JP5054516B2 - Thermosetting resin composition - Google Patents

Description

  The present invention relates to a thermosetting resin composition. More specifically, the present invention can form a uniform protective film excellent in properties such as heat resistance, flexibility, electrical insulation, adhesion, and storage stability and printing work. The present invention relates to a thermosetting resin composition having excellent properties.

  With recent demands for higher performance, more functionality, thinner, lighter, and smaller electronic devices, the demand for flexible and flexible printed wiring boards (FPCs) that are light and bendable is increasing. For example, it is often used in electronic devices that require flexibility and space saving, such as a hinge part of a folding cellular phone and a liquid crystal display. In addition to conventional cable applications, usage methods and shapes are diversified, such as those integrated with a substrate such as a display substrate and a keypad substrate, and those mounted with electronic components such as a driver IC.

  In recent years, the fine patterning of FPC has been progressing. For example, from TAB (Tape Automated Bonding), the use of an FPC package form / processing technique called COF (Chip On Film) is expanding with the demand for finer pitch.

  Thus, there is a demand for higher performance and higher quality of the FPC, and there is a demand for manufacturing processing technology with high production efficiency.

  Amid these technological advances, the method of thermocompression bonding of a film-like cover substrate called coverlay, which has been used for circuit protection so far, is easy to produce by screen printing or the like because of low production efficiency. In addition, a cover coat capable of forming a protective film is being demanded.

  The cover coat is required to have the same electrical insulation, hardness, flexibility, heat resistance (especially soldering heat resistance), etc. as the cover lay. Also, it has excellent printability during printing, and the substrate is warped when the cover coat is formed. It is required to be excellent in adhesion, solvent resistance, acid resistance, plating solution resistance, electrolytic corrosion resistance, flexibility (flexibility), etc., especially in applications where heat resistance is required. Polyimide resin is used.

  However, for example, in order to improve heat resistance, it has been attempted to use a wholly aromatic polyimide resin having excellent heat resistance. However, since this wholly aromatic polyimide resin is insoluble in an organic solvent, the cover coat is formed. In order to prepare an ink for use, it was necessary to dissolve in an organic solvent in the state of polyamic acid which is a polyimide precursor. Such an ink containing polyamic acid has problems such as progress of imidization during storage, increase in viscosity, precipitation of insoluble matter, etc., and thus storage stability is poor and printing is not suitable for printing. It was. Furthermore, the water produced by the imidization reaction during the coating, drying, and curing processes has the drawback of causing voids and swelling in the coating film, resulting in poor adhesion and poor insulation. In addition, when such a polyamic acid type ink is used, generally only a rigid film can be obtained, which is inferior in flexibility (flexibility), and the warpage of the substrate tends to increase when the cover coat is formed. There were problems such as being seen, and it was unsuitable for cover coat applications.

  So far, as a polyimide resin excellent in solvent solubility and processability suitable for a cover coat, a cover coat ink made of a polyimide resin containing an acid anhydride containing an ester group as an acid component (Patent Document 1), A polyimide (Patent Documents 2 to 5) containing a siloxane-containing diamine as a diamine component, a block copolymer (Patent Document 6) containing a polyoxyalkylene diamine as a diamine component, and the like have been proposed.

  Although these have been improved to some extent in terms of solvent solubility and flexibility, the siloxane group-introduced polyimide resin is applied to the substrate, and the coating film is dried and cured. Outgassing occurs due to decomposition, causing voids in the cured film, and has the disadvantage of causing poor adhesion and poor insulation as with the polyamic acid type. In addition, the block copolymer into which a polyoxyalkylene group is introduced has a low Tg, resulting in new defects such as impairing the heat resistance required for the cover coat.

Furthermore, these solvent-soluble polyimide resins have poor solvent resistance and have insufficient performance as protective films for printed wiring boards and the like.
JP-A-8-109259 Japanese Patent Laid-Open No. 9-40777 Japanese Patent Laid-Open No. 10-218993 JP 2000-103848 A Japanese Patent Laid-Open No. 5-331285 JP-A-5-262875

  An object of the present invention is to provide a thermosetting resin composition that has high storage stability and can form a film having excellent properties as a protective film for a printed wiring board.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained the following knowledge in the process of developing a thermosetting resin composition.

(1) As an acid component of a polyimide resin, by using an ester group-containing acid anhydride and a sulfone group-containing acid anhydride in combination, high solvent solubility and high adhesive force (when a film is formed on a substrate, A polyimide resin having high adhesion to the substrate of the coating) is obtained,
(2) As a diamine component of a polyimide resin, by using a polyoxyalkylene group-containing diamine and a specific ether group-containing aromatic diamine in combination, the solvent solubility, flexibility, and heat resistance were excellent. A polyimide resin is obtained.
(3) Storage stability (viscosity stability) of the resulting polyimide resin varnish by making the molar ratio of the acid component of (1) and the diamine component of (2) excessive to the acid component during polyimide formation Improved),
(4) Since the polyimide resin obtained by satisfying the above requirements (1) to (3) has high solvent solubility, an epoxy resin, a filler, or the like is blended into the varnish containing the polyimide resin and the organic solvent. There is no precipitation of polyimide resin, and the width of product design is widened.
(5) Excellent heat resistance, solvent resistance, and chemical resistance by using varnish containing polyimide resin and organic solvent obtained in excess of acid component as in (3) above and mixed with epoxy resin And a flexible coating is obtained,
(6) The thermosetting resin composition containing the polyimide resin, epoxy resin and organic solvent thus obtained is particularly suitable for screen printing for printed wiring boards.

  The present invention has been completed based on such findings, and has been completed. The following thermosetting resin composition, a thermosetting resin molded body obtained by curing the thermosetting resin composition, and the heat An object of the present invention is to provide a cured resin molded body, particularly an electronic component provided with a molded body in the form of a layer or a film, and a cover coat ink for manufacturing a printed wiring board containing the thermosetting resin composition.

Item 1 A thermosetting resin composition comprising a polyimide resin, an epoxy resin, and an organic solvent, wherein the polyimide resin is
(A) component:
(A1) General formula (1)

[Wherein, X ¹ represents a linear or branched alkylene group having ^{1 to} 6 carbon atoms, a 1,3-phenylene group, or a 1,4-phenylene group. ]
And alkylene or phenylenebis (anhydrotrimellitate) represented by formula (2) and (A2)

A tetracarboxylic dianhydride mixture comprising diphenyl sulfone tetracarboxylic dianhydride represented by:
(B) component:
(B1) General formula (3)

[Wherein Y ¹ represents —O—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. ]
And (B2) general formula (4)

[Wherein, Z ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. h, i, and j each represent an integer of 0-50, and the sum of h + i + j is 2-50. ]
A polyimide obtained by subjecting to a diamine mixture containing a polyoxyalkylene diamine represented by the formula (A): component (B) charge molar ratio = 1.01-1.20: 1 and imidation reaction A thermosetting resin composition which is at least one kind of resin.

  Item 2 The thermosetting resin composition according to Item 1, wherein the molar ratio of the component (A1) to the component (A2) is (A1) :( A2) = 95: 5 to 40:60.

  Item 3. The thermosetting resin composition according to Item 1 or 2, wherein a molar ratio of the component (B1) to the component (B2) is (B1) :( B2) = 40: 60 to 90:10.

Item 4 A thermosetting resin composition comprising a polyimide resin, an epoxy resin, and an organic solvent, wherein the polyimide resin is
(A) component:
(A1) General formula (1)

[Wherein, X ¹ represents a linear or branched alkylene group having ^{1 to} 6 carbon atoms, a 1,3-phenylene group, or a 1,4-phenylene group. ]
And alkylene or phenylenebis (anhydrotrimellitate) represented by formula (2) and (A2)

A tetracarboxylic dianhydride mixture containing diphenylsulfone tetracarboxylic dianhydride represented by: and component (B):
(B1) General formula (3)

[Wherein Y ¹ represents —O—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. ]
And (B2) general formula (4)

[Wherein, Z ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. h, i, and j each represent an integer of 0-50, and the sum of h + i + j is 2-50. ]
The molar ratio of the structural unit (AU) derived from the component (A) to the structural unit derived from the component (B) is obtained by subjecting the diamine mixture containing the polyoxyalkylenediamine represented by The thermosetting resin composition which is at least 1 sort (s) of the polyimide resin which is AU: BU = 1.01-1.20: 1.

Item 5 The thermosetting resin composition according to any one of Items 1 or 4, wherein, in General Formula (1), X ¹ is an ethylene group.

  Item 6 The thermosetting resin composition according to Item 1 or 4, wherein, in General Formula (4), h, i, and j are each an integer of 0 to 35, and a total of h + i + j is 5 to 35.

