JP5012819B2 - Polyimide resin composition - Google Patents

Description

  The present invention is a thermosetting polyimide resin composition useful in the fields of various heat-resistant coating materials and electrical insulating materials such as interlayer insulating materials for printed wiring boards, build-up materials, semiconductor insulating materials, heat-resistant adhesives, And it is related with the manufacturing method of the polyimide resin composition used for this.

  In recent years, there has been a demand for improvement in heat resistance and electrical characteristics of resins in various fields mainly in the electrical and electronic industries. Under these circumstances, as a resin composition having heat resistance, a polyisocyanate containing an isocyanurate ring, an aromatic isocyanate, and a polycarboxylic acid containing a lactam and an acid anhydride are synthesized in a cresol solvent. A polyimide amide resin composition containing a cured polyamideimide resin and an epoxy resin is known (see, for example, Patent Document 1).

  In addition, not a strong and toxic solvent such as cresol, but a polyimide resin that can be dissolved in an aprotic polar organic solvent such as a ketone solvent, an ester solvent, or an ether solvent such as a ketone solvent, And a method for producing a polyimide resin obtained by reacting an aliphatic isocyanate compound having two or more isocyanate groups and / or an alicyclic isocyanate compound with a tricarboxylic acid anhydride and / or a tetracarboxylic acid anhydride, and A polyimide resin composition containing a polyimide resin and an epoxy resin is known (for example, see Patent Document 2).

  However, the cured product obtained by curing the polyimide resin composition containing the polyimide resin and the epoxy resin described in Patent Document 1 and Patent Document 2 is excellent in heat resistance, but has a high dielectric constant and dielectric loss tangent. There are challenges.

  In addition, the applicant intends to solve the above-mentioned problem, and includes a thermosetting polyimide resin composition containing a polyimide resin having a carboxyl group and a linear hydrocarbon structure having a number average molecular weight of 300 to 6,000, and an epoxy resin, and Thermosetting polyimide resin containing a polyimide resin production method (Japanese Patent Application No. 2002-368036), a polyimide resin having a carboxyl group and an aliphatic structure having a number average molecular weight of 100 to 1,000 at its terminal, and an epoxy resin We have applied for a composition and a method for producing a polyimide resin (Japanese Patent Application No. 2002-376846).

JP 55-137161 A (page 2-5) JP 2001-316469 A (page 3-9)

  An object of the present invention is a thermosetting polyimide resin composition containing a polyimide resin and an epoxy resin, having excellent heat resistance, low dielectric constant and dielectric loss tangent, and mechanical properties such as tensile strength and tensile elongation. It is providing the thermosetting polyimide resin composition from which the cured | curing material with a favorable linear expansion coefficient is small.

As a result of intensive studies in view of the above problems, the present inventors have found the following findings (a) to (c) and have completed the present invention.
(A) An organic solvent-soluble polyimide resin (X2) and epoxy resin (Y) having a cycloaliphatic structure containing a cycloolefin structure derived from a carboxyl group, an isocyanurate ring, and a dicyclopentadiene resin; The thermosetting polyimide resin composition containing (Z) has a low coefficient of linear expansion, excellent heat resistance and mechanical properties, and a cured product having a low dielectric constant and dielectric loss tangent and good dielectric properties can be obtained.

  (B) As the thermosetting polyimide resin composition, it is preferable to use a polyimide resin composition obtained by previously mixing a polyimide resin (X2) and a petroleum resin (Z). It can be easily produced by reacting an isocyanate compound (A) with a polycarboxylic acid anhydride (B) having three or more carboxyl groups in the presence of a petroleum resin (Z).

  (C) When the polyimide resin composition uses the acid anhydride (B1) having a carboxyl group as the acid anhydride (B) and uses the dicyclopentadiene resin (Z1) as the petroleum resin (Z), It can be easily produced by reacting the acid anhydride (B1) having a carboxyl group with the dicyclopentadiene resin (Z1) and then reacting with the polyisocyanate compound (A).

  That is, the present invention relates to an organic solvent-soluble polyimide resin (X2), epoxy resin (Y), and petroleum having a cycloaliphatic structure containing a cycloolefin structure derived from a carboxyl group, an isocyanurate ring, and a dicyclopentadiene resin. A thermosetting polyimide resin composition comprising a resin (Z) is provided.

  The thermosetting polyimide resin composition of the present invention is excellent in heat resistance, has a low dielectric constant and dielectric loss tangent, and provides a cured product having good mechanical properties such as tensile strength and tensile elongation.

The present invention is described in detail below.
Among the polyimide resins used in the present invention, it is excellent in compatibility with petroleum resin (Z) and epoxy resin (Y), and is aprotic such as general-purpose solvents such as ketone solvents, ester solvents and ether solvents. An organic solvent-soluble polyimide resin (X1) having a cycloaliphatic structure together with a carboxyl group is preferred because of its excellent solubility in polar organic solvents and the excellent heat resistance and mechanical properties of the cured product. More preferred is an organic solvent-soluble polyimide resin (X2) having a cycloaliphatic structure containing a cycloolefin structure derived from an isocyanurate ring and a dicyclopentadiene resin.

  Examples of the polyimide resin (X2) include structural units represented by the following general formulas (I), (II) and (III) [wherein the structure represented by the following general formula (I) is represented by the following general formula (II): And the structure represented by (III) is not included. And a polyimide resin (X3) having any one or more of the terminal structures represented by the following general formulas (IV), (V) and (VI), among which the acid value is 20 -250, a polyimide resin having an isocyanurate ring concentration of 0.3 to 1.2 mmol / g, a number average molecular weight of 1,000 to 30,000, and a weight average molecular weight of 2,000 to 100,000 Is particularly preferred. Further, the polyimide resin is most preferably one having an acid value of 20 to 150, a number average molecular weight of 1,000 to 10,000, and a weight average molecular weight of 2,000 to 50,000.

（ただし、式中のＲ_１は炭素数原子６〜１３の環式脂肪族構造を有する有機基、Ｒ_２はジシクロペンタジエン系樹脂由来のシクロオレフィン構造を有する数平均分子量１００〜５，０００の炭化水素、Ｒ_３はジシクロペンタジエン系樹脂由来のシクロオレフィン構造を有する数平均分子量１００〜５，０００の炭化水素を示す。）

(In the formula, R ₁ is an organic group having a cycloaliphatic structure having 6 to 13 carbon atoms, and R ₂ is a cycloolefin structure derived from a dicyclopentadiene resin having a number average molecular weight of 100 to 5,000. Hydrocarbon, R ₃ represents a hydrocarbon having a cycloolefin structure derived from a dicyclopentadiene resin and having a number average molecular weight of 100 to 5,000.)

In the present invention, the acid value, the isocyanurate ring concentration, the number average molecular weight and the weight average molecular weight of the polyimide resin (X2) are measured by the following methods.
(1) Acid value: Measured according to JIS K-5601-2-1. As a dilution solvent for the sample, a mixed solvent of acetone / water (9/1 volume ratio) having an acid value of 0 is used so that the acid value of the acid anhydride can also be measured.
(2) Concentration of isocyanurate ring: ¹² C-NMR analysis [solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ ) was performed, and a calibration curve was used from the spectral intensity of carbon atoms caused by the isocyanurate ring at 149 ppm. Thus, the concentration (mmol) of the isocyanurate ring per 1 g of the polyimide resin (X) is obtained. The concentration of the imide ring can be similarly determined from the spectral intensity of the carbon atom due to the imide ring at 169 ppm by ¹² C-NMR analysis.
(3) Number average molecular weight and weight average molecular weight: The number average molecular weight and weight average molecular weight in terms of polystyrene are determined by gel permeation chromatography (GPC).

