removed, and the degree of vacuum was set at 4 Torr to recover unreacted EC and diol. After completion of distillation of the unreacted substance, the internal temperature was set to 190 ° C., and the diol was distilled while maintaining the temperature to perform a self-condensation reaction. After carrying out the reaction for 5 hours, a colorless transparent viscous liquid having a number average molecular weight of 1014 (polystyrene conversion) was obtained by GPC (gel permeation chromatography) analysis. The yield was 1200 g. This liquid had the following physical properties. Composition (mol%); HDL: PDL: TMP = 30.0: 21.7: 45.4, 0.4% of other units containing an ether bond, OH value (mgKOH / g) = 198.8, average The number of hydroxyl groups was 3.6.

[Evaluation of molecular weight of polyfunctional hydroxyl group-containing compound]
The molecular weight of the polyfunctional hydroxyl group-containing compound was measured by gel permeation chromatography (manufactured by Tosoh Corporation) and evaluated by the number average molecular weight of the styrene equivalent molecular weight.

As can be seen from Table 3 below, the resin film using the resin composition according to Sample 30 to Sample 35 is excellent in interlayer insulation resistance, through-hole embedding property, solder resistance (that is, heat resistance), and thermal shock resistance. The same effects as those of the resin compositions according to Sample 1 to Sample 21 shown in Table 1 below were obtained. Also, when using polyimide with 100% imidization ratio (sample 33 to sample 35), using trifunctional or higher polyfunctional hydroxyl group-containing compound (sample 35), using bifunctional isocyanate compound (sample) 35), it can be seen that good results can be obtained even when an isocyanate compound other than the blocked isocyanate is used (sample 33 to sample 35).

(Comparative Example 1)
As a comparative example, a cured film was prepared using a resin composition prepared under conditions different from those of Example 1 described above, and the characteristics of the prepared sample were confirmed. In this comparative example, Comparative Sample 1 to Comparative Sample 8 were prepared and their characteristics were confirmed.

[Comparative Sample 1 to Comparative Sample 3]
Comparative samples 1 to 3 were prepared using a resin composition containing polyimide A. The main differences between Comparative Sample 1 to Comparative Sample 3 are components other than polyimide A. Specifically, Comparative Sample 1 was prepared using a resin composition not containing polyfunctional hydroxyl group-containing compound A and isocyanate compound A. The comparative sample 2 was produced using the resin composition which added polyfunctional hydroxyl-containing compound A by 5 mass parts with respect to 100 mass parts of polyimide A. The comparative sample 3 was produced using the resin composition which added the isocyanate compound A at 5 mass parts with respect to 100 mass parts of polyimide A. The preparation method and evaluation method of Comparative Sample 1 to Comparative Sample 3 are the same as those in Example 1.

[Comparative Sample 4 and Comparative Sample 5]
Comparative sample 4 and comparative sample 5 were prepared using a resin composition containing polyimide A, polyfunctional hydroxyl group-containing compound A, and isocyanate compound A. The main difference between the comparative samples 4 and 5 is that the content of the isocyanate compound A with respect to the polyfunctional hydroxyl group-containing compound A (that is, the molar ratio between the hydroxyl group contained in the functional hydroxyl group-containing compound and the isocyanate group contained in the isocyanate compound A). It is. More specifically, the comparative sample 4 adds 10 parts by mass of the polyfunctional hydroxyl group-containing compound A and 6 parts by mass of the isocyanate compound A with respect to 100 parts by mass of the polyimide A, so that the molar ratio between the hydroxyl group and the isocyanate group is increased. It was produced using a resin composition in which hydroxyl group / isocyanate group = 1.4. The comparative sample 5 adds 10 parts by mass of the polyfunctional hydroxyl group-containing compound A and 20 parts by mass of the isocyanate compound A with respect to 100 parts by mass of the polyimide A, whereby the molar ratio of hydroxyl group to isocyanate group is determined by hydroxyl group / isocyanate group = It produced using the resin composition made into 0.4. The preparation method and evaluation method of the comparative samples 4 and 5 are the same as those in Example 1.

[Comparative Sample 6]
Comparative sample 6 was prepared using a resin composition containing polyfunctional hydroxyl group-containing compound A and isocyanate compound A. That is, the comparative sample 6 was produced using the resin composition which does not contain a polyimide. The preparation method and evaluation method of the comparative sample 6 are the same as those in Example 1.

[Comparative Sample 7]
Comparative sample 7 was prepared using a resin composition containing a polyfunctional hydroxyl group-containing compound and a polyimide having a imidization ratio of 100% in which a blocked isocyanate was incorporated into the skeleton (polyimide not containing a polyamic acid structure; hereinafter, polyimide H). did. Polyimide H contains a polyfunctional hydroxyl group-containing compound and a blocked isocyanate, and therefore does not contain a polyfunctional hydroxyl group-containing compound and a blocked isocyanate as a component of the resin composition. The preparation method and evaluation method of the comparative sample 7 are the same as those in Example 1.

[Polyimide H]
The synthesis method of polyimide H is as follows. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. Asahi Kasei Chemicals Co., Ltd. Duranol T5651 (molecular weight 1000) 78.88 g, hexamethylene diisocyanate 26.91 g, γ-butyrolactone (GBL) 177 g was charged. After stirring at 200 rpm for 15 minutes at room temperature in a nitrogen atmosphere, the temperature was raised to 140 ° C. and stirred for 1 hour. Then, 62.04 g (200 mmol) of 4,4′-oxydiphthalic dianhydride and 176 g of GBL were added and reacted at 170 ° C. and 200 rpm with stirring for 1.5 hours. Further, after cooling to room temperature, 5.88 g of BPDA, 40.55 g of APB, 353 g of GBL, 70 g of toluene, 2.2 g of γ-valerolactone and 3.5 g of pyridine were added and reacted for 3.5 hours while stirring at 170 ° C. and 200 rpm. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. Next, the product was pressure filtered through a 5 μm filter to obtain a polyimide H varnish having an imidization rate of 100%. That is, the polyimide H does not contain a polyamic acid structure in the polyimide in the resin composition and incorporates a polyfunctional hydroxyl group-containing compound and a blocked isocyanate into the polyimide skeleton, not as components in the resin composition. It corresponds to.