Item 7 The thermosetting resin composition according to Item 1 or 4, wherein in General Formula (4), Z ¹ is a tetramethylene group.

  Item 8 The number average molecular weight of the polyimide resin is 5,000 to 100,000, the weight average molecular weight is 10,000 to 200,000, and the acid value is 1 to 50 mgKOH / g, The thermosetting resin composition according to claim 1.

  Item 9 The thermosetting resin composition according to any one of Items 1 to 8, wherein the epoxy resin is an epoxy resin having an epoxy equivalent of 100 to 10,000.

  Item 10 The epoxy resin has the general formula (5)

[Wherein, R ⁴ represents a hydroxyl group or a glycidyloxy group. p represents an integer of 0 or 1 or more (particularly 0 to 100, preferably 0 to 50). When p is 2 or more, p R ^{4 s} may be the same or different. R ⁵ represents a halogen atom (particularly a chlorine atom or a bromine atom) or an alkyl group having 1 to 5 carbon atoms. b represents an integer of 0 to 4 (particularly 0 to 2). Z ² represents a single bond, —SO ₂ —, an alkylidene group having 1 to 6 carbon atoms, or a cycloalkylidene group having 3 to 8 carbon atoms. Further,-* and *-indicate that the upper structure and the lower structure are connected by a single bond. ]
Bisphenol type epoxy resin represented by
General formula (6)

[Wherein Ar ¹ is a carbon which may have 1 to 3 substituents selected from the group consisting of a halogen atom (particularly a chlorine atom or a bromine atom), a hydroxyl group and an alkyl group having 1 to 5 carbon atoms. The aromatic group of several 6-30 is represented. q represents an integer of 1 or more. Further, (q + 1) Ar ¹ may be the same or different. ]
Novolac type epoxy resin represented by
General formula (7)

[Wherein Ar ² is a carbon which may have 1 to 3 substituents selected from the group consisting of a halogen atom (especially a chlorine atom or a bromine atom), a hydroxyl group and an alkyl group having 1 to 5 carbon atoms. The aromatic group of several 6-30 is represented. Ar ³ represents a phenylene group, a naphthalene group or a biphenylene group. r represents an integer of 1 or more. ]
Modified novolac-type epoxy resin represented by the general formula (8)

[In the formula, Ar ⁴ may have 1 to 3 substituents selected from the group consisting of a halogen atom (particularly a chlorine atom or a bromine atom), a hydroxyl group, and an alkyl group having 1 to 5 carbon atoms. An aromatic group having 6 to 30 carbon atoms is represented. s represents an integer of 1 or more. ]
Item 10. The thermosetting resin composition according to any one of Items 1 to 9, which is at least one selected from the group consisting of dicyclopentadiene type epoxy resins represented by:

  Item 11 The thermosetting resin composition according to Item 1 or 4, which contains 10 to 200 parts by weight of an epoxy resin with respect to 100 parts by weight of the polyimide resin.

  Item 12 The thermosetting resin composition according to Item 1 or 4, further comprising an epoxy resin curing agent.

  Item 13 The thermosetting resin composition according to Item 1 or 4, further comprising a flame retardant.

  Item 14 The thermosetting according to Item 13, wherein the flame retardant is at least one selected from red phosphorus, phosphorus compounds, halogen compounds, siloxane compounds, nitrogen compounds, boron compounds, tin compounds, and antimony flame retardants. Resin composition.

  Item 15. The thermosetting resin composition according to Item 1 or 4, further comprising a filler.

  Item 16. The thermosetting resin composition according to any one of Items 1 to 15, wherein the organic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone and γ-butyrolactone.

  Item 17 The thermosetting resin composition according to any one of Items 1 to 16, wherein the total weight of the polyimide resin and the epoxy resin is 1 to 150 parts by weight with respect to 100 parts by weight of the organic solvent.

  Item 18. A thermosetting resin molded article obtained by drying and curing the thermosetting resin composition according to any one of Items 1 to 17.

  Item 19. The thermosetting resin molded article according to Item 18, which is in the form of an electrically insulating layer or film.

  Item 20 A cover coat ink for producing a printed wiring board, comprising the thermosetting resin composition according to any one of Items 1 to 17.

  Item 21 An electronic component comprising a thermosetting resin molding in the form of a layer or film according to Item 19.

  Item 22. The electronic component according to Item 21, which is a flexible printed wiring board, a TAB substrate, or a COF substrate provided with the thermosetting resin molded body in the form of the layer or film according to Item 19 as a cover coat.

  In the present specification and claims, the number of moles of component (A) is the sum of the number of moles of component (A1) and the number of moles of component (A2). Similarly, the number of moles of component (B) is: (B1) The total number of component moles and (B2) component moles. Therefore, the “molar ratio of the component (A) to the component (B)” is the ratio of [(A1) component mole number + (A2) component mole number] to [(B1) component mole number + (B2) component mole number]. Refers to the ratio.

  According to the present invention, the following excellent effects are exhibited.

  (a) Since the polyimide resin produced from the component (A1), component (A2), component (B1) and component (B2) used in the present invention contains a structure derived from these four components in a well-balanced manner. In addition to the high heat resistance and electrical insulation inherent in polyimide, it also has the advantage of high solubility in solvents despite not being a polyamic acid type.

  (b) Furthermore, since the polyimide resin is obtained with an excess of acid component, the storage stability (viscosity stability) of the resulting polyimide resin varnish is particularly improved.

  (c) Due to the high solvent solubility of the above (a) and the high storage stability of the above (b), an epoxy resin or the like may be added to the polyimide resin varnish composed of the obtained polyimide resin and an organic solvent. , The precipitation of the polyimide resin is suppressed.

  (d) Since a varnish having a high resin concentration can be obtained, the amount of solvent to be evaporated is small, and energy saving can be achieved in the drying and curing steps.

  (e) Since the polyimide resin is neither a polyamic acid type nor a siloxane-containing type, water and siloxane-based outgas are not substantially generated in the coating, drying, and curing steps.

  (f) The thermosetting resin composition of the present invention obtained by blending an epoxy resin with the polyimide resin varnish is excellent in printability, particularly in printability in screen printing for printed wiring boards.

  (g) The thermosetting resin composition of the present invention can be printed, coated, etc., thereby providing heat resistance, solvent resistance, adhesion to a substrate, acid resistance, plating solution resistance, electric corrosion resistance, Excellent physical properties such as bleeding and gives a flexible coating film. In addition, there is little warping of the substrate when forming the cover coat.

  (h) Therefore, the thermosetting resin composition of the present invention is very excellent as an ink for a cover coat of a printed wiring board, particularly a flexible printed wiring board (FPC), and further, an FPC base film and other uses. Can also be used.

FIG. 1 is a schematic view showing a circuit board A. FIG. 2 is a schematic view showing the circuit board B-1. FIG. 3 is a schematic view showing the circuit board B-2. FIG. 4 is an enlarged view of a portion E in FIG. 2 showing the circuit board B-1.

  1-4, the symbols have the following meanings.

DESCRIPTION OF SYMBOLS 10 Comb pattern part 11 Conductor part 11 'Conductor part 12 Terminal part 12' Terminal part 13 Cured film of thermosetting resin composition 20 Comb pattern part 21 Conductor part 21 'Conductor part 22 Terminal part 22' Terminal part 23 Thermosetting Cured film of resin composition 24 Cured film of thermosetting resin composition 21s Space part 23e End part 25 of cured film 23 Bleeding part 25e Tip of bleeding part

Polyimide resin The polyimide resin according to the present invention (hereinafter referred to as “the present imide”) is a solvent-soluble polyimide random obtained by imidizing a tetracarboxylic dianhydride (A) and a diamine (B) according to a conventional method. It is a copolymer. The polyimide random copolymer uses alkylene or phenylene glycol bis (anhydrotrimellitate) (A1) and diphenylsulfone tetracarboxylic dianhydride (A2) as component (A), and component (B) As an ether group-containing aromatic diamine (B1) and polyoxyalkylene diamine (B2), a mixture containing these (A) component (acid component) and (B) component (diamine component) is preferably nitrogen. It is prepared by subjecting to an imidization reaction with heating and stirring in an organic solvent under an inert gas atmosphere such as.

<(A) component: tetracarboxylic dianhydride>
The component (A1) according to the present invention has the general formula (1)

[Wherein, X ¹ represents a linear or branched alkylene group having ^{1 to} 6 carbon atoms, a 1,3-phenylene group, or a 1,4-phenylene group. ]
Specifically, 1,2-ethylene bis (anhydro trimellitate), 1,3-propylene bis (anhydro trimellitate), 1,4-tetramethylene bis (anhydro trimellitate) ), 1,5-pentamethylene bis (anhydro trimellitate), 1,6-hexamethylene bis (anhydro trimellitate), 1,3-phenylene bis (anhydro trimellitate), 1,4- And phenylenebis (anhydrotrimellitate). These acid dianhydrides are all known and readily available compounds. Among these, 1,2-ethylenebis (anhydrotrimellitate) is recommended from the viewpoint of adhesion and flexibility.