  Although the manufacturing method of the said polyimide resin (X2) used for the thermosetting polyimide resin composition of this invention is not specifically limited, The polyimide resin containing petroleum resin (Z) with a polyimide resin (X2) by the following manufacturing method (1). It can be produced as a composition or a polyimide resin composition containing an unreacted dicyclopentadiene resin (Z1) together with a polyimide resin modified with a dicyclopentadiene resin (Z1) by this production method (2). preferable. In addition, in this manufacturing method (1), the method of making it react using resin which has an unsaturated bond as petroleum resin (Z), for example, dicyclopentadiene-type resin (Z1), is more preferable.

  Production method (1): Polyimide resin composition characterized by reacting polyisocyanate compound (A) with polycarboxylic acid anhydride (B) having three or more carboxyl groups in the presence of petroleum resin (Z) Manufacturing method.

  Production method (2): Production of a polyimide resin composition characterized by reacting an acid anhydride (B1) having a carboxyl group with a dicyclopentadiene resin (Z1) and then reacting with a polyisocyanate compound (A). Method.

  In order to produce the polyimide resin (X2), for example, a polyisocyanate having an isocyanurate ring derived from a diisocyanate having a cyclic aliphatic structure as the polyisocyanate compound (A) in the production method (1) or (2). May be used. Furthermore, in order to produce the polyimide resin (X3), for example, in the production method (1) or (2), as the component (A), (B) or (B1), and (Z) or (Z1), Polyisocyanate having an isocyanurate ring derived from a diisocyanate having a cycloaliphatic structure having 6 to 13 carbon atoms, a tricarboxylic acid anhydride, and a dicyclopentadiene system having a number average molecular weight of 100 to 5,000 Each resin may be used. In addition, when manufacturing these polyimide resins (X), you may contain an organic solvent.

  The polyisocyanate compound (A) used in the production method (1) or (2) is a compound having two or more isocyanate groups in the molecule. For example, aromatic polyisocyanate, aliphatic polyisocyanate (cycloaliphatic) Including polyisocyanates); nurate bodies, burette bodies, adduct bodies, and allophanate bodies of these polyisocyanates.

  Examples of the aromatic polyisocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4. '-Diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (crude MDI), polymethylene polyphenyl isocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'- Diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, tetramethylxylylene diisocyanate, di Eniren'eteru-4,4'-diisocyanate, naphthalene diisocyanate, and the like.

  Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylenemethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and norbornylene diisocyanate.

  As the polyisocyanate compound (A), an aliphatic polyisocyanate is obtained because a polyimide resin having a good organic solvent solubility and compatibility with an epoxy resin or an organic solvent and a low dielectric constant and dielectric loss tangent of the cured product can be obtained. Is preferred. In addition, an isocyanurate type polyisocyanate is preferable because a polyimide resin having a cured product having good heat resistance can be obtained.

  As the polyisocyanate compound (A), a polyimide resin having good solubility in organic solvents, compatibility with epoxy resins and organic solvents, low dielectric constant and dielectric loss tangent of cured products, and good heat resistance is obtained. Therefore, the polyisocyanate compound (A1) having an isocyanurate ring derived from an aliphatic polyisocyanate is more preferable, and a polyisocyanate compound having an isocyanurate ring derived from a cyclic aliphatic polyisocyanate is more preferable. Examples of the polyisocyanate compound having an isocyanurate ring derived from the cycloaliphatic polyisocyanate include those having a cyclic aliphatic structure of 2 to 3 moles per mole of the isocyanurate ring. What has a cycloaliphatic structure 2.5-3 mol times is more preferable.

  As the polyisocyanate compound (A1), for example, one or more aliphatic diisocyanate compounds are isocyanurated in the presence or absence of an isocyanuration catalyst such as a quaternary ammonium salt. And those composed of a mixture of isocyanurates such as trimer, pentamer, and heptamer. Specific examples of the polyisocyanate compound (A1) include isocyanurate type polyisocyanate of isophorone diisocyanate, isocyanurate type polyisocyanate of hexamethylene diisocyanate, isocyanurate type polyisocyanate of hydrogenated xylene diisocyanate, isocyanurate type polyisocyanate of norbornane diisocyanate. An isocyanate etc. are mentioned.

  As the polyisocyanate compound (A1), a polyimide resin excellent in organic solvent solubility and heat resistance of a cured product can be obtained. Therefore, 30 trimers of isocyanurate in 100 parts by weight of the polyisocyanate compound (a1). Those containing at least 50 parts by weight are preferred, and those containing at least 50 parts by weight are particularly preferred.

  Moreover, as said polyisocyanate compound (A1), it is more preferable that the content rate of an isocyanate group is 10 to 30 weight% because the polyimide resin with favorable organic solvent solubility and heat resistance of hardened | cured material is obtained. . Accordingly, the polyisocyanate compound (a11) is most preferably a polyisocyanate compound having an isocyanurate ring derived from a cycloaliphatic polyisocyanate having an isocyanate group content of 10 to 30% by weight. preferable.

  The polyisocyanate having an isocyanurate ring may be used in combination with other polyisocyanates, but isocyanurate type polyisocyanates are preferably used alone.

  Furthermore, as said polyisocyanate compound (A) used by this manufacturing method (1) or (2), it is obtained by making a hydroxyl-containing compound (a2) react with various polyisocyanate compounds (a1), and is 2 or more at the terminal. It is also possible to use a prepolymer (A2) having an isocyanate group of

  The molar ratio (NCO / OH) of the isocyanate groups in the polyisocyanate compound (a1) to the total number of hydroxyl groups in the hydroxyl group-containing compound (a2) used at this time is usually 1.2 to 20, preferably 1.5 to 10. is there. The reaction temperature of the polyisocyanate compound (a1) and the hydroxyl group-containing compound (a2) is usually 50 to 150 ° C, preferably 60 to 100 ° C. In this case, various urethanization catalysts can be used.

  As the use ratio of the hydroxyl group-containing compound (a2), a polyisocyanate compound (a1), a hydroxyl group-containing compound (a2) and three or more are obtained because a polyimide resin having good film forming properties, mechanical properties and heat resistance is obtained. 10 to 50 parts by weight is preferable, and 10 to 40 parts by weight is more preferable, based on 100 parts by weight of the total polycarboxylic acid anhydride (B) having a carboxyl group.

  As the polyisocyanate compound (a1), any of the various polyisocyanate compounds described above as the polyisocyanate compound (A) can be used, and preferred as the polyisocyanate compound (A), for example, isocyanurate type polyisocyanate is preferred, A polyisocyanate compound (A1) having an isocyanurate ring derived from an aliphatic polyisocyanate is more preferred, and a polyisocyanate compound having an isocyanurate ring derived from a cyclic aliphatic polyisocyanate is more preferred.

  Moreover, as said hydroxyl-containing compound (a2), the compound which has 1-6 hydroxyl groups in a molecule | numerator is mentioned, for example, It is hard to gelatinize at the time of manufacture of a prepolymer (A) or a polyimide resin (X2). To a compound having 1 to 4 hydroxyl groups in the molecule, and examples thereof include a monoalcohol compound, a polyol compound, and a phenol compound. These hydroxyl group-containing compounds (a2) may have a polyether structure, a polyester structure, a polycarbonate structure, a polyolefin structure, a polydiene structure, a hydrogenated polydiene structure, a polysiloxane structure and the like together with a hydroxyl group. These hydroxyl group-containing compounds (a2) may be used alone or in combination of two or more.

  Among the hydroxyl group-containing compounds (a2), monoalcohol compounds and / or polyol compounds are preferable.

  As the monoalcohol compound, various monoalcohol compounds can be used, and are not particularly limited, but are monoalcohol compounds having an aliphatic structure, wherein the primary molecular weight of the aliphatic structure portion is 100 to 1,000 or Secondary monoalcohol compounds are preferred, and in particular, a polyimide resin having a good balance between mechanical properties and dielectric properties of the cured product can be obtained. Therefore, it has a cyclic aliphatic structure and has a non-cyclic aliphatic structure portion. An aliphatic monoalcohol compound having an average molecular weight of 200 to 700 is preferred. Here, the aliphatic structure may be linear or branched, and may be a saturated aliphatic structure or an unsaturated aliphatic structure, but it is difficult to change physical properties upon heating and is excellent in stability. A saturated aliphatic structure is more preferable.