The evaluation results of Comparative Sample 1 to Comparative Sample 7 are shown in Table 4 below. From Comparative Samples 1 to 3 and 6, it was confirmed that when any of polyimide, polyfunctional hydroxyl group-containing compound and isocyanate compound was missing, a good cured product could not be obtained. Further, from Comparative Samples 4 and 5, when the hydroxyl group / isocyanate group is excessive in the isocyanate compound = 0.4, the warpage occurs due to the reaction between the isocyanate compounds, and the hydroxyl group / isocyanate group in which the polyfunctional hydroxyl group-containing compound is excessive = In 1.4, it was confirmed that unreacted substances increased and the chemical resistance decreased. That is, it was confirmed that when the hydroxyl group / isocyanate group was not 0.5 to 1, a good cured product could not be obtained. Further, from Comparative Sample 7, when a polyfunctional hydroxyl group-containing compound and an isocyanate compound are incorporated into the skeleton and the resin composition does not contain a polyfunctional hydroxyl group-containing compound and an isocyanate compound, a good cured product is obtained. It was confirmed that it was not possible.

As can be seen from Tables 1 to 4, the evaluation results of Example 1 and Comparative Example 1 contain a polyimide having a polyimide structure and a polyamic acid structure as structural units, a polyfunctional hydroxyl group-containing compound, and an isocyanate compound. By using a resin composition in which the molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the isocyanate group contained in the isocyanate compound is hydroxyl group / isocyanate group = 0.5 to 1, warpage is sufficiently suppressed. It was confirmed that a cured film having excellent heat resistance was obtained.

Further, as can be seen from Table 1 to Table 3, in the resin films according to Sample 1 to Sample 35 using the resin composition according to Example 1, the viscosity of 120 ° C. to 220 ° C., the elastic region of the resin film, and the plasticity It can be seen that the resin flowability, through-hole embedding property, and thermal shock resistance are improved. For this reason, when it uses for the manufacturing process of a wiring board, the embedding property to a through hole and the prevention of the outflow of the resin composition from the edge part of a wiring board can be made compatible.

The resin composition according to the second embodiment of the present invention will be described with reference to the following Example 2 to Example 12 and Comparative Example 2 to Comparative Example 6. In addition, the following Examples 2 to 12 are resin compositions according to the second aspect.

<Reagent>
In the examples and comparative examples, the reagents used are as follows. In addition, in the following Example 2 to Example 12, Comparative Example 2 to Comparative Example 6, and Tables 5 and 6, abbreviations of the following reagents are indicated.

(A) Polyimide component: BPDA (manufactured by Mitsui Chemicals), APB (trade name: APB-N, manufactured by Mitsui Chemicals), diamine represented by the general formula (5): polyetheramine (trade name: polyetheramine) D-400 (hereinafter simply referred to as “D-400”), manufactured by BASF, m + n + p = 6.1), Jeffamine (trade name: Jeffamine D-230 (hereinafter simply referred to as “D-230”) ), Manufactured by Huntsman, m + n + p = 2.5), Jeffermin (trade name: Jeffamine XTJ-542 (hereinafter simply referred to as “XJT-400”), manufactured by Huntsman, m + n + p = 15), Jeffermin (Product name: Jeffermin D-2000, manufactured by Huntsman, m + n + p = 33)
(B) Bifunctional hydroxyl group-containing compound: polycarbonate diol (trade name: Duranol T5651 (hereinafter simply referred to as “T5651”), manufactured by Asahi Kasei Chemicals), polycarbonate diol (trade name: Duranol T4671 (hereinafter simply “T4671”) And Asahi Kasei Chemicals)
(C-1) Isocyanate compound: Blocked isocyanate (trade name: Duranate SBN-70D (hereinafter simply referred to as “SBN-70D”), manufactured by Asahi Kasei Chemicals), Block isocyanate (trade name: Duranate TPA-B80E (hereinafter referred to as “Duranate TPA-B80E”) , Simply referred to as “TPA-B80E”), manufactured by Asahi Kasei Chemicals Corporation)
(D) Photosensitive agent 1 (compound having two double bonds): EO-modified bisphenol A dimethacrylate (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
(D) Photosensitive agent 2 (compound having three or more double bonds): trimethylolpropane PO-modified triacrylate (trade name: Aronix M-310 (hereinafter simply referred to as “M-310”), Toagosei Co., Ltd. Manufactured, equivalent to a compound having three double bonds)
(E) Photopolymerization initiator: Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (trade name: IRGACURE OXE-02 , Made by Ciba Japan)
(F) Phosphorus compound: Phosphazene compound (trade name: FP-300, manufactured by Fushimi Pharmaceutical Co., Ltd.)
(Others): Toluene (Wako Pure Chemical Industries, for organic synthesis), γ-butyrolactone (Wako Pure Chemical Industries), sodium carbonate (Wako Pure Chemical Industries)

<Weight average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the weight average molecular weight, was measured 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. 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 (made by Showa Denko)
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).

<Film thickness measurement>
The film thickness of the cured product was measured using a film thickness meter (ID-C112B manufactured by Mitutoyo).

<Method for producing photosensitive film>
The coating method of the photosensitive resin composition was performed by a doctor blade method using FILMCOATER (manufactured by TESTER SANGYO, PI1210). The photosensitive resin composition was dropped onto a PET film (Teijin Deyupon Film Co., Ltd., G2) and coated with a clearance of 150 μm. The coated film was dried at 95 ° C. for 12 minutes using a dryer (manufactured by ESPEC, SPHH-10 l) to obtain a photosensitive film.