  The component (A2) according to the present invention has the general formula (2)

Specifically, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic dianhydride, 2,3 ', 3,4'-diphenylsulfonetetracarboxylic dianhydride is exemplified. These acid dianhydrides are all known and readily available compounds.

  In addition to the above components (A1) and (A2), other tetracarboxylic dianhydrides can be used as necessary, as long as the effects of the present invention are not impaired. Examples of such other tetracarboxylic dianhydrides include aliphatic or alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides having aromatic rings, and aromatic tetracarboxylic dianhydrides. Etc.

  Specific examples of the aliphatic or alicyclic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,1] -heptane-2,3,5,6 − Tracarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc., bicyclo [2,2,2] -octene-2 3,5,6-tetracarboxylic dianhydride and the like.

  Specific examples of the aliphatic tetracarboxylic dianhydride having an aromatic ring include 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho 1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho 1,2-c] furan-1,3-dione and the like.

  Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4′-oxydiphthalic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1 , 4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3 , 3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'- Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether Anhydrides, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride and the like can be mentioned.

<(B) component: diamine component>
The component (B1) according to the present invention has the general formula (3)

[Wherein Y ¹ represents —O—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. ]
Specifically, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone Bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] trifluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] trifluoropropane, and the like. These diamines are all known and readily available compounds. Among these, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and (4- (4-aminophenoxy) phenyl) sulfone are recommended from the viewpoint of imparting heat resistance and flexibility to the produced polyimide resin. Is done.

  The component (B2) according to the present invention has the general formula (4)

[Wherein, Z ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. h, i, and j each represent an integer of 0-50, and the sum of h + i + j is 2-50. ]
A polyoxyalkylene group-containing diamine represented by the above, that is, repeating at least one oxyalkylene group selected from the group consisting of an oxyethylene group, an oxypropylene group and an oxytetramethylene group having a primary amino group at both ends. The diamine which has as a unit is illustrated. These diamines are all known and readily available compounds.

Among the above polyoxyalkylene diamines, a polyoxyalkylene group-containing diamine containing a tetramethylene group from the viewpoint of imparting excellent flexibility to both the resulting polyimide resin and the film obtained from the curable resin composition of the present invention. Is preferred. That is, in the general formula (4), it is preferable that Z ¹ is a tetramethylene group.

  h, i, and j are each an integer of 0 to 50, preferably 0 to 35, and the sum of h + i + j is 2 to 50, preferably 5 to 35, and more preferably 12 to 35. Within such a range, there is a tendency that a polyimide random copolymer having an excellent balance between flexibility and heat resistance is obtained.

  In addition, the component (B2) is commercially available. Specific examples of commercially available products include HUNTSMAN (seller: Mitsui Chemicals Fine Co., Ltd.), product Jeffamine D-230, D-400, D-2000, XTJ- Examples include 500 (ED-600), XTJ-502 (ED2003), EDR-148, XTJ-542, XTJ-533, and XTJ-536.

  The said diamine component can be used for imidation reaction individually or in combination of 2 or more types, respectively.

  Furthermore, if necessary, in addition to the above components (B1) and (B2), known diamines used in this field can be used as long as the effects of the present invention are not impaired. For example, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobiphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxybenzene), 9,9- Bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diamino-3,3′5,5′-tetramethyldiphenylmethane, 4,4′-diamino-3 , 3'5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'5,5'-tetrapropyldiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3' Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( Aromatic diamines such as 4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, hexamethylenediamine, octamethylenediamine, decamethylenediamine, Aliphatic or alicyclic such as diaminocyclohexane, diaminodicyclohexylmethane, diaminodicyclohexylpropane, bisaminomethylcyclohexane, diaminobicyclo [2,2,1] heptane, bis (aminomethyl) -bicyclo [2,2,1] heptane Diamines .

<Imidation reaction>
The polyimide resin of the present invention can be obtained by imidizing the tetracarboxylic acid component and the diamine component, and the imidization reaction itself can be performed according to a known method. For example, a method of polycondensation reaction of a tetracarboxylic acid component and a diamine component in an organic solvent can be mentioned, and the imidization method at that time includes (1) tetracarboxylic acid (component (A)) and diamine ( (B) Component) is heated in an organic solvent to distill off the generated water. (2) After the polyamic acid, which is a polyimide precursor, is produced, a dehydrating compound such as acetic anhydride is used. There are ways to do this.

  Of the production methods (1) and (2), the method (1) is particularly industrially preferable. As a more specific method of (1), after dissolving the component (A) and the component (B) in an organic solvent, the mixture is heated to 100 to 200 ° C., and the generated water in the reaction system is distilled with an azeotropic solvent. The solvent-soluble polyimide random copolymer of the present invention can be obtained by leaving a polycondensation reaction.

  In the imidization reaction, the use ratio of the component (A1) to the component (A2) is not particularly limited, but the molar ratio of the component (A1) to the component (A2) at the start of the reaction is 95: 5 to 40:60. A range is preferred. The molar ratio of the component (A1) :( A2) is preferably 60:40 to 40:60 in terms of the flexibility of the resulting polyimide random copolymer and the viscosity stability of the polyimide varnish. .

  In addition, when using other tetracarboxylic dianhydrides other than (A1) component and (A2) component, the usage-amount can be suitably selected from a wide range, but generally (A1) component and (A2) component The total weight is preferably 1 to 100% by weight, particularly preferably 5 to 50% by weight.

  Further, the use ratio of the component (B1) and the component (B2) is not particularly limited, but the molar ratio of the component (B1) to the component (B2) at the start of the reaction is in the range of 40:60 to 90:10. preferable. From the viewpoint of melt processability and heat resistance of the resulting polyimide copolymer, the molar ratio of the component (B1) :( B2) is preferably 40:60 to 70:30.

  In addition, when using diamine other than (B1) component and (B2) component, the usage-amount can be suitably selected from a wide range, However, Generally with respect to the total weight of (B1) component and (B2) component The content is preferably 1 to 100% by weight, particularly 5 to 50% by weight.

  Further, in the present invention, the use ratio of the component (A) to the component (B) is such that the molar ratio of the component (A) to the component (B) at the start of the reaction is (A) :( B) = 1.01. It is important that ˜1.20: 1, preferably (A) :( B) = 1.01 to 1.05: 1.

  Thus, by using (A) component as a slight excess, the viscosity stability improvement effect of a polyimide varnish is show | played. Moreover, when it is set as the thermosetting resin composition of this invention, in the application | coating, drying, and a hardening process, since the terminal acid group of a polyimide and an epoxy resin react, the solvent resistance of a cured film, heat resistance, etc. The effect to improve is show | played.

  In addition, in this invention, in the range which does not impair the effect of this invention, end cap agents, such as monofunctional acid anhydride and amine, can be used together for the purpose of heat resistance, adhesive improvement, molecular weight control, etc. Specific examples of the end cap agent include phthalic anhydride, maleic anhydride, nadic anhydride, hexahydrophthalic anhydride and the like as acid anhydrides, and aniline, methylaniline, allylamine and the like as amines.

  As the organic solvent used in the imidization reaction according to the present invention, an aprotic polar solvent is preferably used. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2 -Pyrrolidone, diglyme, triglyme, cyclohexanone, cyclopentanone, γ-butyrolactone and the like are exemplified, and these can be used alone or as a mixed system. Of these, N-methyl-2-pyrrolidone and γ-butyrolactone are particularly preferred from the viewpoints of polymerizability and viscosity stability.

  The amount of the organic solvent used is usually 100 to 2,000% by weight, particularly 120 to 500% by weight, preferably 130 to 300% by weight based on the total weight of the tetracarboxylic acid component (A) and the diamine component (B). A weight percent range is recommended.

  In the reaction, a part of the organic solvent can be replaced with an azeotropic solvent for the purpose of efficiently taking out water generated by the imidization reaction out of the system. Examples of the azeotropic solvent include aromatic hydrocarbons such as toluene, xylene and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and dimethylcyclohexane. When these azeotropic solvents are used, the amount used is usually 1 to 30% by weight, preferably 5 to 20% by weight in the organic solvent.

  The reaction time varies depending on the type of the tetracarboxylic acid component, the type of the diamine component, or the molecular weight of the imide of the present invention, but is usually preferably 0.5 to 24 hours.

<Polyimide resin>
As described above, the polyimide resin used in the present invention comprises the component (A) and the component (B), wherein the molar ratio of the component (A): component (B) is (A) :( B) = 1. It is at least 1 type of polyimide resin obtained by using for imidation reaction with the preparation ratio which is 01-1.20: 1.