  Specific examples of the monoalcohol compound having an aliphatic structure include higher alcohols derived from natural fats and oils such as lauryl alcohol and oleyl alcohol, higher alcohols derived from petrochemical products, and the like. Moreover, as these commercially available products, for example, Diamond Doll series (Diadol 7, 9, 11, 13, 135, 911, 115H, 115L, etc.) manufactured by Mitsubishi Chemical Corporation, Dovanol series (Dovanol 23, 25). , 45, etc.); Calcole series manufactured by Kao Corporation (Calcor 2098, 4098, 6098, 6870, 6850, 8098, 8688, 200GD, 220-80, etc.); Conol series manufactured by Shin Nippon Rika Co., Ltd. ( Conol 10M, 10W, 10WS, 10D, 1098, 20F, 1275, 20P, 1465, 1495, 30CK, 1668, 1695, 30T, 30TD, 30F, 30SS, 2265, 2280, 30RC, 30OC, 30CK-R, etc.), Angers Call series (Angekor 50A, 60AN, 70AN, 8 AN, 85AN, 90N, 90NR, 90NHR, etc.), Ricacoal series (Ricacoal 90B, 90BR, 90BRHR, etc.), Enjecoal series (Enjecole 160B, 160BR, 200A, 200AT, 240A, C32-36, etc.); It is done.

  Moreover, various polyol compounds can be used as the polyol compound, and it is not particularly limited. However, the polyol compound has a linear hydrocarbon structure, and the number average molecular weight of the linear hydrocarbon structure portion is 300 to 6,000. Polyol compounds are preferable. Among them, a polyimide resin excellent in film-forming properties can be obtained, in which organic solvent solubility, compatibility with epoxy resins and organic solvents, mechanical properties are good, and the cured product has low dielectric constant and dielectric loss tangent. Therefore, a polyol compound having a linear hydrocarbon structure portion having a number average molecular weight of 700 to 4,500 is more preferable.

  Examples of the polyol compound include compounds having an average of 1.5 or more hydroxyl groups bonded to the terminal and / or side chain of the linear hydrocarbon structure per molecule in total. The linear hydrocarbon structure may be linear or branched. Further, the linear hydrocarbon structure may be a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, but a saturated hydrocarbon chain is more preferable from the viewpoints of changes in physical properties and stability during heating.

  Examples of the polyol compound include a polyol compound having a polyolefin structure or a polydiene structure and a hydrogenated product thereof. Specific examples thereof include polyethylene polyol, polypropylene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and the like. These may be used alone or in combination of two or more.

  Examples of commercially available polyol compounds include liquid polybutadiene having hydroxyl groups at both ends, such as NISSO PB (G series) manufactured by Nippon Soda Co., Ltd., Poly-bd manufactured by Idemitsu Petrochemical Co., Ltd .; Hydrogenated polybutadiene having hydroxyl groups at both ends, such as NISSO PB (GI series) manufactured by Mitsubishi Chemical Corporation, polytail H manufactured by Mitsubishi Chemical Corporation, and polytail HA; both ends such as Poly-iP manufactured by Idemitsu Petrochemical Co., Ltd. Liquid C5 polymer having a hydroxyl group at the end; Epol made by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene having hydroxyl groups at both ends of TH-1, TH-2, TH-3, etc. made by Kuraray Co., Ltd. Is mentioned.

  Examples of acid anhydrides (B) of polycarboxylic acids having three or more carboxyl groups used in production method (1) or (2) include tricarboxylic acid anhydrides and tetracarboxylic acid anhydrides. It is done.

  Examples of the acid anhydride of tricarboxylic acid include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  Examples of the tetracarboxylic acid anhydride include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3', 4,4'- Tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-2,2', 3,3′-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1, 4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride,

2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6 7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,3,9,10-tetracarboxylic dianhydride, berylene-3,4,9,10-tetracarboxylic Acid dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3 4-dicarboxyphenyl) Anhydrous tetracarboxylic acid having an aromatic organic group in the molecule such as lopan dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Things. One or more of these can be used. Further, a tricarboxylic acid anhydride and a tetracarboxylic acid anhydride may be mixed and used.

  The petroleum resin (Z) used in the present invention does not isolate diolefins and monoolefins contained in cracked oil fractions by-produced from an ethylene plant that produces ethylene, propylene, etc. by petroleum steam cracking. And those polymerized. These are broadly divided into those obtained by using C5 fraction as a raw material (aliphatic or C5 petroleum resin), those using C9 fraction (aromatic or C9 petroleum resin), and both. The raw material (C5C9 copolymer petroleum resin) and the dicyclopentadiene fraction obtained by dimerizing the cyclopentadiene contained in the C5 fraction are purified and polymerized (dicyclopentadiene) Are generally classified into four types of resin).

  Specific examples of the polymerizable fractions include C5 fractions such as 1-pentene, 2-pentene, 1-methylbutene, 2-methylbutene, isoprene, t-1,3-pentadiene, c- 1,3-pentadiene, cyclopentene, cyclopentadiene and the like can be mentioned. Examples of the C9 fraction include styrene, α, β-methylstyrene, vinyltoluene, indene, methylindene and the like, and further, as a dicyclopentadiene fraction. Include dicyclopentadiene, isopropenyl norbornene, dimethyldicyclopentadiene, tricyclopentadiene, and the like.

  As the petroleum resin (Z), there is no limitation on the combination of polymerization such as various fractions, and various resin systems or mixed resin systems can be used. In the polymerization of each fraction or the like, it is possible to use a polymerization catalyst such as sulfuric acid, boron fluoride complex, aluminum chloride catalyst.

  As the number average molecular weight of the petroleum resin (Z), those having a molecular weight of 300 to 5,000 are usually used, but those having a compatibility with the polyimide resin (X2) are preferably 350 to 2,000. .

  The amount of petroleum resin (Z) used in the thermosetting polyimide resin composition of the present invention and the production method (1) or (2) is 100 parts by weight in total of polyimide resin (X2) and petroleum resin (Z). In contrast, the petroleum resin (Z) is usually in a proportion of 10 to 90 parts by weight, and further from 15 to 70 parts by weight because a thermosetting polyimide resin composition having excellent cured properties and heat resistance is obtained. A proportion is preferred.

  As the petroleum resin (Z), a petroleum resin having an unsaturated bond is preferable because a cured product having good heat resistance, low dielectric constant and dielectric loss tangent, and excellent dielectric properties can be obtained. Resin (Z1) is more preferable. The number average molecular weight of the dicyclopentadiene-based resin (Z1) is preferably 100 to 5,000 because it is excellent in solubility in an organic solvent and mechanical properties of a cured product. In addition, the unsaturated bond amount of the petroleum resin or dicyclopentadiene resin (Z1) having an unsaturated bond is preferably 3 to 20 mmol / g because the resin has a good balance between reactivity and stability. . The amount of unsaturated bonds can be determined by measuring the iodine value or bromine value of the resin.

  Examples of the dicyclopentadiene resin (Z1) include resins obtained by polymerizing dicyclopentadiene fractions such as dicyclopentadiene, isopropenyl norbornene, dimethyldicyclopentadiene, tricyclopentadiene, and dicyclopentadiene fractions. And other monomers having an unsaturated bond, preferably resins obtained by polymerizing unsaturated cyclic olefins.