<Lamination conditions>
Lamination was performed using a vacuum press (manufactured by Meiki Seisakusho). The press temperature was 70 ° C., the press pressure was 0.5 MPa, and the press time was 30 seconds.

<Developability evaluation>
Evaluation of developability was carried out by laminating on a copper-clad laminate using a photosensitive film under the above-mentioned laminating conditions, followed by exposure at 30-300 mJ / cm ² , followed by alkaline with 1% by mass sodium carbonate aqueous solution. Development and rinsing with water were performed, and after drying, the pattern was evaluated with an optical microscope. A circular pattern having a 100 μm diameter (interval of 100 μm pitch) was used as the mask. The development shows that the copper surface appears in the unexposed area and the remaining film rate is 90% or more and the pattern is not destroyed. The result is ○, and the remaining film rate is 90% or more, but the pattern is broken. △ was given.

<Measurement of warpage after firing>
The obtained photosensitive film was laminated on Kapton (registered trademark) (12 μm) under the above laminating conditions, and then baked at 180 ° C. for 2 hours. This film was cut into 5 cm squares, and those having a floating height of 5 mm or less at the end were indicated by ◯, those having a height of 5 to 10 mm or less were indicated by Δ, and those having a floating height higher than that were indicated by ×.

<Insulation reliability (IM resistance) evaluation>
The insulation reliability evaluation was performed as follows. A photosensitive film was laminated on the comb substrate having a line and space of 20 μm / 20 μm under the above laminating conditions, then exposed and developed under the above conditions, and baked at 180 ° C. for 2 hours. A migration tester cable was soldered to the film, and an insulation reliability test was conducted under the following conditions.
Insulation deterioration 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 insulation resistance: 1.0 × 10 was less than ⁶ Omega and ×, less than ^{1.0 × 10 6 Ω ~ 1.0 ×} 10 7 Ω △ and then, 1.0 × 10 ⁷ Ω ~ 1 less than .0 × 10 ⁸ Ω and ○, was 1.0 × 10 ⁸ Ω or more ◎ with.

Appearance (Dendrite): Comb substrate after IM test is observed with an optical microscope (ECLIPS LV100, manufactured by Nikon Corp.) under the conditions of transmitted light, 200 times. ○.

Appearance (swelling and discoloration): Comb substrate after IM test is observed with an optical microscope (ECLIPS LV100, manufactured by Nikon) under conditions of 100 times bright field. The case where only the swelling of the film was observed was indicated by Δ, and the case where no swelling or discoloration was observed was indicated by ○.

<Polyimide (1)>
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (255 g), toluene (51.0 g), polyetheramine D-400 (86.8 g (201.9 mmol)), BPDA. (120 g (407.9 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 40 ° C., APB-N (48.4 g (165.7 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours. Obtained. The weight average molecular weight of the obtained polyimide (1) is shown in Table 5 below.

<Polyimide (2)>
Under a nitrogen atmosphere, in a separable flask equipped with a Dean Stark apparatus and a refluxer, γ-butyrolactone (87.0 g), toluene (17.0 g), polyetheramine D-400 (5.00 g (11.63 mmol)) BPDA (30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 40 ° C., APB-N (23.5 g (80.39 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours. Obtained. The weight average molecular weight of the obtained polyimide (2) is shown in Table 5 below.

<Polyimide (3)>
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (99.0 g), toluene (20.0 g), and polyetheramine D-400 (32.0 g (74.42 mmol)). BPDA (30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 40 ° C., APB-N (5.00 g (17.10 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide (3) solution. Obtained. The weight average molecular weight of the obtained polyimide (3) is shown in Table 5 below.

<Polyimide (4)>
Under a nitrogen atmosphere, in a separable flask equipped with a Dean Stark apparatus and a refluxer, γ-butyrolactone (80.0 g), toluene (16.0 g), polyetheramine D-230 (16.8 g (73.04 mmol)) BPDA (30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene, which is an azeotropic solvent, the solution was cooled to 40 ° C., then APB-N (5.60 g (19.16 mmol) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide (4) solution. The weight average molecular weight of the obtained polyimide (4) is shown in Table 5 below.

<Polyimide (5)>
In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with γ-butyrolactone (107 g), toluene (21.0 g), Jeffamine XTJ-542 (25.7 g (25.70 mmol)), BPDA ( 30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene, which is an azeotropic solvent, the solution was cooled to 40 ° C., then APB-N (18.9 g (64.65 mmol) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide (5) solution. The weight average molecular weight of the obtained polyimide (5) is shown in Table 5 below.

<Polyimide (6)>
In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with γ-butyrolactone (120 g), toluene (24.0 g), Jeffamine D-2000 (27.4 g (13.70 mmol)), BPDA ( 30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 40 ° C., APB-N (22.2 g (75.94 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide (6) solution. The weight average molecular weight of the obtained polyimide (6) is shown in Table 5 below.

[Example 2]
With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Example 3]
T4671 (6 parts by mass), SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1) with respect to 100 parts by mass of polyimide (1) Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Example 4]
With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), TPA-B80E (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Example 5]
With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), SBN-70D (10 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Example 6]
With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), OXE-02 (1 part by mass), FP-300 (25 Part by mass) was mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Example 7]
With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), SBN-70D (6 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 Part by mass) was mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Examples 8 to 12]
For each 100 parts by mass of polyimide (2) to (6), T5651 (6 parts by mass), SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Comparative Example 2]
BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass) are mixed with 100 parts by mass of polyimide (1). A photosensitive resin composition was prepared. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Comparative Example 3]
With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 Part by mass) was mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Comparative Example 4]
SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 with respect to 100 parts by mass of polyimide (1) (25 parts by mass) was mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Comparative Example 5]
With respect to 100 parts by mass of polyimide (1), T5651 (6 parts by mass), SBN-70D (15 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

[Comparative Example 6]
With respect to 100 parts by mass of polyimide (1), T5651 (15 parts by mass), SBN-70D (6 parts by mass), BPE-500 (40 parts by mass), M-310 (20 parts by mass), OXE-02 (1 Part by mass) and FP-300 (25 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. The photosensitive film was evaluated for developability, warpage after firing, and insulation reliability (IM resistance) by the above-described methods. The results are shown in Table 6 below.