  According to the inventor's research, the polyimide resin of the present invention obtained by subjecting the component (A) and the component (B) to the imidation reaction as described above is a raw material monomer after the imidization reaction ( Since the A) component and the (B) component do not remain in the reaction system, and substantially all are converted to a polyimide resin, the imidation reaction starts from the (A) component used as a raw material to the (B) component. It can be considered that the molar ratio of time coincides with the molar ratio of the structural unit derived from the component (A) in the polyimide resin obtained by the imidation reaction to the structural unit derived from the component (B).

  Therefore, in the polyimide resin of the present invention obtained by the imidization reaction, the molar ratio of the structural unit (AU) derived from the component (A) to the structural unit (BU) derived from the component (B) is AU: BU = 1. It is considered to be in the range of .01 to 1.20: 1, preferably 1.01 to 1.05: 1.

  Similarly, the molar ratio of the component (A1) to the component (A2) at the start of the imidation reaction is also the structural unit derived from the component (A1) in the polyimide resin obtained by the imidization reaction: the structure derived from the component (A2). The molar ratio of the unit (B1) component: (B2) component at the start of the imidization reaction is also derived from the component (B1) in the polyimide resin obtained by the imidization reaction. It can be considered that this corresponds to the molar ratio of the structural unit derived from the component (B2).

  Therefore, when the molar ratio of the component (A1) to the component (A2) at the start of the reaction is 95: 5 to 40:60, preferably 60:40 to 40:60, The molar ratio of structural unit (A1U) derived from component (A1): structural unit (A2U) derived from component (A2) is A1U: A2U = 95: 5 to 40:60, preferably 60:40 to 40:60. Can be considered. Similarly, when the molar ratio of component (B1): component (B2) at the start of the reaction is 40:60 to 90:10, preferably 40:60 to 70:30, The molar ratio of the structural unit (B1U) derived from the component (B1) to the structural unit (B2U) derived from the component (B2) is B1U: B2U = 40: 60 to 90:10, preferably 40:60 to 70:30. It is thought that.

  Although there is no restriction | limiting in particular in the molecular weight of the polyimide resin (this imide) used by this invention, In terms of being excellent in the balance of solvent solubility, mechanical strength, and heat resistance, the number average molecular weight is 5,000 to 100,000. 000, preferably 7,000 to 50,000 (especially 8,000 to 50,000), particularly preferably 8,000 to 35,000 (especially 10,000 to 35,000) is recommended, and the weight average A molecular weight of 10,000 to 200,000, preferably 15,000 to 100,000, particularly preferably 18,000 to 80,000 (especially 25,000 to 80,000) is recommended. This molecular weight is measured by the GPC method described in the section <Evaluation of physical properties of polyimide resin> in Examples described later. Adjusting the molecular weight of the polyimide resin used in the present invention to the above range can be easily performed by appropriately selecting the reaction time, reaction temperature, type of organic solvent and the amount of the organic solvent used in the imidization reaction. it can.

  The acid value of the polyimide resin is not particularly limited, but the acid value is 1 to 50 mgKOH / g, preferably 5 to 5 in terms of excellent balance between solvent resistance and thermal properties of the resulting thermosetting resin. 30 mg KOH / g, particularly preferably 10-25 mg KOH / g is recommended. This acid value is measured by the method described in the section <Evaluation of physical properties of polyimide resin> in Examples described later.

  Further, the glass transition temperature of the polyimide resin of the present invention is not particularly limited, but the glass transition temperature is about -20 to 150 ° C, particularly 20 to 110 ° C, from the viewpoint of excellent flexibility of the resulting thermosetting resin. It is preferable that it is a grade. The glass transition temperature was measured by the method described in the section <Evaluation of physical properties of polyimide resin> in Examples described later.

  The polymerization solution thus obtained is represented by the present imide, that is, the structural unit derived from the acid component represented by the general formula (1) and the general formula (2), and the general formula (3) and the general formula (4). A polyimide resin solution obtained by dissolving a solvent-soluble polyimide random copolymer having a structural unit derived from a diamine component in the organic solvent used in the imidization reaction, and usually 100 parts by weight of the organic solvent. The imide is dissolved in 1 to 100 parts by weight. From the viewpoint of handleability of the polyimide resin solution, the imide is preferably 5 to 90 parts by weight, more preferably 20 to 80 parts by weight, and particularly preferably 30 to 75 parts by weight with respect to 100 parts by weight of the organic solvent. It is recommended that it be dissolved in

  The polyimide resin solution can be used as a polyimide varnish as it is, and the organic solvent used for the imidization reaction is a low boiling point solvent (for example, aromatic hydrocarbons such as toluene, xylene, solvent naphtha, cyclohexane, methylcyclohexane, etc. , Cycloaliphatic hydrocarbons such as dimethylcyclohexane, propylene glycol monomethyl ether, or ketones such as methyl ethyl ketone and methyl isobutyl ketone), or the polyimide resin solution is heated and dried or a poor solvent (for example, methanol In addition, the polyimide random copolymer of the present invention is isolated by adding a lower alcohol such as isopropyl alcohol, or an acetate ester such as ethyl acetate or butyl acetate), and then dissolved in another desired organic solvent. Polyimide resin varnish Can be, the concentration of the polyimide resin at that time, be in the same concentration range as the polyimide resin solution is recommended.

  The viscosity of the polyimide resin varnish of the present invention varies depending on the concentration of the polyimide resin, the type of organic solvent, and the like, but when measured at 25 ° C. using a B-type viscometer, it is about 1 to 100 Pa · s, particularly 2 to 30 Pa. -It preferably has a viscosity of about s. In particular, the viscosity change (viscosity increase) when the varnish is stored for 1 month immediately after production under the conditions of 25 ° C. and 60% RH is preferably 25% or less, particularly 20% or less. The polyimide resin varnish of the present invention is excellent in storage stability as shown in Examples described later.

Epoxy resin In producing the thermosetting resin composition of the present invention, an epoxy resin is mixed with the polyimide resin varnish.

  Various epoxy resins known in this field can be used as the epoxy resin used in the present invention, and the epoxy equivalent of the epoxy resin can be appropriately selected from a wide range. Generally, the epoxy equivalent is 100 to 10000, particularly 100 to 3000. It is preferable to use an epoxy resin.

  As the epoxy compound constituting the epoxy resin, an epoxy compound having two or more epoxy groups in one molecule can be preferably used. Examples of the epoxy compound having two or more epoxy groups in one molecule include (a) polyphenol type epoxy resin, (b) polyglycidylamine type epoxy resin, (c) polyol type epoxy resin, and (d) glycidyl. Examples thereof include ester type epoxy resins, (e) isocyanuric type epoxy resins, and (f) alicyclic epoxy resins.

  Examples of the polyphenol type epoxy resin (a) include bisphenol type epoxy resins, novolac type epoxy resins, modified novolac type epoxy resins, dicyclopentadiene type epoxy resins and the like.

  As a bisphenol type epoxy resin, for example, the general formula (5)

[Wherein, R ⁴ represents a hydroxyl group or a glycidyloxy group. p represents an integer of 0 or 1 or more (particularly 0 to 100, preferably 0 to 50). When p is 2 or more, p R ^{4 s} may be the same or different. R ⁵ represents a halogen atom (particularly a chlorine atom or a bromine atom) or an alkyl group having 1 to 5 carbon atoms. b represents an integer of 0 to 4 (particularly 0 to 2). Z ² represents a single bond, —SO ₂ —, an alkylidene group having 1 to 6 carbon atoms, or a cycloalkylidene group having 3 to 8 carbon atoms. Further,-* and *-indicate that the upper structure and the lower structure are connected by a single bond. ]
These are generally obtained by the reaction of a bisphenol compound and an epihalohydrin.

Examples of the bisphenol compound include biphenol, bisphenol A, bisphenol F, bisphenol S, and bisphenol AD, which are selected from the group consisting of halogen atoms (particularly chlorine atoms or bromine atoms) and alkyl groups having 1 to 5 carbon atoms. You may have 1-4 substituents (especially 1-2) chosen. In particular, the polyfunctional bisphenol-type epoxy resin having 3 or more glycidyloxy groups (that is, p is 1 or more and at least one of p R ⁴ is a glycidyloxy group) It is preferable at the point which gives the heat resistance and solvent resistance which were excellent in the thermosetting resin molding of invention.

As the novolac type epoxy resin, for example, the general formula (6)

[In the formula, Ar ¹ may have 1 to 3 substituents selected from the group consisting of a halogen atom (particularly a chlorine atom or a bromine atom), a hydroxyl group, and an alkyl group having 1 to 5 carbon atoms. An aromatic group having 6 to 30 carbon atoms (particularly 6 to 15 carbon atoms) is represented. q represents an integer of 1 or more (particularly 1 to 50, preferably 1 to 10). In addition, (q + 1) Ar ¹ may be the same or different. ]
These are generally obtained by glycidyl etherification of a polycondensate of a phenolic compound and formaldehyde.