  Examples of the unsaturated cyclic olefins include cyclopentadiene; 2-norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenylnorbornene, 5-propenyl-2-norbornene, and 5-ethylidene-2. -Norbornene-based monomers such as norbornene; Triborates other than dicyclopentadiene fractions such as diethyldicyclopentadiene and dihydrodicyclopentadiene, and tetracycles such as tetracyclododecene; , Pentacycles such as tricyclopentadiene, heptacycles such as tetracyclopentadiene, and alkyl-substituted, alkylidene-substituted, aryl-substituted, etc. of these polycycles. Examples of the polycyclic alkyl-substituted product include methyl, ethyl, propyl, and butyl-substituted products, and examples of the polycyclic alkylidene-substituted product include ethylidene-substituted products, and the like. Examples of the polycyclic aryl-substituted product include phenyl, tolyl, and naphthyl-substituted products.

  Furthermore, as another monomer having an unsaturated bond, an olefin having 3 to 12 carbon atoms may be copolymerized. For example, propylene, butene-1, pentene-1, 1,3-pentadiene, hexene-1, Heptene-1, octene-1, diisobutylene, nonene-1, decene-1, 4-phenylbutene-1, 6-phenylhexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methyl Pentene-1,3-methylhexene-1,4-methylhexene-1,5-methylhexene-1,3,3-dimethylpentene-1,3,4-dimethylpentene-1,4,4-dimethylpentene- 1, α-olefins such as vinylcyclohexane and vinylcyclohexene; hexafluoropropene, 2-fluoropropene, 3-fluoropropene, 3 Halogen substituted α- olefins such as such as 4-dichloro-butene-1 and the like.

  Examples of other monomers having an unsaturated bond other than the above include ethylene, tetrafluoroethylene, fluoroethylene, 1,1-difluoroethylene, trifluoroethylene; styrene, p-methylstyrene, o-methylstyrene, m- Alkyl styrene such as methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, pt-butylstyrene; p-chlorostyrene, m-chloro Halogenated styrene such as styrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene Maleic anhydride, maleic acid, fumaric acid, Lil alcohol, 3-buten-2-ol, methylbutene-1-ol, vinyl acetate, and vinyl chloride.

  The said other monomer which has an unsaturated bond may be used independently, and may use 2 or more types together.

  Specific examples of the dicyclopentadiene resin (Z1) include Marukaretsu M series (M-100A, M-510, M-525A, M-890A, M-845A) manufactured by Maruzen Petrochemical Co., Ltd., Nippon Zeon Co., Ltd. ) Quinton 1000 series (Quinton 1325, Quinton 1345, Quinton 1500, Quinton 1525L, Quinton 1700) and the like.

  In the thermosetting polyimide resin composition of the present invention, the petroleum resin (Z) may be mixed with the polyimide resin (X2) and the epoxy resin (Y), but the polyimide resin (X) and the petroleum resin (Z ) Is preferably used as a polyimide resin composition.

  As the polyimide resin composition, a polyimide resin (X2) and a petroleum resin (Z) may be blended, but a cured product having a low dielectric constant and dielectric loss tangent and excellent dielectric properties can be obtained. A polyimide resin composition obtained by the production method (1) is preferable. In particular, a petroleum resin having an unsaturated bond as the petroleum resin (Z) in the production method (1), for example, a dicyclopentadiene resin (Z1) is used. In the polyimide resin composition obtained and the polyimide resin composition obtained by the production method (2), the carboxyl group in the reaction system undergoes an addition reaction with the unsaturated bond in the petroleum resin or dicyclopentadiene resin (Z1). As a result, a part of the polyimide resin modified with petroleum resin or dicyclopentadiene resin (Z1) is produced, so epoxy resin (Y) or unreacted petroleum Improved compatibility with fat or dicyclopentadiene-based resins (Z1), particularly preferred since the thermosetting polyimide resin composition having excellent stability.

  In the production method (1), the reaction temperature of the polyisocyanate compound (A) and the acid anhydride (B) of a polycarboxylic acid having three or more carboxyl groups is usually 80 to 250 ° C, preferably 100 to 200 ° C. It is. In the production method (2), the reaction temperature of the acid anhydride (B1) having a carboxyl group and the dicyclopentadiene resin (Z1) is usually 80 to 250 ° C, preferably 100 to 200 ° C. The reaction product obtained by the reaction and the polyisocyanate compound (A) have a reaction temperature of usually 80 to 250 ° C, preferably 100 to 200 ° C.

  In the production methods (1) and (2), the molecular weight and acid value of the resulting polyimide resin are changed by changing the weight ratio between the polyisocyanate compound (A) and the polycarboxylic acid anhydride (B). Can be adjusted. In this case, a catalyst such as an amine compound, a phosphorus compound, a metal compound or water may be used, and an antioxidant or a polymerization inhibitor may be used in combination.

  In the production methods (1) and (2), the weight ratio (A) / (B) of the polyisocyanate compound (A) to the polycarboxylic acid anhydride (B) is usually 90/10 to 50/50. Among them, 80/20 to 60/40 is preferable because a polyimide resin excellent in various physical properties such as heat resistance and mechanical properties can be obtained.

  The acid value of the polyimide resin obtained by the production method (1) or (2) is preferably 10 to 200, preferably 10 to 150 (KOH) in terms of solid matter in order to improve organic solvent solubility and cured properties. -Mg / g) is more preferred. The molecular weight of the polyimide resin is preferably a number average molecular weight of 1,000 to 30,000 and a weight average molecular weight of 2,000 to 100,000 in order to improve solvent solubility. More preferably, the number average molecular weight is 1,000 to 10,000 and the weight average molecular weight is 2,000 to 50,000.

  In the production methods (1) and (2), it is preferable to use an organic solvent because a uniform reaction can proceed. Here, the organic solvent may be preliminarily present in the system before the chemical reaction or may be introduced in the middle, and there is no particular limitation on the timing and amount of use, but the polyisocyanate compound (A) and It is preferably present at the start of the reaction of the polycarboxylic acid anhydride (B) having three or more carboxyl groups. In order to maintain an appropriate reaction rate during this reaction, the proportion of the organic solvent in the system is preferably 80% by weight or less, more preferably 10 to 70% by weight of the reaction system. As such an organic solvent, since a compound containing an isocyanate group is used as a raw material component, an aprotic polar solvent having no active proton such as a hydroxyl group or an amino group is preferable.

  Examples of the aprotic polar solvent include ether solvents, ester solvents, ketone solvents, petroleum solvents, and the like. Among them, the ether solvent has a weak polarity and provides an excellent reaction field in the imidation reaction between the polyisocyanate compound (A) and the polycarboxylic acid anhydride (B) having three or more carboxyl groups. .

  Examples of such ether solvents include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl. Polyethylene glycol dialkyl ethers such as ether and triethylene glycol dibutyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate Polyethylene glycol monoalkyl ether acetates such as triethylene glycol monoethyl ether acetate and triethylene glycol monobutyl ether acetate;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol Polypropylene glycol dialkyl ethers such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate;

Polypropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate Acetates; Dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of copolymerized polyether glycols; Ether glycol monoalkyl ester monoalkyl ethers, etc. It is.

Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone. In addition, polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and γ-butyrolactone can be used in combination.
Further, as the petroleum solvent, it is also possible to use toluene, xylene, other high-boiling aromatic solvents, and aliphatic and alicyclic solvents such as hexane and cyclohexane.

Next, the thermosetting polyimide resin composition of the present invention will be described.
The thermosetting polyimide resin composition of the present invention comprises a polyimide resin (X2) having a carboxyl group, an epoxy resin (Y), and a petroleum resin (Z) as essential components, and further having two or more phenolic hydroxyl groups as necessary. Examples of the resin composition include other components such as (W).

  Examples of the epoxy resin (Y) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type novolak. Novolak-type epoxy resins such as: Epoxy products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; Biphenyls such as epoxidized products of 2,2 ′, 6,6′-tetramethylbiphenol Type epoxy resin; epoxy resin having naphthalene skeleton; aromatic epoxy resin such as epoxy resin having fluorene skeleton and hydrogenated products of these aromatic epoxy resins; neopentyl glycol diglycy Aliphatic epoxy resins such as ether, 1,6-hexanediol diglycidyl ether; Fats such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate Cyclic epoxy resins; and heterocyclic ring-containing epoxy resins such as triglycidyl isocyanurate. Among these, an aromatic epoxy resin is preferable because a thermosetting polyimide resin composition having excellent heat resistance can be obtained.