From the results shown in Tables 5 and 6, it can be seen that Examples 2 to 12 have better developability, warpage, and insulation reliability than Comparative Examples 2 to 6. In particular, in Examples 2 to 12, it can be seen that in any case of 0.10 ≦ (A + B) / (A + B + C) ≦ 0.85, developability, warpage, and insulation reliability are obtained.

On the other hand, warpage and dendrite occurred in the photosensitive composition containing no bifunctional hydroxyl group-containing compound and isocyanate compound (see Comparative Example 2). Even in the case of containing a bifunctional hydroxyl group-containing compound, in the photosensitive resin composition not containing an isocyanate compound, an improvement was seen in warpage, but dendrite was generated (see Comparative Example 3). Even in the case of containing an isocyanate compound, in the photosensitive resin composition not containing a bifunctional hydroxyl group-containing compound, dendrite was improved, but warping occurred (Comparative Example 4). reference). These results are considered that warpage and dendrite were caused because they did not contain a bifunctional hydroxyl group-containing compound effective in reducing warpage or an isocyanate compound that forms a crosslinked structure with polyimide and a bifunctional hydroxyl group-containing compound. Yeah.

Further, even when the bifunctional hydroxyl group-containing compound and the isocyanate compound are contained, in the photosensitive resin composition, the molar ratio of the hydroxyl group of the bifunctional hydroxyl group-containing compound to the isocyanate group of the isocyanate compound is smaller than 0.5. As a result, warping occurred (see Comparative Example 5), and in the photosensitive resin composition exceeding 1.0, dendrites were generated (see Comparative Example 6). These results show that warping occurred because the proportion of the bifunctional hydroxyl group-containing compound effective in reducing warpage was small, or that dendrites were not formed because a sufficient crosslinking structure could not be formed with polyimide because the proportion of isocyanate compound was small. Conceivable.

The resin composition according to the third embodiment of the present invention will be described with reference to the following Example 13 to Example 24, Comparative Example 7, and Comparative Example 8. In addition, the following Example 13 to Example 24 are resin compositions according to the second aspect.

<Reagent>
In Examples and Comparative Examples, silicone diamine (manufactured by Shin-Etsu Chemical Co., Ltd., KF-8010), 1,3-bis (3-aminophenoxy) benzene (manufactured by Mitsui Chemicals, APB-N), Tetramethylene oxide-di-p-aminobenzoate (Ihara Chemical Co., abbreviation PMAB, the following general formula (22)), 4,4′-oxydiphthalic dianhydride (Manac Co., abbreviation ODPA), 3,3 ′ , 4,4'-biphenyltetracarboxylic dianhydride (Mitsui Chemicals, abbreviation BPDA), pyromellitic anhydride (Daicel Chemical Industries, abbreviation PMDA), ethylene glycol bis (trimellitic acid monoester anhydride) ) (Manufactured by Shin Nippon Chemical Co., Ltd., Ricacid TMEG-100, abbreviated TMEG), tris (butoxyethyl) phosphate (manufactured by Daihachi Chemical Co., XP), phosphazene compound (Fushimi Pharmaceutical Co., Ltd., Rabitle (registered trademark) FP-300, abbreviated FP-300), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl] -1- (O-acetyloxime) (manufactured by Ciba Japan, trade name: IRGACURE OXE 02, abbreviation OXE-02), 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (new Nakamura Chemical Co., Ltd., trade name: BPE-500), ethylene oxide (EO) modified bisphenol A dimethacrylate (Shin Nakamura Chemical Co., trade name: BPE-500), heptapropylene glycol dimethacrylate (Shin Nakamura Chemical) Manufactured by Kogyo Co., Ltd., trade name: 9PG), pentaerythritol tri / tetra (meth) acrylate (Toagoi) Manufactured by Seisha Co., Ltd., trade name: Aronix M-306, abbreviated name M-306), trimethylolpropane EO modified triacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-350, abbreviated name M-350), trimethylolpropane PO modified Triacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-310, abbreviation M-310), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMMT), EO-modified glycerol tri (meth) acrylate (Manufactured by Shin-Nakamura Chemical Co., Ltd., A-GLY-9E (EO-modified 9 mol)) polycarbonate diol (Asahi Kasei Chemicals, Duranol T5651), hexamethylene diisocyanate block isocyanate (Asahi Kasei Chemicals, Duranate SBN-70D) toluene ( Wako Jun Manufactured by Kogyo Co., Ltd., for organic synthesis), γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.), triethylene glycol dimethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) Used in reaction without performing.

<Weight average molecular weight measurement>
The measurement was performed under the same conditions as in the example according to the second embodiment.

<Photosensitive film manufacturing method>
It was produced in the same manner as the example according to the second embodiment.

<Lamination conditions>
It implemented similarly to the Example which concerns on the said 2nd Embodiment.

<Evaluation of insulation reliability (HAST resistance)>
The insulation reliability evaluation was performed as follows. A photosensitive dry film was laminated on the comb substrate having a line-and-space of 20 μm / 20 μm under the above-mentioned laminating conditions, then exposed and developed under the above conditions, and baked at 180 ° C. for 1 hour. A migration tester cable was soldered to the photosensitive dry film, and an insulation reliability test was performed under the following conditions.
Insulation deterioration evaluation system: SIR-12 (Enomoto Kasei Co., Ltd.)
HAST chamber: EHS-211M (Espec Corp.)
Temperature: 110 ° C
Humidity: 85%
Applied voltage: 2V
Application time: 528 hours

Insulation resistance: 1.0 × a × less than 10 ⁶ Omega, less than ^{1.0 × 10 6 Ω ~ 1.0 ×} 10 7 Ω △ and ^{then, 1.0 × 10 7 Ω ~ 1.0} × 10 8 A value less than Ω was rated as ◯, and a value of 1.0 × 10 ⁸ Ω or more was rated as ◎.