  The phenolic compounds include phenol, cresol, xylenol, butylphenol, pentylphenol, resorcin, catechol, hydroquinone, phenylphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, biphenol, tetramethylbiphenol, hydroxynaphthalene, dihydroxynaphthalene Etc. are exemplified. These phenolic compounds are 1 to 3 substituents selected from the group consisting of halogen atoms (particularly chlorine atoms or bromine atoms), alkyl groups having 1 to 5 carbon atoms, and hydroxyl groups. It may be substituted with a halogen atom (particularly a chlorine atom or a bromine atom).

Therefore, Ar ¹ is typically a residue obtained by removing one hydroxyl group and one hydrogen atom on the aromatic ring from these phenolic compounds. Among these novolac type epoxy resins, the bisphenol A-novolac type epoxy resin whose phenolic compound is bisphenol A is preferable in terms of giving excellent heat resistance and solvent resistance to the thermosetting resin.

  Examples of the modified novolac type epoxy resin include a general formula (7)

[Wherein Ar ² may have 1 to 3 substituents selected from the group consisting of a halogen atom (particularly a chlorine atom or a bromine atom), a hydroxyl group, and an alkyl group having 1 to 5 carbon atoms. An aromatic group having 6 to 30 carbon atoms (particularly 6 to 15 carbon atoms) is represented. Ar ³ represents a phenylene group, a naphthalene group or a biphenylene group. r represents an integer of 1 or more (particularly 1 to 50, preferably 1 to 10). ]
These are generally obtained by glycidyl etherification of a polycondensate of a phenol compound and an aromatic dimethylol compound.

Examples of the phenol compounds include phenol, cresol, xylenol, butylphenol, pentylphenol, resorcin, catechol, hydroquinone, phenylphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, biphenol, tetramethylbiphenol, hydroxynaphthalene, dihydroxynaphthalene. Etc. are exemplified. These phenolic compounds are 1 to 3 substituents selected from the group consisting of halogen atoms (particularly chlorine or bromine atoms), hydroxyl groups and alkyl groups having 1 to 5 carbon atoms, It may be substituted with a halogen atom (particularly a chlorine atom or a bromine atom). Therefore, Ar ² is typically a residue obtained by removing one hydroxyl group and one hydrogen atom on the aromatic ring from these phenolic compounds.

Examples of the aromatic dimethylol compound include xylylene glycol, dimethylol naphthalene, and dimethylol biphenyl. Accordingly, —CH ₂ —Ar ³ —CH ₂ — is typically a residue obtained by removing two hydroxyl groups (hydroxyl groups constituting a methylol group) of these aromatic dimethylol compounds.

Among these modified novolak-type epoxy resins, biphenylene group-modified novolak-type epoxy resins in which Ar ³ is a biphenylene group or a naphthylene group, and naphthylene group-modified novolak-type epoxy resins have excellent heat resistance in the resulting thermosetting resin molding of the present invention. It is preferable at the point which gives property and solvent resistance.

  As the dicyclopentadiene type epoxy resin, for example, the general formula (8)

[Wherein Ar ⁴ may have 1 to 3 substituents selected from the group consisting of a halogen atom (particularly a chlorine atom or a bromine atom), a hydroxyl group, and an alkyl group having 1 to 5 carbon atoms. An aromatic group having 6 to 30 carbon atoms (particularly 6 to 15 carbon atoms) is represented. s represents an integer of 1 or more (particularly 1 to 50, preferably 1 to 10). ]
These are generally obtained by glycidyl etherification of a polycondensate of dicyclopentadiene and a phenolic compound.

The phenolic compounds include phenol, cresol, xylenol, butylphenol, pentylphenol, resorcin, catechol, hydroquinone, phenylphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, biphenol, tetramethylbiphenol, hydroxynaphthalene, dihydroxynaphthalene Etc. are exemplified. These phenolic compounds are 1 to 3 substituents selected from the group consisting of halogen atoms (particularly chlorine or bromine atoms), hydroxyl groups and alkyl groups having 1 to 5 carbon atoms, It may be substituted with a halogen atom (particularly a chlorine atom or a bromine atom). Therefore, Ar ⁴ is typically a residue obtained by removing one hydroxyl group and one hydrogen atom on the aromatic ring from these phenolic compounds. Such dicyclopentadiene type epoxy resins are commercially available, and examples thereof include “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “HP-7200” manufactured by Dainippon Ink & Chemicals, Inc., and the like.

  Moreover, as another polyphenol type epoxy resin, what is represented by the following general formula (9) or (10) can be illustrated, for example.

  General formula (9)

[In the formula, Ar ⁵ and Ar ⁶ are the same or different from each other and are each selected from the group consisting of a halogen atom (particularly a chlorine atom or a bromine atom), a hydroxyl group, and an alkyl group having 1 to 5 carbon atoms. Represents an aromatic group having 6 to 30 carbon atoms which may have one substituent. t represents an integer of 1 or more (particularly 1 to 50). ]
Epoxy resin represented by Specific examples thereof include glycidyl etherified products of polyphenol compounds obtained by dehydration condensation of hydroxybenzaldehydes such as hydroxybenzaldehyde, methylhydroxybenzaldehyde and dimethylhydroxybenzaldehyde and phenolic compounds (for example, “EPPN” manufactured by Nippon Kayaku Co., Ltd.). -502H ").

The phenolic compounds include phenol, cresol, xylenol, butylphenol, pentylphenol, resorcin, catechol, hydroquinone, phenylphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, biphenol, tetramethylbiphenol, hydroxynaphthalene, dihydroxynaphthalene Etc. are exemplified. These phenolic compounds are 1 to 3 substituents selected from the group consisting of halogen atoms (particularly chlorine or bromine atoms), hydroxyl groups and alkyl groups having 1 to 5 carbon atoms, It may be substituted with a halogen atom (particularly a chlorine atom or a bromine atom). Therefore, Ar ⁵ and Ar ⁶ are typically residues obtained by removing one hydroxyl group and one hydrogen atom on the aromatic ring from one of these phenol compounds, One of these is a residue obtained by removing one hydroxyl group and one formyl group on the aromatic ring from hydroxybenzaldehydes.

  General formula (10)

[Wherein R ⁷ represents an aliphatic group having 1 to 4 carbon atoms. u represents an integer of 3 to 4. ]
Epoxy resin represented by Specific examples thereof include glycidyl ethers of polyhydric phenols such as tris (hydroxyphenyl) methane and tetrakis (hydroxyphenyl) ethane (for example, “Tactex-742” and “XD-9053” manufactured by Dow Chemical Company). "Japan Epoxy Resin" 1031 "etc.).

  Examples of the polyglycidylamine-type epoxy resin (b) include reaction products of aniline derivatives such as aniline, toluidine, methylenedianiline, aminophenol and epihalohydrin.

  Examples of the polyol type epoxy resin (c) include hydrogenated bisphenol A, alkylene oxide adducts of bisphenol A, trimethylolpropane, neopentyl glycol, polyalkylene glycol, sorbitol, glycidyl ether of polyhydric alcohol such as glycerin. Is done.

  Examples of the glycidyl ester type epoxy resin (d) include glycidyl esters of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid and hexahydrophthalic acid.

  Examples of the isocyanuric epoxy resin (e) include triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate.

  Examples of the alicyclic epoxy resin (f) include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, di (3,4-epoxycyclohexylmethyl) adipate, and tetra (3,4- Examples thereof include epoxycyclohexylmethyl) butanetetracarboxylate, di (3,4-epoxycyclohexylmethyl) -4,5-epoxytetrahydrophthalate, “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.

  In addition to these, a vinyl polymer having an epoxy group, and an epoxy resin obtained by modifying or crosslinking the epoxy resin are exemplified.

  The various epoxy resins used in the present invention are all known and readily available, or can be produced according to known methods. Among the above epoxy resins, polyphenol type epoxy resins are preferable. Among them, bisphenol A type epoxy resins represented by general formula (5), novolac type epoxy resins represented by general formula (6), and general formula (7) The modified novolac type epoxy resin represented by the formula (1) and the dicyclopentadiene type epoxy resin represented by the general formula (8) are preferable in that they are excellent in heat resistance, solvent resistance, and electric corrosion resistance of the thermosetting resin.

  These epoxy resins can be used alone or in admixture of two or more.

  The blending amount of the epoxy resin in the thermosetting composition of the present invention is recommended to be in the range of 10 to 200 parts by weight, particularly 10 to 100 parts by weight, preferably 20 to 80 parts by weight with respect to 100 parts by weight of the polyimide resin. Is done. Within this range, the thermosetting resin composition of the present invention has particularly excellent heat resistance, flexibility and storage stability.