  As a ratio of polyimide resin (X2), epoxy resin (Y), and petroleum resin (Z), it is preferable that each component exists in the range of 10 to 80% by weight with respect to 100% by weight in total of these three components. More preferably, the polyimide resin (X) is 20 to 70% by weight, the epoxy resin (Y) is 10 to 50% by weight, and the petroleum resin (Z) is 20 to 70% by weight. The molar ratio (x2) / (y) of the carboxyl group (x2) in the polyimide resin (X2) and the epoxy group (y) in the epoxy resin (Y) is 0.7 to 1.3. Is more preferable.

  As the thermosetting polyimide resin composition of the present invention, a compound (W) having two or more phenolic hydroxyl groups is used in combination for the purpose of controlling the crosslink density during curing of the polyimide resin (X2) and the epoxy resin (Y). It is preferable. It is possible to increase the crosslink density between the polyimide resin (X2) and the epoxy resin (Y) by using a compound (W) having two or more phenolic hydroxyl groups, and thereby a line at a temperature above the glass transition point. It is possible to reduce the expansion coefficient and the like. In order to increase the crosslinking density and decrease the linear expansion coefficient, etc., the polyimide resin (X2), the epoxy resin (Y), the petroleum resin (Z), and the phenolic hydroxyl group in the thermosetting polyimide resin composition have two or more. The compounding ratio of the compound (W) is 10 to 80% by weight of the polyimide resin (X2), 10 to 40% by weight of the epoxy resin (Y), and 10 of the petroleum resin (Z) with respect to 100% by weight of the total. It is preferable that the compound (W) having ˜80 wt% and two or more phenolic hydroxyl groups is 5 to 20 wt%. Moreover, the sum total of the hydroxyl group (w) in the compound (W) which has two or more of the carboxyl groups (x2) and the phenolic hydroxyl groups in the polyimide resin (X2) and the epoxy group (y) in the epoxy resin (Y). The ratio (x2 + w) / (y) is more preferably 0.7 to 1.3.

  Examples of the compound (W) having two or more phenolic hydroxyl groups include bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S; phenol novolac resins, cresol novolac resins, bisphenol novolac resins, phenol salicylaldehyde novolac resins, Examples include novolak resins such as terpene diphenol novolac resins; biphenol compounds such as biphenol, biphenol novolac, tetramethylbiphenol, and derivatives thereof; and fluorene compounds such as phenol fluorene and cresol fluorene. Among these, a compound having three or more phenolic hydroxyl groups is preferable because a thermosetting polyimide resin composition having excellent heat resistance can be obtained.

  The method for preparing the thermosetting polyimide resin composition of the present invention is not particularly limited, but various components may be mechanically mixed, mixed by hot melting, or diluted after being mixed with a solvent. Although it is good, as the petroleum resin (Z), it is preferable that the polyimide resin (X) is previously produced in the presence of the petroleum resin (Z) as in the production methods (1) and (2). . In this case, the petroleum resin (Z) may be further added or not added at the stage of preparing the composition, and the preparation method is not limited as long as it is finally within the range of the various components described above.

  The thermosetting polyimide resin composition of the present invention can be used in combination with a curing agent and a curing accelerator other than those described above, if necessary. For example, melamine, dicyandiamide, guanamine and derivatives thereof, amines, and hydroxyl groups are 1 Specific examples include phenols, organic phosphines, phosphonium salts, quaternary ammonium salts, polybasic acid anhydrides, photocationic catalysts, cyanate compounds, isocyanate compounds, and blocked isocyanate compounds.

  Moreover, the thermosetting polyimide resin composition of this invention can add a various filler, an organic pigment, an inorganic pigment, an extender pigment, a rust preventive agent, etc. further as needed. These may be used alone or in combination of two or more.

  Examples of the filler include barium sulfate, barium titanate, silicon oxide powder, fine particulate silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like. It is done.

  Examples of the organic pigment include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and quinacridone pigments.

  Examples of the inorganic pigment include chromates such as chrome lead, zinc chromate and molybdate orange; ferrocyanides such as bitumen, titanium oxide, zinc white, bengara, iron oxide; metal oxides such as chromium carbide green, Cadmium yellow, cadmium red; metal sulfides such as mercury sulfide; selenides; sulfates such as lead sulfate; silicates such as ultramarine; carbonates, cobalt biored; phosphates such as manganese purple; aluminum powder, zinc dust Metal powders such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

  In addition, any of other coloring, rust prevention, and extender pigments can be used. These may be used alone or in combination of two or more.

  The thermosetting polyimide resin composition of the present invention is usually applied by a method such as casting, impregnation, or coating. The curing temperature is 80 to 300 ° C., and the curing time is 20 minutes to 5 hours.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Example 1
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 1532 g of diethylene glycol monoethyl ether acetate (hereinafter abbreviated as EDGA), 1532 g of petroleum-based aromatic solvent (Solvesso 150), and isocyanurate of isophorone diisocyanate Type polyisocyanate (hereinafter abbreviated as IPDI-N. Isocyanate group content 18.2%, isocyanurate ring-containing triisocyanate content 85%) 1398 g (6 mol as isocyanate group) and Quinton 1325 [Nippon Zeon Corporation ) Copolymer of cyclopentadiene and dicyclopentadiene, number average molecular weight 460, unsaturated bond concentration 3.4 mmol / g, softening point 125 ° C.] 707 g, trimellitic anhydride (hereinafter abbreviated as TMA) 960 g (5 models ) And it was charged, the temperature was raised paying attention to heat generation while stirring 80 ° C., and dissolved in 1 hour at this temperature, after heating to further over 2 hours 160 ° C., and the reaction was continued for 4 hours. The reaction proceeded with foaming, the system became a brown liquid, and a polyimide resin composition solution containing a polyimide resin partially modified with quinton 1325 and unreacted quinton 1325 was obtained.

The obtained polyimide resin composition solution was coated on a KBr plate and the infrared absorption spectrum of a sample obtained by volatilizing the solvent was measured. As a result, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely, and 725 cm ^−1. and 1780 cm ^-1 and 1720 cm ^-1 in the characteristic absorption of an imide ring, characteristic absorption of the isocyanurate ring was observed at 1690 cm ^-1 and 1460 cm ^-1. The acid value of the polyimide resin is 92 mg KOH / g in terms of solid content, the concentration of the isocyanurate ring is 0.724 mmol / g (in terms of resin solid content), and the number average molecular weight (hereinafter abbreviated as Mn) is 1,670. The weight average molecular weight (hereinafter abbreviated as Mw) was 3,200. Hereinafter, the solution of this polyimide resin composition is abbreviated as (XZ-1).

Example 2
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 1965 parts of EDGA, 1965 g of petroleum aromatic solvent (Sorvesso 150), 1398 g of IPDI-N (6 mol as an isocyanate group), 1572 g of Quinton 1325, 960 g (5 mol) of TMA was charged and heated to 80 ° C. while paying attention to heat generation while stirring, dissolved at this temperature for 1 hour, and further heated to 160 ° C. over 2 hours. Reacted for hours. The reaction proceeded with foaming, the system became a brown liquid, and a polyimide resin composition solution containing a polyimide resin partially modified with quinton 1325 and unreacted quinton 1325 was obtained.

As a result of measuring the infrared absorption spectrum using the obtained polyimide resin composition solution in the same manner as in Example 1, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and 725 cm ⁻¹ and 1780 cm ⁻¹ . 1720 cm ^-1 to the characteristic absorption of an imide ring, characteristic absorption of the isocyanurate ring was observed at 1690 cm ^-1 and 1460 cm ^-1. The acid value of the polyimide resin was 75 in terms of solid content, the concentration of the isocyanurate ring was 0.553 mmol / g (in terms of resin solid content), Mn was 2,140, and Mw was 4,740. Hereinafter, this polyimide resin composition solution is abbreviated as (XZ-2).