Appearance (Dendrite): The comb substrate after the HAST test is observed with an optical microscope (ECLIPS LV100, manufactured by Nikon Corp.) under the conditions of transmitted light and 200 times. ○.

Appearance (swelling and discoloration): Comb substrate after HAST test is observed with an optical microscope (ECLIPS LV100, manufactured by Nikon), bright field, 100 times condition, swelling and / or swelling of insulating film having a diameter of 50 μmφ or more Those in which discoloration was observed were evaluated as x, those in which swelling and / or discoloration of an insulating film of 10 μmφ or more and less than 50 μmφ were observed were evaluated as Δ, and those having swelling and discoloration of 10 μmφ or less were evaluated as ◯.

<Measurement of warpage after firing>
The obtained photosensitive dry film was laminated on Kapton (registered trademark) under the above-mentioned lamination conditions, and then baked at 180 ° C. for 1 hour. A photosensitive dry film was cut out into 5 cm squares, and those with a floating height of less than 5 mm were marked with ◎, those with a height of less than 5 to 10 mm were marked with ○, and those with a floating height higher than that were marked with ×.

<Resolution evaluation>
The resolution evaluation was performed as follows. A photosensitive dry film was laminated on the copper clad laminate under the above-mentioned lamination conditions, and then exposed at 30 to 270 mJ / cm ² . Subsequently, alkaline development with a 1% by mass aqueous sodium carbonate solution and rinsing with water were performed, and the pattern was evaluated with an optical microscope after drying. A 50 μm to 100 μm line and space (L / S) pattern was used for the mask. The remaining film ratio of the exposed part (cured part) was 100% by development, and the part where the copper surface of the unexposed part (dissolved part) appeared was read. The case where 70 μm L / S could be resolved was marked with ◎, the case where 100 μm L / S pattern could be resolved was marked with ○, and the case where 100 μm could not be resolved was marked with ×.

<Polyimide (7)>
Under a nitrogen atmosphere, in a separable flask, triethylene glycol dimethyl ether (15 g), γ-butyrolactone (35 g), toluene (20.0 g), silicone diamine (KF-8010 (11.30 g (13.78 mmol)), ODPA ( 10.86 g (35.00 mmol)) was added, and the mixture was heated and stirred for 1 hour at 120 ° C. Subsequently, the Dean-Stark apparatus and the reflux were attached, and the mixture was heated and stirred for 1 hour at 180 ° C. Toluene as an azeotropic solvent was removed. After cooling to 25 ° C., APB-N (6.00 g (20.52 mmol)) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of polyimide (7). The weight average molecular weight is shown in Table 7 below.

<Polyimide (8)>
Under a nitrogen atmosphere, a separable flask was charged with triethylene glycol dimethyl ether (15 g), γ-butyrolactone (35 g), toluene (20.0 g), silicone diamine (KF-8010 (11.00 g (13.41 mmol)), BPDA ( 10.30 g (35.00 mmol)) was added and stirred for 1 hour at 120 ° C. Subsequently, a Dean-Stark apparatus and a reflux were attached, and the mixture was heated and stirred for 1 hour at 180 ° C. Toluene, an azeotropic solvent, was removed. After cooling to 25 ° C., APB-N (6.10 g (20.87 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of polyimide (8). The weight average molecular weight is shown in Table 7 below.

<Polyimide (9)>
Under a nitrogen atmosphere, a separable flask was charged with triethylene glycol dimethyl ether (15 g), γ-butyrolactone (35 g), toluene (20.0 g), silicone diamine (KF-8010 (9.50 g (11.59 mmol)), PMDA ( 7.63 g (35.00 mmol)) was added and stirred for 1 hour at 120 ° C. Subsequently, a Dean-Stark apparatus and a reflux were attached, and the mixture was heated and stirred for 1 hour at 180 ° C. Toluene, an azeotropic solvent, was removed. After cooling to 25 ° C., APB-N (6.65 g (22.75 mmol) was subsequently added and stirred for 8 hours at 25 ° C. to obtain a solution of polyimide (9). The weight average molecular weight is shown in Table 7 below.

<Polyimide (10)>
Under a nitrogen atmosphere, a separable flask was charged with triethylene glycol dimethyl ether (15 g), γ-butyrolactone (35 g), toluene (20.0 g), silicone diamine (KF-8010 (13.15 g (16.04 mmol)), TMEG ( 14.36 g (35.00 mmol)) was added, and the mixture was stirred with heating for 1 hour at 120 ° C. Subsequently, the Dean-Stark apparatus and the reflux were attached, and the mixture was stirred with heating for 1 hour at 180 ° C. Toluene as an azeotropic solvent was removed. After cooling to 25 ° C., APB-N (5.34 g (18.27 mmol)) was added, followed by stirring at 25 ° C. for 8 hours to obtain a solution of polyimide (10). The weight average molecular weight is shown in Table 7 below.

<Polyimide (11)>
Under a nitrogen atmosphere, a separable flask was charged with triethylene glycol dimethyl ether (15 g), γ-butyrolactone (35 g), toluene (20.0 g), PMAB ((12.00 g (9.69 mmol)), ODPA (10.86 g ( 35.00 mmol)) was added and stirred for 1 hour at 120 ° C. Subsequently, a Dean-Stark apparatus and a reflux were attached, and the mixture was heated and stirred for 1 hour at 180 ° C. After removing toluene, which is an azeotropic solvent, up to 25 ° C. After cooling, APB-N (7.20 g (24.63 mmol) was added and stirred at 25 ° C. for 8 hours to obtain a solution of polyimide (11). The weight average molecular weight of the obtained polyimide (11) was It shows in Table 7 below.