Epoxy resin curing agent The thermosetting resin composition of the present invention may contain a curing agent for an epoxy resin, if necessary.

  There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which concerns on this invention, As long as it has the effect | action which hardens or accelerates | stimulates an epoxy resin, what is conventionally well-known or marketed can be used widely. Specific examples of the epoxy resin curing agent include amine compounds, acid anhydride compounds, phenol compounds, and the like.

  Examples of amine compounds include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, and trimethylhexamethylenediamine; diethylenetriamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepenta Mine, aliphatic polyamines such as polyoxyalkylenediamine represented by the general formula (4); fats containing aromatic rings such as metaxylylenediamine, valaxylylenediamine, 1,3,5-tris (aminomethyl) benzene Diamines; cycloaliphatic diamines such as diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, isophoronediamine, mensendiamine, norbornenediamine; phenylenediamine, methyle Aromatic amines such as dianiline, diaminodiphenylsulfone, and metaaminobenzylamine; triethylamine, benzyldimethylamine, tris (dimethylaminomethyl) phenol, triethanolamine, pyridine, picoline, N, N′-dimethylpiperazine, 1,4- Tertiary amines such as diazabicyclo [2,2,2] octane and 1,8-diazabicyclo [5,4,0] undecene; 2-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-ethyl-4 -Imidazol compounds such as methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole; Acid hydrazite, disiamine diamide compounds, melamine compounds, amine adducts obtained by reacting these amine compounds with epoxy resins, urea, isocyanate compounds or acid anhydrides (Ajinomoto Co., “Amicure PN-23”, Amicure “MY” -24 ", manufactured by Fuji Kasei Co., Ltd.," Fujicure FXE "," Fujicure FXR ", etc.," HT-939 "manufactured by Ciba Specialty Chemicals Co., Ltd.), salt of the above amine compound and polycarboxylic acid (Ajinomoto Co., Inc. ATU "), a molecular compound of an amine compound and isocyanuric acid, and the like.

  Examples of acid anhydride compounds include aliphatic acid anhydrides such as alkenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Alicyclic acid anhydrides such as acid, methylhexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydro An aromatic acid anhydride such as trimellitate is exemplified.

  As the phenolic compound, a phenolic compound in which the glycidyloxy group is substituted with a hydroxyl group in the above general formulas (6) to (10) (that is, the hydroxyl group is bonded to the position where the glycidyloxy group is bonded). Illustrated. These phenolic compounds are also known and easily available.

  In addition, onium salts such as benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt, and benzylphosphonium salt are also exemplified as the epoxy resin curing agent.

  When using these epoxy resin hardening | curing agents, the addition amount is 0.01-200 weight part normally with respect to 100 weight part of epoxy resins, Especially the range of 0.1-100 weight part is preferable.

Filler Furthermore, a filler can be blended in the thermosetting resin composition of the present invention, if necessary. The filler according to the present invention is not particularly limited, and conventionally known fillers can be widely used. Specific examples of such fillers include barium sulfate, natural silica, synthetic silica, talc, mica, kaolin, clay, titanium oxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, light calcium carbonate, calcium bicarbonate, water Examples include lastonite, calcium titanate, aluminum borate, sepiolite, and zonotlite. These fillers may be surface-treated with fatty acids, phosphate esters, titanate coupling agents, silane coupling agents and the like.

  The shape of the filler is not particularly limited, and may be any shape such as a plate shape or a needle shape. The average particle size is not particularly limited, and is usually 0.001 to 500 μm, preferably 0.1 to 100 μm, but using a conventionally known method such as an intercalation method or a sol-gel method, You may disperse | distribute to the average particle diameter of about 100 nm.

  In addition, the said average particle diameter is an average particle diameter measured by the analysis of the laser diffraction scattering method particle size distribution measuring apparatus or the transmission electron microscope image.

  When these fillers are used, the addition amount may be appropriately selected from a wide range, but usually 0.1 to 200 parts by weight, particularly 1 to 100 parts by weight with respect to 100 parts by weight of the polyimide resin. preferable.

Organic solvent The organic solvent according to the present invention is, in principle, the organic solvent used in the imidization reaction, but is not limited to this, and various types can be used, and of these, aprotic polar solvents are preferred. Used for. Specific examples of the aprotic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, and N-methyl. Examples include 2-pyrrolidone (hereinafter referred to as NMP), diglyme, triglyme, cyclohexanone, cyclopentanone, γ-butyrolactone (hereinafter referred to as GBL), and the like. These may be used alone or as a mixed system. Among these, NMP and GBL are particularly preferable from the viewpoint of storage stability of the obtained cover coat. In addition to storage stability, the combined use of NMP and GBL is more preferable from the viewpoint of excellent balance of hygroscopicity and wettability of the cover coat to the base film.

  In addition, for the purpose of efficiently performing the drying process, a part of the solvent can be replaced with a low boiling point solvent. Examples of the low boiling point solvent include aromatic hydrocarbons such as toluene, xylene and solvent naphtha, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and dimethylcyclohexane, propylene glycol monomethyl ether, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. Examples are given. The amount of these low-boiling solvents used is usually recommended in the range of 1 to 30% by weight, preferably 5 to 20% by weight, based on the total amount of organic solvents.

  In the thermosetting resin composition of the present invention, the total weight of the polyimide resin and epoxy resin is 1 to 150 parts by weight, preferably 20 to 120 parts by weight, particularly preferably 50 to 100 parts by weight of the organic solvent. 110 parts by weight is recommended.

Flame retardant The thermosetting resin composition of the present invention preferably contains a flame retardant. The flame retardant is not particularly limited as long as it is a substance that can be mixed with the thermosetting resin composition according to the present invention to exhibit flame retardancy, and specifically includes red phosphorus and phosphorus. Examples include compounds (phosphorus compounds), compounds containing halogen (halogen compounds), compounds containing siloxane structures (siloxane compounds), nitrogen compounds, boron compounds, zinc compounds, tin compounds, and antimony flame retardants.

<Phosphorus compounds>
Specific examples of the phosphorus compound include phosphorus compounds such as red phosphorus, phosphine, phosphine oxide, phosphazene compounds, phosphate esters (including condensed phosphate esters), and phosphite esters.

  These phosphorus compounds are known, and various types are commercially available. Specifically, for example, red phosphorus flame retardant such as Nova Excel F5 (trade name, manufactured by Phosphor Chemical Co., Ltd.), triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2, 6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis (t-butylphenyl) phenyl phosphate, tris (t-butylphenyl) phosphate, isopropyl diphenyl phosphate, bis (isopropylphenyl) phenyl phosphate , Tris (isopropylpyrophenyl) phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) Phosphate esters such as phosphate; non-halogen condensed phosphate esters such as resorcinol bis (diphenyl phosphate), resorcinol bis (xylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (xylenyl phosphate) A (meth) acryloylalkyl phosphate ester such as diphenyl- (meth) acryloyloxyethyl phosphate; and a phosphite ester such as phosphorous acid triphenyl ester.

<Halogen compounds>
As the halogen compound, an organic compound containing chlorine or bromine is generally used, but a compound containing bromine (bromine-containing compound) is preferable from the viewpoint of imparting flame retardancy.

  These bromine-containing compounds are known and various types are commercially available. Specific examples of such commercially available bromine-containing compounds include tribromophenyl (meth) acrylate (for example, New Frontier BR-30 and BR-30M manufactured by Daiichi Kogyo Seiyaku), polyoxyethylene-modified tribromo Brominated monomers such as phenyl (meth) acrylate (for example, New Frontier BR-31 manufactured by Daiichi Kogyo Seiyaku) and polyoxyethylene-modified tetrabromo (meth) acrylate (for example, New Frontier BR-42M manufactured by Daiichi Kogyo Seiyaku); Brominated aromatic triazines such as Pyroguard SR-245 (trade name, manufactured by Daiichi Kogyo Seiyaku); Brominated aromatic polymers such as Piroguard SR-250 and SR-400A (both trade names, manufactured by Daiichi Kogyo Seiyaku); Brominated aromatic compounds such as Pyroguard SR-990A (trade name, manufactured by Daiichi Kogyo Seiyaku); It is not limited in particular.

A halogenated bisphenol-type epoxy resin represented by the general formula (5) in which R ⁵ represents a halogen atom, and a halogen represented by the general formula (6) in which Ar ¹ represents an aromatic group having a halogen atom as a substituent. Epoxy resin, Ar ² represents a halogenated epoxy resin represented by the general formula (7) showing an aromatic group having a halogen atom as a substituent, and Ar ⁴ represents an aromatic group having a halogen atom as a substituent. Since the halogenated epoxy resin represented by the formula (8) also functions as a flame retardant, even when these resins are used, even if the flame retardant is not used or the amount of the flame retardant used is small, Flame retardancy is demonstrated.