Example 3
In a 15 liter flask equipped with a stirrer, thermometer and condenser, from 3042 g of EDGA, 3042 g of petroleum aromatic solvent (Solvesso 150), 1398 g of IPDI-N (6 mol as isocyanate group), and norbornylene diisocyanate Polyisocyanate having an isocyanurate ring derived (isocyanate group content 18.75%, isocyanurate ring-containing triisocyanate content 65.5%) 1344 g (6 mol as isocyanate group), Quinton 1325 1825 g, TMA 1920 g (10 mol) was charged, dissolved by heating at 80 ° C., heated to 150 ° C. while stirring, and then reacted for 8 hours. The reaction proceeded with foaming, the system became a brown liquid, and a polyimide resin composition solution containing a polyimide resin partially modified with quinton 1325 and unreacted quinton 1325 was obtained.

As a result of measuring the infrared absorption spectrum using the obtained polyimide resin composition solution in the same manner as in Example 1, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and 725 cm ⁻¹ and 1780 cm ⁻¹ . 1720 cm ^-1 to the characteristic absorption of an imide ring, characteristic absorption of the isocyanurate ring was observed at 1690 cm ^-1 and 1460 cm ^-1. The acid value of the polyimide resin was 84 in terms of solid content, the concentration of the isocyanurate ring was 0.676 mmol / g (in terms of resin solid content), Mn was 1,770, and Mw was 3,890. Hereinafter, this polyimide resin composition solution is abbreviated as (XZ-3).

Example 4
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 1965 g of EDGA, 1965 g of petroleum-based aromatic solvent (Solvesso 150), 1398 g of IPDI-N (6 mol as an isocyanate group), Quinton 1700 [Nippon Zeon Copolymer of cyclopentadiene, dicyclopentadiene, and allyl alcohol manufactured by Co., Ltd., number average molecular weight 380, unsaturated bond concentration 3.4 mmol / g, softening point 100 ° C.] 471 g, Quinton 1325 1101 g, TMA 960 g (5 The reaction mixture was heated to 80 ° C. while paying attention to heat generation while stirring, dissolved at this temperature for 1 hour, further heated to 150 ° C. over 2 hours, and reacted for 4 hours. The reaction proceeds with foaming, the inside of the system becomes a brown liquid, and a polyimide resin composition solution containing polyimide resin partially modified with quinton 1700 and quinton 1325, unreacted quinton 1700 and unreacted quinton 1325 is obtained. It was.

As a result of measuring the infrared absorption spectrum using the obtained polyimide resin composition solution in the same manner as in Example 1, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and 725 cm ⁻¹ and 1780 cm ⁻¹ . 1720 cm ^-1 to the characteristic absorption of an imide ring, characteristic absorption of isocyanurate ring at 1690 cm ^-1 and 1460 cm ^-1, characteristic absorption of the urethane bond at 1550 cm ^-1. The acid value of the polyimide resin was 90 in terms of solid content, the isocyanurate ring concentration was 0.676 mmol / g (in terms of resin solid content), Mn was 2,100, and Mw was 8,700. Hereinafter, this polyimide resin composition solution is abbreviated as (XZ-4).

Example 5
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 1938 g of EDGA, 1938 g of petroleum aromatic solvent (Sorvesso 150), 1398 g of IPDI-N (6 mol as isocyanate group), 1,6-hexane 260 g (isocyanate group 1.5 mol) of polyisocyanate derived from diisocyanate (isocyanate group content 22.9%, isocyanurate ring-containing triisocyanate content 63.3%), Quinton 1345 [manufactured by Nippon Zeon Co., Ltd. Copolymer of cyclopentadiene and dicyclopentadiene, number average molecular weight 500, unsaturated bond concentration 3.4 mmol / g, softening point 145 ° C.] 1163 g, TMA 1056 g (5.5 mol), pyromellitic dianhydride Charge 109g (0.5mol) and stir Note reluctant heating temperature was raised to 80 ° C., and dissolved in 1 hour at this temperature, after heating to further over 2 hours 160 ° C., and the reaction was continued for 4 hours. The reaction proceeded with foaming, and the system became a brown liquid, and a polyimide resin composition solution containing a polyimide resin partially modified with quinton 1345 and unreacted quinton 1345 was obtained.

As a result of measuring the infrared absorption spectrum using the obtained polyimide resin composition solution in the same manner as in Example 1, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and 725 cm ⁻¹ and 1780 cm ⁻¹ . 1720 cm ^-1 to the characteristic absorption of an imide ring, characteristic absorption of the isocyanurate ring was observed at 1690 cm ^-1 and 1460 cm ^-1. The acid value of the polyimide resin was 72 in terms of solid content, the concentration of the isocyanurate ring was 0.691 mmol / g (in terms of resin solid content), Mn was 1,250, and Mw was 4,350. Hereinafter, the solution of this polyimide resin composition is abbreviated as (XZ-5).

Example 6
In a 10-liter flask equipped with a stirrer, a thermometer and a condenser, 2096 g of EDGA, 2096 g of petroleum-based aromatic solvent (Solvesso 150), 1398 g of IPDI-N (6 mol as isocyanate group), 4,4′- 262 g of dicyclohexylmethane diisocyanate (2 moles as isocyanate group) and Marcaretz M-510 [Copolymer of cyclopentadiene and dicyclopentadiene manufactured by Maruzen Petrochemical Co., Ltd., number average molecular weight 420, unsaturated bond concentration 7.1 mmol / g , 1572 g (softening point 110 ° C.) and 1152 g (6 mol) of TMA, heated to 80 ° C. while stirring, reacted for 3 hours, further heated to 160 ° C. over 2 hours, then 7 hours Reacted. The reaction proceeded with foaming, the system became a brown liquid, and a polyimide resin composition solution containing a polyimide resin partially modified with Marcaretz M-510 and unreacted Marcaretz M-510 was obtained.

As a result of measuring the infrared absorption spectrum using the obtained polyimide resin composition solution in the same manner as in Example 1, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and 725 cm ⁻¹ and 1780 cm ⁻¹ . 1720 cm ^-1 to the characteristic absorption of an imide ring, characteristic absorption of the isocyanurate ring was observed at 1690 cm ^-1 and 1460 cm ^-1. The acid value of the polyimide resin was 61 in terms of solid content, the concentration of the isocyanurate ring was 0.503 mmol / g (in terms of resin solid content), Mn was 1,150, and Mw was 3,350. Hereinafter, this polyimide resin composition solution is abbreviated as (XZ-6).

Example 7
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 957 g of a petroleum aromatic solvent (Solvesso 150) and Marcaretz M-845A (a copolymer of cyclopentadiene and dicyclopentadiene manufactured by Maruzen Petrochemical Co., Ltd.) , 2750 g of number average molecular weight 450, unsaturated bond concentration 7.5 mmol / g, softening point 145 ° C.], dissolved at 150 ° C., 1075 g (5.6 mol) of TMA was added, and 180 ° C. over 1 hour. The mixture was heated up to react for 5 hours. At this time, the solution turned black. Next, after cooling the temperature to 120 ° C., it was diluted with 878 g of petroleum aromatic solvent (Sorvesso 150) and 1835 g of dipropylene glycol monomethyl ether acetate, and after confirming dissolution of the resin component in the system, 1678 g of IPDI-N ( 7.2 mol) was added as an isocyanate group, and the temperature was raised to 160 ° C. over 1 hour, followed by reaction for 6 hours. The reaction proceeded with foaming, the system became a black liquid, and a solution of a polyimide resin composition containing a polyimide resin partially modified with Marcaretz M-845A and unreacted Marcaretz M-845A was obtained.