[Examples 13 to 15]
BPE-500 (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass) with respect to 100 parts by mass of polyimide (7), polyimide (8), polyimide (9), FP-300 (25 parts by mass) and TBXP (15 parts by mass) were mixed to prepare a photosensitive resin composition. The obtained photosensitive resin composition was made into a dry film by the dry film manufacturing method described above to obtain a photosensitive film. This photosensitive film was laminated on a comb-type substrate under the above-mentioned laminating conditions. The insulation reliability of the obtained laminated film was evaluated. The results are shown in Table 8 below. In Examples 13 and 14, the warpage was ◎ and the resolution was ◎, and in Example 15 the warp was ○ and the resolution was ◎.

[Example 16]
BPE-500 (40 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts by mass) are mixed with 100 parts by mass of polyimide (7). A resin composition was prepared. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ◎ and the resolution was x.

[Example 17]
M-310 (40 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts by mass) are mixed with 100 parts by mass of polyimide (7). A resin composition was prepared. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, the warpage was ○, and the resolution was ○.

[Example 18]
BPE-900 (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ◎ and the resolution was ○.

[Example 19]
9PG (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts by mass) with respect to 100 parts by mass of polyimide (7) ) Was mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was ◎ and the resolution was ○.

[Example 20]
BPE-500 (20 parts by mass), M-350 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was で and the resolution was ◎.

[Example 21]
BPE-500 (20 parts by mass), M-306 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was で and the resolution was ◎.

[Example 22]
BPE-500 (20 parts by weight), A-TMMT (20 parts by weight), OXE-02 (1 part by weight), FP-300 (25 parts by weight), TBXP (15 parts per 100 parts by weight of polyimide (7) Part by mass) was mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was で and the resolution was ◎.

[Example 23]
BPE-500 (20 parts by mass), A-GLY-9E (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP with respect to 100 parts by mass of polyimide (7) (15 parts by mass) was mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was で and the resolution was ◎.

[Example 24]
BPE-500 (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts by mass), TBXP (15 parts) with respect to 100 parts by mass of polyimide (7) Part by mass), T5651 (3 parts by mass), and SBN-70D (3 parts by mass) were mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition by the same method as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. The warpage was で and the resolution was ◎.

[Comparative Example 7, Comparative Example 8]
BPE-500 (20 parts by mass), M-310 (20 parts by mass), OXE-02 (1 part by mass), FP-300 (25 parts per 100 parts by mass of polyimide (10) and polyimide (11) Part by mass) and TBXP (15 parts by mass) were mixed to prepare a photosensitive resin composition. A laminated film was produced from the obtained photosensitive resin composition in the same manner as in Examples 13 to 15, and the insulation reliability was evaluated. The results are shown in Table 8 below. Further, in both Comparative Example 7 and Comparative Example 8, the warpage was ◎, and the resolution was ◎.

From the results of Tables 7 and 8, Examples 13 to 13 using photosensitive resin compositions containing the polyimide structure represented by the general formula (7) and the polyamic acid structure represented by the general formula (8) were used. In Example 24, it can be seen that the insulation reliability (HAST resistance) is excellent as compared with Comparative Example 7 and Comparative Example 8. Moreover, when Example 13 and Example 20 are compared with Example 22 and Example 23, resin containing the (meth) acrylate compound which has three or more double bonds of the structure shown by the said General formula (10). It can be seen that the composition has better insulation reliability (HAST resistance).

The resin composition according to the fourth embodiment of the present invention will be described with reference to the following Example 25, Example 26, and Comparative Examples 9 to 11. In addition, the following Example 25 and Example 26 are the resin compositions which concern on a 2nd aspect.

[Example 25]
In this example, as a resin composition, a varnish of polyimide Z having an imidization ratio of 100%, a bifunctional hydroxyl-containing compound, both-end type phenol-modified silicone X-22-1821 (hydroxyl value 38 mgKOH) manufactured by Shin-Etsu Chemical Co., Ltd. / G), 1,3-bis (4,5-dihydro-2-oxazolyl) benzene (hereinafter referred to as BPO) as an oxazoline compound, and flame retardant A (see Example 1) were used. A material obtained by adding 5 parts by mass of double-end type phenol-modified silicone X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd., 13 parts by mass of BPO, and 33 parts by mass of flame retardant A to 100 parts by mass of polyimide Z was used. This resin composition was applied to a copper foil and dried at 95 ° C. for 12 minutes to obtain a resin film having a thickness of 30 μm. This resin film was used for evaluation of antkari solubility. Furthermore, the resin film was heated at 180 ° C. for 60 minutes to obtain a cured product. This cured product was used for evaluation of alkali resistance. Hereinafter, a method for synthesizing polyimide Z will be described.

[Polyimide Z]
A method for synthesizing polyimide Z will be described. First, a ball-mounted cooling tube equipped with a nitrogen introduction tube, a thermometer, and a water separation trap was attached to a three-necked separable flask. At room temperature 25 ° C., 15 g of triethylene glycol dimethyl ether, 35 g of γ-butyrolactone, 20.0 g of toluene, and 10.86 g (35.00 mmol) of 4,4′-oxydiphthalic dianhydride (manac, ODPA) Stir until uniform. Thereafter, the temperature was raised to 80 ° C., 12.05 g (14.7 mmol) of silicone diamine (manufactured by Shin-Etsu Chemical Co., Ltd., abbreviated as KF-8010) was added, and the mixture was further stirred for 0.5 hours, and then heated to 170 ° C. Heated for hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. After standing at room temperature for 25 hours and cooling, 7.56 g (20.65 mmol) of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 35 g of γ-butyrolactone, 20.0 g of toluene Was added. After stirring for 0.5 hour, the temperature was raised to 170 ° C. and heated for 4 hours. During the reaction, by-product water was azeotroped with toluene and dehydrated under reflux using a ball-mounted condenser equipped with a water separation trap. After draining by-product water, the reflux was stopped and toluene was completely removed. Next, the product was pressure filtered through a 5 μm filter to obtain a polyimide Z varnish having an imidization rate of 100%.