  Various commercially available products can be used as the halogenated epoxy resin, and examples thereof include Etototo YDB-360, YDB-400, and YDB408 manufactured by Tohto Kasei.

  Moreover, as a flame retardant, the compound which straddles the category of the said halogen-type compound and the category of a phosphorus compound may be sufficient. That is, it may be a phosphorus compound having a halogen atom in one molecule. Specific examples of such compounds include halogen-containing phosphate esters such as tris (2-chloroethyl) phosphate) tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneopentyl) phosphate, and the like. Examples thereof include halogen-containing condensed phosphate esters, but are not particularly limited thereto.

<Siloxane compound>
Although it does not specifically limit as a siloxane compound used as a flame retardant, from the point which can provide heat resistance effectively in addition to a flame retardance, General formula (11)

[Wherein, v and w represent an integer of 1 or more (particularly 1 to 100). ]
The methyl phenyl silicone oil represented by these is preferable. Among them, the ratio of the number of moles of w to the total number of moles of v and w (that is, [w / (w + v)] × 100) is 10 mol% or more, preferably 20 mol% or more, more preferably 25 It is more preferable that it is methylphenyl silicone oil which is more than mol%. The smaller the phenyl group content, the smaller the flame retardant effect. The higher the phenyl group content, the higher the flame retardant effect, which is desirable.

  Various commercially available methylphenyl silicone oils can be used. Specific examples include trade names KF50-100S, KF54, KF56, HIVAC F4, HIVAC F5, and X-22 manufactured by Shin-Etsu Silicone Co., Ltd. 1824B, KR211, KR311, and the like.

<Nitrogen compounds>
Examples of nitrogen compounds include guanidine flame retardants, guanane urea flame retardants, melamine cyanurate (for example, MC-860 manufactured by Nissan Chemical Industries), melamine polyphosphate (for example, PMP-100 manufactured by Nissan Chemical Industries), melamine, melam, Melamine-based flame retardants such as melem's polyphosphate (for example, PMP-200 manufactured by Nissan Chemical Co., Ltd.) can be mentioned.

<Boron compound>
Examples of the boron compound include boric acid flame retardants such as zinc borate.

<Zinc compound>
Examples of the zinc compound include zinc-based flame retardants such as zinc hydroxystannate, zinc stannate, and zinc oxide.

<Tin compounds>
Examples of tin compounds include tin-based flame retardants such as tin oxide.

<Antimony flame retardant>
Examples of the antimony flame retardant include antimony oxide flame retardants such as antimony trioxide and antimony pentoxide, and sodium antimonate.

Various commercially available antimony flame retardants can be used, such as Sun Epoch NA-3181, NA-4800, NA-1030 as antimony pentoxide, and NA-1070L as sodium antimonate (all are trade names, Nissan Chemical).
These flame retardants may be used alone or in combination of two or more.

<Content ratio of flame retardant>
In the thermosetting resin composition according to the present invention, when the flame retardant is used, the content ratio is not particularly limited, but the thermosetting resin composition of the present invention (that is, an essential component). The total amount of polyimide resin, epoxy resin and organic solvent) is preferably within the range of 1 to 50 parts by weight, more preferably within the range of 5 to 20 parts by weight. These flame retardants may be used alone or in combination of two or more.

  When the flame retardant is used in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the thermosetting resin composition, flame retardancy can be imparted to the cured film of the thermosetting resin composition, and the thermosetting resin composition The solder heat resistance and electric corrosion resistance of the cured film of the product are also improved.

Other components or components commonly used in this field may be added to the thermosetting resin composition of the present invention, if necessary. For example, tolylene diisocyanate blocked with caprolactam, oxime, malonic acid ester, morpholine diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate blocked isocyanate, n-butylated melamine resin, isobutylated melamine resin, butylated urea resin , Thermosetting components such as amino resin such as butylated melamine urea co-condensation resin and benzoguanamine co-condensation resin, and styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid resin, diallyl Phthalate resin, phenoxy resin, melamine resin, urethane resin, fluorine resin, polyester resin, polyamide resin, polyimide resin (other than the polyimide resin used in the present invention), polyamideimide resin, It can be added to polymer compounds such as phenol resin. Leveling agents such as silicon and acrylate copolymers, fluorosurfactants; adhesion-imparting agents such as silane coupling agents; thixotropic agents such as aerosil; antifoaming agents; various additives such as antioxidants; dispersion stability A surfactant, a polymer dispersing agent, etc. may be added to improve the viscosity.

  When these other components are used, they may be used in amounts that are usually used, but are preferably used in amounts that do not impair the effects of the present invention.

Thermosetting resin composition of the present invention The thermosetting resin composition of the present invention includes, for example, the above components (polyimide resin, epoxy resin and organic solvent, and if necessary, a curing agent, a filler, other components, etc. Can be prepared by a known kneading method using a three-roll, ball mill, sand mill or the like.

  In that case, there is no particular limitation on the mixing order of the polyimide resin, epoxy resin, organic solvent and other components added as necessary (epoxy resin curing agent, filler, various additives). You may mix in order. For example, a mixture of a part of polyimide resin and an epoxy resin curing agent is prepared in advance, and apart from this, the remaining amount of polyimide resin, epoxy resin, and other components such as fillers and additives as necessary. Examples thereof include a method of preparing a mixture obtained by mixing, and preparing the mixture by mixing the above two mixtures at the time of use.

Thermosetting resin molded body of the present invention can be obtained by drying and curing the thermosetting resin composition of the present invention thus obtained according to a conventionally known method.

  For example, the thermosetting resin composition of the present invention is directly applied to the surface of the adherend by a known method, or the adherend is applied by dipping in the thermosetting resin composition of the present invention. By drying and curing, a thermosetting resin molded body (that is, a resin molded body cured by heat) can be obtained. In this case, the obtained thermosetting resin molded body is usually in the form of an electrically insulating layer or film. The thickness of the layer or film depends on the purpose of use, but it is generally recommended to be 0.1 to 500 μm, particularly 1 to 30 μm, preferably 3 to 30 μm.

  In addition, the thermosetting resin composition of the present invention is formed into a sheet shape or a film shape, or is impregnated into glass fiber, aramid fiber or the like pre-formed into a sheet shape, and then dried and cured. It can also be used after being molded into an adhesive sheet or the like. In this case, the obtained thermosetting resin molding is usually in the form of a film or sheet. The thickness of the film or sheet depends on the purpose of use, but is generally 0.1 to 500 μm, particularly preferably 1 to 30 μm.

  Here, “drying and curing” is to volatilize the organic solvent from the thermosetting resin composition and to chemically react the polyimide resin, epoxy resin, and a curing agent used as necessary. Operation is not strictly distinguished. The drying and curing conditions vary depending on the type of substrate and the method of use, but examples are typically 60 to 200 ° C. (preferably 100 to 180 ° C.) and 10 to 200 minutes (preferably 60 to 120 minutes). .

  The thermosetting resin molded body of the present invention obtained by drying and curing is excellent in the balance between heat resistance and flexibility, insulation, solvent resistance, etc., and is useful as a coating material. It can be suitably used as a coating material such as a material, an adhesive material, metal or plastic.

Electronic components Further, the thermosetting resin composition of the present invention, the adhesive between the polyimide film and the metal foil, FPC base film, the coating material of the printed wiring board is suitable for electronic component applications, such as protective film capacitor, etc. . Accordingly, the present invention provides a thermosetting resin layer or film (generally having a thickness of 0.1 to 500 μm, particularly 1 to 30 μm, preferably 3 to 3) obtained by drying and curing the thermosetting resin composition of the present invention. It also provides an electronic component with 30 μm).

  Examples of the electronic component include a wide range, for example, a layer or film of a thermosetting resin obtained by drying and curing the thermosetting resin composition of the present invention or a film or sheet of the present invention. Examples of the electronic component using the molded body as a base film include a single-sided flexible printed wiring board, a double-sided flexible printed wiring board, a flexible printed wiring board (FPC) such as a multilayer flexible printed wiring board, and a flex-rigid wiring board. Electronic components provided with a layer or film formed by drying and curing the thermosetting resin composition of the invention as a coating (for example, as a cover coat) include printed wiring boards, flexible printed wiring boards, flex-rigid wiring boards, TAB ( Tape Automated Bonding (COF) substrate, COF (chip-on-film) substrate, ceramic Printed wiring board, capacitors and the like. Among these, a printed wiring board (particularly a flexible printed wiring board), a TAB board, a COF board, and the like provided with the thermosetting resin layer or film of the present invention as a cover coat are preferable.