As a result of measuring the infrared absorption spectrum using the obtained polyimide resin composition solution in the same manner as in Example 1, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappeared, and 725 cm ⁻¹ and 1780 cm ⁻¹ . 1720 cm ^-1 to the characteristic absorption of an imide ring, characteristic absorption of the isocyanurate ring was observed at 1690 cm ^-1 and 1460 cm ^-1. The acid value of the polyimide resin was 32 in terms of solid content, the concentration of the isocyanurate ring was 0.463 mmol / g (in terms of resin solid content), Mn was 1,570, and Mw was 21,000. Hereinafter, this polyimide resin composition solution is abbreviated as (XZ-7).

Comparative Example 1
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser were charged 1496 g of dimethylformamide, 888 g of isophorone diisocyanate (8 mol as an isocyanate group), and 960 g (5 mol) of TMA, and the temperature was raised to 160 ° C. The reaction was performed for 4 hours. The reaction proceeded with foaming, and the inside of the system became a light brown clear liquid to obtain a polyimide resin solution.

As a result of measuring the infrared absorption spectrum in the same manner as in Example 1 using the obtained polyimide resin solution, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely, and 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ^−1. The absorption of the imide group was confirmed. The acid value of the polyimide resin was 94 in terms of solid content, Mn was 770, and Mw was 2500. Hereinafter, this polyimide resin solution is abbreviated as (X′-1).

Comparative Example 2
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 1496 g of EDGA, 2760 g of IPDI-N (12 mol as an isocyanate group) and 1728 g of TMA (9 mol as a hydroxyl group) were charged, and the temperature was raised to 150 ° C. Thereafter, the reaction was allowed to proceed for 8 hours. The reaction proceeded with foaming, and the inside of the system became a light brown clear liquid to obtain a polyimide resin solution.

As a result of measuring the infrared absorption spectrum in the same manner as in Example 1 using the obtained polyimide resin solution, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely, and 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ^−1. absorption of an imide ring, characteristic absorption of isocyanurate ring at 1690 cm ^-1 and 1460 cm ^-1, characteristic absorption of the urethane bond to 1550 cm ^-1 was confirmed on. The acid value of the polyimide resin was 95 in terms of solid content, the concentration of the isocyanurate ring was 0.64 mmol / g, Mn was 4,100, and Mw was 12,000. Hereinafter, this polyimide resin solution is abbreviated as (X′-2).

Examples 8 to 20 and Comparative Examples 3 to 4
Thermosetting polyimide resin compositions 1 to 13 of the present invention and comparative thermosetting polyimide resin compositions 1 'to 2' were prepared according to the formulations shown in Tables 1 to 3. In addition, 1 part of triphenylphosphine was added to all the resin compositions as a curing catalyst. Moreover, the numerical value in a table | surface all represents the compounding quantity in a solid conversion part.

Footnotes in Tables 1 to 3 N680: Cresol novolak epoxy resin manufactured by Dainippon Ink and Chemicals, Inc. EPICLON N-680 (softening point 80 ° C., epoxy equivalent 213 g / eq)
・ HP7200: Dainippon Ink & Chemicals, Inc. dicyclopentadiene modified epoxy resin EPICLON HP-7200 (softening point 61 ° C., epoxy equivalent 257 g / eq)
-EXA4700: Dainippon Ink and Chemicals Co., Ltd. polyfunctional naphthalene novolak type epoxy resin EPICLON EXA-4700 (epoxy equivalent 162 g / eq)
TD2090: Dainippon Ink & Chemicals, Inc. Phenol novolac resin Phenolite TD-2090 (softening point 120 ° C., hydroxyl group equivalent 105 g / eq)

Test Examples 1-13 and Comparative Test Examples 1-2
Using the thermosetting polyimide resin compositions 1 to 13 of the present invention and the comparative thermosetting polyimide resin compositions 1 'to 2', a compatibility test and a film-forming property test are carried out by the following methods. Glass transition point (Tg) measurement, tensile test, pressure cooker resistance test (PCT), solder heat resistance test, and conductive property measurement were performed. The results are shown in Tables 4-6.

(1) Compatibility test When the thermosetting polyimide resin composition was prepared according to the formulations shown in Tables 1 to 3, the glass plate was coated with the obtained resin composition and 120 ° C. The state of the coating film after drying was evaluated according to the following evaluation criteria.
Evaluation criteria A: Uniformity is easily achieved by stirring, and no foreign matter or the like is observed on the coating surface.
○: Uniform by stirring and no foreign matter or the like is seen on the coating surface.
(Triangle | delta): It becomes difficult to become uniform by stirring, and a foreign material etc. are seen a little on the coating-film surface.
X: It does not melt | dissolve uniformly, but a coating film surface can confirm a repelling, a foreign material, and an insoluble matter.

(2) Coating Film Forming Test A test piece obtained by applying a thermosetting polyimide resin composition to a tin plate with an applicator so that the film thickness after drying was 30 μm, and then drying at 110 ° C. for 30 minutes. The film was allowed to stand at room temperature for 24 hours, and the appearance of the coating film was evaluated according to the following evaluation criteria.
Evaluation criteria ○: No abnormalities such as cracks are observed in the coating film.
Δ: Some cracks are observed in the coating film.
X: Cracks occurred on the entire surface of the coating film.

(3) Glass transition point (Tg) measurement
<Preparation of test specimen>
The thermosetting polyimide resin composition was coated on a tin plate so that the film thickness after curing was 50 μm, dried for 20 minutes with a 120 ° C. dryer, and then cured at 150 ° C. and 170 ° C. for 1 hour, respectively. Two types of cured coating films were prepared and cooled to room temperature, and then the cured coating film was cut out from the coated plate to obtain a sample for Tg measurement.
<Tg measurement method>
Using the Tg measurement sample, dynamic viscoelasticity was measured under the following conditions, and the maximum temperature of Tan δ of the obtained spectrum was defined as Tg.
Measuring instrument: RSA-II manufactured by Rheometric
Jig: Pull Chuck spacing: 20 mm
Measurement temperature: 25-300 ° C
Measurement frequency: 1Hz
Temperature increase rate: 3 ° C / min

(4) Tensile test
<Preparation of test specimen>
The thermosetting polyimide resin composition was coated on the tin substrate so that the film thickness after curing was 50 μm. Next, this coated plate was dried with a 120 ° C. dryer for 20 minutes, and then a two-level cured coating film was prepared by curing at 150 ° C. and 170 ° C. for 1 hour. After cooling to room temperature, the cured film was cut into a predetermined size, isolated from the substrate, and used as a measurement sample.
<Tensile test measurement method>
Five measurement samples cured for 1 hour at 170 ° C. were prepared in the same manner as the Tg measurement sample, and a tensile test was performed under the following conditions to determine the breaking strength and breaking elongation.
Measuring instrument: Tensilon manufactured by Toyo Baldwin, Inc. Sample shape: 10 mm x 70 mm
Between chucks: 20 mm
Tensile speed: 10 mm / min
Measurement atmosphere: 22 ° C., 45% RH

(5) Pressure cooker resistance test (PCT)
The thermosetting polyimide resin composition was coated on a glass epoxy printed board formed with a pre-etched copper circuit pattern so that the film thickness after curing was 50 μm. Next, this coated plate was dried for 20 minutes with a 120 ° C. dryer, and then cured at 170 ° C. for 1 hour to prepare a test piece. The pressure cooker tester (PC-304RIII, manufactured by Hirayama Seisakusho) was used at 121 ° C. and 100 ° C. After being treated with% RH (under saturated vapor pressure) for 50 hours, it was returned to room temperature, and the change in appearance was visually evaluated according to the following evaluation criteria. In addition, a cross-like cross cut is made on the coating film on the test piece at intervals of 1 mm, a cellophane tape is applied thereon, a peeling test is performed, the number of peeling of the coating film is counted, and the coating film is measured according to the following criteria. The adhesion of was evaluated.
1. Appearance evaluation criteria A: No change or abnormality was observed before and after the test.
○: After the test, coating film abnormalities such as blistering, whitening and dissolution can be confirmed within a range of less than 5% of the coating film area.
(Triangle | delta): After a test, coating film abnormalities, such as blister, whitening, and melt | dissolution, can be confirmed in 5% or more and less than 30% of coating film areas.
X: After the test, coating film abnormalities such as blistering, whitening, and dissolution can be confirmed in a range of 30% or more of the coating film area.
2. Adhesive evaluation criteria A: No peeling of the grid-like coating film.
○: The number of coating films peeled from 100 grid-like coating films is less than 20.
(Triangle | delta): The number of the coating films peeled with respect to 100 grid-like coating films is 20 or more and less than 70.
X: 70 or more coating films peeled from 100 grid-like coating films.