[Evaluation of warpage]
The warpage was evaluated by lifting the four corners of the resin film. Specifically, the sample 1 described above was cut into 5 cm × 5 cm in an environment of 23 ° C. and a humidity of 50%, and the distance at which the corner was raised relative to the central portion was measured as a 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 solder resistance]
The solder resistance was evaluated by immersing a cured product cut to 3 cm × 3 cm in a solder bath at 260 ° C. for 60 seconds in accordance with the JPCA-BM02 standard. Visually inspect the external appearance to confirm the presence or absence of changes such as deformation and dissolution traces. If no change is observed in 90% or more of the total area, the circle is marked as ○, and the area is 50% to 90%. The case where no change was observed was indicated by Δ, and the case where the region where no change was observed was less than 50% was indicated by ×.

[Evaluation of alkali solubility]
The resin film was immersed in a 3% aqueous sodium hydroxide solution at 48 ° C., and the dissolution rate of the film thickness was measured to evaluate alkali solubility. When the dissolution rate of the film thickness was 0.2 μm / sec or more, “◯” was given, and when it was less than 0.2 μm / sec, “x” was given.

[Evaluation of alkali resistance]
The cured product was immersed in a 3% aqueous sodium hydroxide solution at 48 ° C. for 1 minute, and the change in film thickness before and after immersion was measured to evaluate the alkali resistance. The case where the change was 2 μm or less was evaluated as ◯, and the case where the change exceeded 2 μm was evaluated as x.

[Through hole embedding]
The measurement was performed under the same conditions as in Example 1 according to the first embodiment.

[Cool thermal shock test]
The measurement was performed under the same conditions as in Example 1 according to the first embodiment.

[Resin flow]
The measurement was performed under the same conditions as in Example 1 according to the first embodiment.

[Example 26]
In this example, as a resin composition, 10 parts by mass of a both-end type phenol-modified silicone X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd. as a bifunctional hydroxyl group-containing compound and 100 parts by mass of polyimide Z as an oxazoline compound A product obtained by adding 20 parts by mass of BPO and 33 parts by mass of flame retardant A was used. Others were produced and evaluated in the same manner as in Example 25 by preparing resin films and cured products.

[Comparative Example 9]
In this example, as the resin composition, one obtained by adding 33 parts by mass of flame retardant A without adding a bifunctional hydroxyl group-containing compound to 100 parts by mass of polyimide Z was used. Others were produced and evaluated in the same manner as in Example 25 by preparing resin films and cured products.

[Comparative Example 10]
In this example, polyimide Z was not used as the resin composition, and 10 parts by mass of a both-end type phenol-modified silicone X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd. as a bifunctional hydroxyl group-containing compound was used as an oxazoline compound. What added 20 mass parts of BPO and the flame retardant A33 mass part was used. Others were produced and evaluated in the same manner as in Example 25 by preparing resin films and cured products.

[Comparative Example 11]
In this example, as a resin composition, 10 parts by mass of a both-end type phenol-modified silicone X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd. as a bifunctional hydroxyl group-containing compound with respect to 100 parts by mass of polyimide Z, and flame retardant A33 What added the mass part was used. Others were produced and evaluated in the same manner as in Example 25 by preparing resin films and cured products.

Table 9 below shows the evaluation results of Example 25, Example 26, and Comparative Examples 9 to 11. As can be seen from Table 9 below, the resin films using the resin compositions according to Example 25 and Example 26 show alkali-solubility while the cured product exhibits alkali resistance, and further has low warpage and excellent solder resistance. The effect similar to the resin composition which concerns on the other Example mentioned above was acquired. On the other hand, as can be seen from Comparative Examples 9 to 11, it can be seen that the evaluation of solder resistance, warpage, and the like deteriorates when any of the polyimide, bifunctional hydroxyl group-containing compound and oxazoline compound is not included.

It should be noted that the present invention is not limited to the above embodiment, and can be implemented with various modifications. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.

INDUSTRIAL APPLICABILITY The present invention has an effect that a sufficient warpage reduction during curing and a resin composition capable of realizing excellent heat resistance can be realized, and in particular, a surface protection film for semiconductor elements, an interlayer insulating film, a bonding sheet It can be suitably used as 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.

This application includes Japanese Patent Application No. 2011-007862 filed on January 18, 2011, Japanese Patent Application No. 2011-062186 filed on March 22, 2011, Japanese Patent Application No. 2011-107290 filed on May 12, 2011, and July 2011. Based on Japanese Patent Application No. 2011-160730 filed on May 22nd. All these contents are included here.

Claims

(A) a polymer compound, (B) a polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups, and (C) the polymer compound and / or the polyfunctional hydroxyl group-containing compound 2 A polyfunctional crosslinkable compound having the above crosslinkable functional group, and the polyfunctional crosslinkable compound forms a three-dimensional crosslink between the polymer compound and / or the polyfunctional hydroxyl group-containing compound. A resin composition obtained.
The resin composition according to claim 1, wherein the polymer compound has an imide group and / or an amide group, and the three-dimensional crosslinking includes a C = O group and / or an NH group.
The resin composition according to claim 1 or 2, wherein the polyfunctional hydroxyl group-containing compound and / or the polyfunctional crosslinkable compound is trifunctional or more.
The resin composition according to any one of claims 1 to 3, wherein the polymer compound has a hydroxyl group and / or a carboxyl group.
5. The compound according to claim 1, wherein the polyfunctional hydroxyl group-containing compound includes at least one selected from a phenol-modified silicone at both terminals, a polybutadiene polyol, a hydrogenated polybutadiene polyol, and a polycarbonate polyol. Resin composition.
The resin composition according to any one of claims 1 to 5, wherein the polyfunctional hydroxyl group-containing compound contains an aliphatic structure.
The resin composition according to any one of claims 1 to 6, wherein the polyfunctional hydroxyl group-containing compound is a polycarbonate polyol.
The resin composition according to any one of claims 1 to 7, 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 1 to 8, wherein the polyfunctional crosslinkable compound contains two or more blocked isocyanate groups.
The molar ratio of the hydroxyl group contained in the polyfunctional hydroxyl group-containing compound to the crosslinkable functional group contained in the polyfunctional crosslinkable compound is hydroxyl group / crosslinkable functional group = 0.5 to 1. The resin composition according to any one of claims 1 to 9.
11. The resin composition according to claim 1, wherein the content of the polyfunctional hydroxyl group-containing compound is 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polymer compound. object.
The resin composition according to any one of claims 1 to 11, wherein the content of the polyfunctional crosslinkable compound is 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polymer compound. object.
The resin composition according to any one of claims 1 to 12, wherein the polyfunctional hydroxyl group-containing compound has a number average molecular weight of 500 to 3,000.
The resin composition according to any one of claims 1 to 13, wherein the polymer compound has a repeating structure represented by the following general formula (1).