(6) Solder heat resistance test A test piece prepared in the same manner as the pressure cooker resistance test and cut to a size of 25 × 25 mm is floated in a solder bath at 260 ° C. for 10 seconds with the coating surface facing down. As a cycle, three cycles were performed, and defects such as swelling of the coating film and adhesion were evaluated according to the following evaluation criteria.
Evaluation criteria A: No change is observed before and after the test.
○: After the test, defects, peeling, etc. are observed in a range of less than 5% of the coating film area.
(Triangle | delta): A defect, peeling, etc. are seen in 5% or more and less than 30% of coating-film areas after a test.
X: After the test, defects, peeling, etc. are observed in the range of 30% or more of the coating film area.

(7) Dielectric property measurement A thermosetting polyimide resin composition was coated on a tin plate so that the film thickness after curing was 200 μm, dried for 20 minutes with a 120 ° C. dryer, and then cured at 150 ° C. for 1 hour. After cooling and cooling, a measurement sample obtained by cutting out the peeled cured coating film was measured for dielectric constant (ε) and dielectric loss (Tanδ) under the condition of a frequency of 1 GHz using 4291B manufactured by Agilent Technologies.

(8) Linear expansion coefficient measurement
<Preparation of test specimen>
The thermosetting polyimide resin composition was coated on a tin plate so that the film thickness after curing was 50 μm, dried for 20 minutes with a 120 ° C. dryer, cured at 170 ° C. for 1 hour, cooled, and then peeled off. The cured coating film was cut into a width of 5 mm and a length of 30 mm to obtain a measurement sample.
<Method of measuring linear expansion coefficient>
Using a thermal analysis system TMA-SS6000 manufactured by Seiko Electronics Co., Ltd., measurement was performed by the TMA (Thermal Mechanical Analysis) method under the conditions of a sample length of 10 mm, a heating rate of 10 ° C./min, and a load of 49 mN. In addition, the temperature range used for the linear expansion coefficient was calculated | required from the displacement of the sample length in 40-50 degreeC.

  As is clear from the results in Tables 4 to 6, the cured coating film made of the thermosetting polyimide resin composition of the example shows a very high Tg and can exhibit heat resistance even at high temperatures. It can be said. Furthermore, while having such a high Tg, the dielectric constant and dielectric loss tangent are low, the dielectric properties are good, and the mechanical properties are also high. Also, it has very high resistance in PCT resistance and solder heat resistance tests, and has a low linear expansion coefficient.

  On the other hand, the cured coating film made of the thermosetting polyimide resin composition of Comparative Test Example 1 has a lower Tg compared to the cured coating film of the Examples, and the elongation at break, PCT resistance, solder heat resistance, dielectric constant, The dielectric loss tangent was also a bad result. Further, the cured coating film made of the thermosetting polyimide resin composition of Comparative Test Example 2 shows a very high Tg, but has a PCT resistance (adhesiveness), dielectric constant as compared with the cured coating film of Examples. It was a bad result in dielectric loss tangent.

Claims (9)

Contains organic solvent-soluble polyimide resin (X2), epoxy resin (Y), and petroleum resin (Z) having cycloaliphatic structure including cycloolefin structure derived from carboxyl group, isocyanurate ring and dicyclopentadiene resin A thermosetting polyimide resin composition characterized by comprising: The structure of the polyimide resin (X2) represented by the following general formulas (I), (II) and (III) [However, the structure represented by the following general formula (I) is represented by the following general formulas (II) and (III). Does not include The thermosetting polyimide resin composition according to claim 1, which is a polyimide resin having any one or more of terminal structures represented by the following general formulas (IV), (V) and (VI): object.

(In the formula, R ₁ is an organic group having a cycloaliphatic structure having 6 to 13 carbon atoms, and R ₂ is a cycloolefin structure derived from a dicyclopentadiene resin having a number average molecular weight of 100 to 5,000. Hydrocarbon, R ₃ represents a hydrocarbon having a cycloolefin structure derived from a dicyclopentadiene resin and having a number average molecular weight of 100 to 5,000.)

The polyimide resin (X2) has an acid value of 10 to 200, an isocyanurate ring concentration of 0.3 to 1.2 mmol / g, a number average molecular weight of 1,000 to 30,000, and a weight average molecular weight of 2. The thermosetting polyimide resin composition according to claim 2, which is a polyimide resin of 1,000,000 to 100,000. The polyimide resin (X2) has a number average molecular weight obtained from a polyisocyanate having an isocyanurate ring derived from a cyclic aliphatic diisocyanate and an acid anhydride (B) obtained from a polycarboxylic acid having three or more carboxyl groups. The thermosetting polyimide resin composition according to claim 1, which is a polyimide resin obtained by reacting in the presence of 100 to 5,000 dicyclopentadiene-based resin. The polyimide resin (X2) is a polyimide resin having an acid value of 10 to 200, and the weight ratio (X2 + Z) / (Y) of the total of the polyimide resin (X2) and the petroleum resin (Z) and the epoxy resin (Y) is It is 1.5-10, The thermosetting polyimide resin composition of any one of Claims 1-4. A mixture of the polyimide resin (X2) and the petroleum resin (Z) and the epoxy resin (Y) are mixed, and the mixture of the polyimide resin (X2) and the petroleum resin (Z) is composed of the polyisocyanate compound (A) and 3 Mixture of polyimide resin and petroleum resin obtained by reacting acid anhydride (B) obtained from polycarboxylic acid having at least one carboxyl group in the presence of petroleum resin (Z), or acid anhydride having carboxyl group 5. A mixture of a polyimide resin and a petroleum resin obtained by reacting the product (B1) with the dicyclopentadiene resin (Z1) and then reacting with the polyisocyanate compound (A). 5. The thermosetting polyimide resin composition described in 1. Furthermore, the thermosetting polyimide resin composition of any one of Claims 1-4 containing the compound (W) which has 2 or more of phenolic hydroxyl groups. A compound in which the polyimide resin (X2) is a polyimide resin having an acid value of 10 to 200, and has a total of the polyimide resin (X2) and petroleum resin (Z), an epoxy resin (Y), and two or more phenolic hydroxyl groups ( The thermosetting polyimide resin composition according to claim 7, wherein the total weight ratio (X2 + Z) / (Y + W) of W) is 1.5 to 10. A mixture of a polyimide resin (X2) and a petroleum resin (Z), an epoxy resin (Y), and a compound (W) having two or more phenolic hydroxyl groups, and a polyimide resin (X) and a petroleum resin (Z A polyimide resin obtained by reacting a polyisocyanate compound (A) with an acid anhydride (B) obtained from a polycarboxylic acid having three or more carboxyl groups in the presence of a petroleum resin (Z), A mixture of petroleum resins, or an acid anhydride (B1) having a carboxyl group and a dicyclopentadiene resin (Z1) are reacted and then reacted with a polyisocyanate compound (A) to obtain a polyimide resin and a petroleum resin. The thermosetting polyimide resin composition according to claim 7, which is a mixture.