(In Formula (1), Y 1 represents a divalent organic group, Z 1 represents a tetravalent organic group, and a represents an integer of 1 to 50.)
The resin composition according to claim 1, wherein the polymer compound is polyimide.
The resin composition according to any one of claims 1 to 15, wherein the polymer compound has a repeating structure represented by the following general formula (2).

(In Formula (2), Z 1 and Z 2 represent a tetravalent organic group, and Y 1 , Y 2 , Y 3 , Y 4 , and Y 5 each independently represent 1 to 5 carbon atoms. And may be branched. B, c and d each independently represents an integer of 1 to 50.)
The polymer compound has a polyimide structure represented by the following general formula (3) and a polyamic acid structure represented by the following general formula (4) as repeating structural units, respectively. The resin composition in any one of 16.

(In Formula (3) and Formula (4), R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently a hydrogen atom. Alternatively, it represents a monovalent organic group having 1 to 20 carbon atoms, and R 3 , R 6 , R 9 , R 12 , and R 15 are each independently a tetravalent organic group having 1 to 20 carbon atoms. M, n, and p each independently represents an integer of 0 to 100. R 16 represents a tetravalent organic group, and R 17 represents a divalent group having 1 to 90 carbon atoms. Represents an organic group of
The resin composition according to claim 17, comprising a diamine represented by the following general formula (5) as a diamine component constituting the polyimide represented by the general formula (3).

(In formula (5), R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 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 15 each independently represents a tetravalent organic group having 1 to 20 carbon atoms; , N and p are each independently an integer of 0 or more and 30 or less and satisfy 1 ≦ (m + n + p) ≦ 30.)
The resin composition according to any one of claims 1 to 18, wherein the polymer compound has a structure represented by the following general formula (6) as a repeating unit.

(In formula (6), R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 , R 11 , R 13 , and R 14 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 15 represent a tetravalent organic group having 1 to 20 carbon atoms, m, n, p Each independently represents an integer of 0 or more and 30 or less, R 16 represents a tetravalent organic group, and R 17 represents a divalent organic group having 1 to 90 carbon atoms. , C represents mol% of each unit, and satisfies 0.10 ≦ (A + B) / (A + B + C) ≦ 0.85.)
The polymer compound has a polyimide structure represented by the following general formula (7) and a polyamic acid structure represented by the following general formula (8) as structural units. The resin composition in any one.

(In formula (7) and formula (8), Z 3 and Z 4 are tetravalent organic groups derived from tetracarboxylic dianhydride represented by the following general formula (9), and are the same as each other. R 18 is a divalent organic group having 1 to 30 carbon atoms, R 19 is a monovalent organic group having 1 to 30 carbon atoms, and e is 1 or more and 20 or less. Represents an integer.)
21. The method according to claim 1, further comprising (D) a (meth) acrylate compound having two or more unsaturated double bonds capable of photopolymerization, and (E) a photopolymerization initiator. A resin composition according to claim 1.
The resin composition according to claim 21, comprising a (meth) acrylate compound having three or more double bonds as the (meth) acrylate compound having two or more unsaturated double bonds capable of photopolymerization. .
The resin composition according to claim 22, comprising a compound represented by the following general formula (10) as the (meth) acrylate compound having three or more double bonds.

(In the formula (10), R 20 represents a hydrogen atom or a methyl group, and a plurality of E's each independently represents an alkylene group having 2 to 5 carbon atoms, which may be the same or different. f is an integer of 1 to 10.)
As the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, a (meth) acrylate compound having two double bonds and a (meth) acrylate compound having three or more double bonds The resin composition according to any one of claims 21 to 23, which is contained.
(F) The resin composition according to any one of claims 1 to 24, which contains a phosphorus compound.
26. The resin composition according to claim 25, wherein the phosphorus compound comprises a phosphate ester compound and / or a phosphazene compound.
Interlaminar insulation resistance in an insulation reliability test at a temperature of 85 ° C., humidity of 85%, and 1000 hours is 10 9 Ω or more, and a viscosity at 120 ° C. to 220 ° C. is 5000 Pa · S to 100000 Pa · S,
A resin composition comprising an elastic region having an elongation of less than 20% and a plastic region having an elongation of 50% or more, and a film thickness of an interlayer insulating layer of 40 μm or less.
The resin composition according to any one of claims 1 to 27 is obtained by heating at 100 ° C to 130 ° C for 5 minutes to 60 minutes and then heating at 160 ° C to 200 ° C for 15 minutes to 60 minutes. A cured product characterized by that.
A resin film comprising: a base material; and the resin composition according to claim 1 provided on the base material.
30. The resin film according to claim 29, wherein the substrate is a carrier film.
The resin film according to claim 29 or 30, further comprising a cover film provided on the resin composition.
32. The resin film according to claim 29, wherein the substrate 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 27 provided so as to cover the wiring.