  In the present specification and claims, unless otherwise specified, the term “printed wiring board” only forms a conductor circuit, and does not mount components such as an integrated circuit, a resistor, and a capacitor. In addition, it is intended to indicate both of the components in which components such as an integrated circuit, a resistor, and a capacitor are mounted on a conductor circuit.

Cover coat ink for printed wiring board As described above, the thermosetting resin composition of the present invention is useful for forming a cover coat for a printed wiring board or the like. In particular, the thermosetting resin composition of the present invention is particularly useful as an ink for a cover coat of a flexible printed wiring board. Below, the usage method of the thermoplastic resin composition of this invention with a flexible printed wiring board is demonstrated.

  The thermosetting resin composition of the present invention is used for a printed wiring board as it is or in a form diluted by further using an appropriate organic solvent (for example, the organic solvent described in the above-mentioned “organic solvent”). Can be used as cover coat ink.

  The printed wiring board that can be used in the present invention, particularly the flexible printed wiring board, is not particularly limited, and conventionally known ones can be widely used. For example, on a flexible printed wiring board with a metal foil (as examples of metals, copper, aluminum, silver, gold, iron, nickel, chromium, and alloys thereof) created by a metalizing method, a casting method, or a laminate method, A photoresist is applied, a circuit pattern is exposed, developed, and etched to form a circuit pattern. Then, the photoresist is peeled off to manufacture a circuit board using a printed wiring board.

  A cover coat ink for a printed wiring board containing the thermosetting resin composition of the present invention is applied onto the substrate by dipping, spraying, spin coater, roll coater, curtain coater, screen printing or the like, followed by drying and curing. By doing so, a layer or a film formed by drying and curing the thermosetting resin composition of the present invention can be formed on the substrate. Incidentally, the drying process means volatilization of the organic solvent from the thermosetting resin composition, and the curing process means reaction curing of the polyimide resin and the epoxy resin. There is no strict division, and it is often performed in a continuous process. Examples of the drying and curing conditions include 60 to 200 ° C. (preferably 100 to 180 ° C.) and 10 to 200 minutes (preferably 60 to 120 minutes).

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. “Part” and “%” shown below mean “part by weight” and “% by weight”, respectively, unless otherwise specified.

  In the following synthesis examples, examples and comparative examples, the abbreviations of the compounds and the measuring methods of the respective properties are as follows.

(1) Explanation of abbreviations Abbreviations in synthesis examples of polyimides are as follows:
TMEG: 1,2-ethylenebis (anhydrotrimellitate) (component (A1))
DSDA: 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (component (A2))
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane (component (B1))
BAPS: Bis [4- (4-aminophenoxy) phenyl] sulfone (component (B1))
D-400: manufactured by HUNTSMAN, trade name “Jeffamine D-400”, Z ¹ = 1,2-propylene group, R ^{1 to} R ³ = methyl group, h + i + j = 5 or 6 in the general formula (4) Polyoxyalkylenediamine (component (B2))
D-2000: manufactured by HUNTSMAN, “Jeffamine D-2000”,
In general formula (4), Z ¹ = 1,2-propylene group, R ^{1 to} R ³ = methyl group, and polyoxyalkylene diamine in which the sum of h + i + j is 33) (component (B2))
XTJ-542: manufactured by HUNTSMAN, "Jeffamine XTJ-542")
In the general formula (4), Z ¹ = tetramethylene group, R ^{1 to} R ³ = methyl group, and polyoxyalkylenediamine having a total of h + i + j of 14 (component (B2))
GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone.

(2) Physical property evaluation of polyimide resin
(A ) About 2 g of a polyimide resin solution (polyimide varnish), which is a reaction product after completion of the acid value imidization reaction, is precisely weighed and diluted with 60 ml of THF, and then the acid value is measured according to JIS K 0070-1966. Converted to pure polyimide resin.

(B) About 1 g of a polyimide resin solution (polyimide varnish), which is a reaction product after completion of the molecular weight imidization reaction, was diluted with 30 ml of dimethylformamide to obtain a sample for molecular weight measurement. For these measurement samples, the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polyethylene oxide were determined by gel permeation chromatography (GPC) using dimethylformamide as a solvent.

(C) Glass transition temperature After applying a polyimide resin solution (polyimide varnish) as a reaction product after imidization reaction on a polytetrafluoroethylene (PTFE) sheet, at 120 ° C. for 1.5 hours. It dried and peeled from the PTFE sheet to obtain a polyimide film having a thickness of 50 μm. The sample for glass transition point measurement was obtained by cut | disconnecting the obtained film. For these measurement samples, a differential scanning calorimeter (DSC-7) manufactured by Perkin Elmer was used, and the inflection point when the temperature was raised from 5 ° C. at a rate of 10 ° C. per minute was defined as the glass transition temperature. .

(D) Varnish viscosity (storage stability)
About the polyimide resin solution which is a reaction product after completion | finish of imidation reaction, the viscosity was measured on 25 degreeC conditions using the B-type viscosity meter. The polyimide solution was stored for 1 month at 25 ° C. and 60% RH, and then the viscosity was measured again.

Synthesis example 1
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 135 g, NMP 135 g, xylene 30 g, (A) component (A1) TMEG 20.9 g (0.051 mol) And (A2) DSDA 18.2 g (0.051 mol), and (B1) BAPP 24.6 g (0.060 mol) and (B2) D-400 16.0 g (0.040 mol) as component (B). The temperature was raised to 180 ° C. while stirring and stirring under a nitrogen stream. The imidization reaction was carried out for 5 hours while distilling the produced water out of the system to obtain a polyimide resin solution having a resin concentration of about 20% by weight. The viscosity immediately after synthesis of the polyimide solution was 4.3 Pa · s, and the viscosity after 1 month storage was 4.5 Pa · s. The obtained polyimide resin had an acid value of 4.1 mgKOH / g, Mn = 22,100, Mw = 48,600, and a glass transition temperature of 88 ° C.

  In addition, in the polyimide resin of the present invention obtained in Synthesis Example 1, after the imidation reaction, the raw material monomer (A) component and (B) component do not remain in the reaction system, and substantially all Since it has been converted to a polyimide resin, the molar ratio at the start of the imidization reaction to the component (B) of the component (A) used as a raw material, and the structural unit (B) derived from the component (A) in the polyimide resin It can be considered that the molar ratio of the component to the structural unit is the same (the same applies to the following Synthesis Examples 2 to 4 (product of the present invention) and Synthesis Examples 5 and 6 (Comparative product)).

  Furthermore, the molar ratio of the component (A1) to the component (A2) at the start of the imidation reaction is also considered to coincide with the molar ratio of the structural unit derived from the component (A1) in the polyimide resin: the structural unit derived from the component (A2). In addition, the molar ratio of the component (B1) to the component (B2) at the start of the imidization reaction is also the structural unit derived from the component (B1) in the polyimide resin: the molar ratio of the structural unit derived from the component (B2). (The same applies to the following synthesis examples 2 to 5 (product of the present invention) and synthesis examples 6 and 7 (comparative product)).

Synthesis example 2
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 270 g, xylene 30 g, (A) component, TMEG 20.9 g (0.051 mol), and DSDA 18.2 g (0.051 mol) As a component (B), 24.6 g (0.060 mol) of BAPP and 80.0 g (0.040 mol) of D-2000 were charged, and the temperature was raised to 180 ° C. while stirring in a nitrogen stream. did. The imidization reaction was carried out for 5 hours while distilling the produced water out of the system to obtain a polyimide resin solution having a resin concentration of about 20% by weight. The obtained polyimide resin had an acid value of 4.0 mgKOH / g, Mn = 22,300, Mw = 56,500, and a glass transition temperature of 27 ° C.

Synthesis example 3
In a 500 ml four-necked flask equipped with a nitrogen introduction tube, a stirrer, a distillation outlet and a thermometer, GBL 270 g, xylene 30 g, (A) component, TMEG 20.9 g (0.051 mol)), and DSDA 18. 2 g (0.051 mol), BPP 34.9 g (0.085 mol) and XTJ-542 15.1 g (0.015 mol) were charged as component (B), and the mixture was heated to 180 ° C. while stirring under a nitrogen stream. Warm up. The imidization reaction was carried out for 5 hours while distilling the produced water out of the system to obtain a polyimide resin solution having a resin concentration of about 20% by weight. The obtained polyimide resin had an acid value of 4.6 mgKOH / g, Mn = 19,600, Mw = 42,700, and a glass transition temperature of 107 ° C.

Synthesis example 4
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 270 g, xylene 30 g, (A) component, TMEG 37.7 g (0.092 mol) (A1), and DSDA 3.64 g (0.010 mol) (A2), as component (B), 24.6 g (0.060 mol) of BAPP and 40.3 g (0.040 mol) of XTJ-542 were charged and stirred under a nitrogen stream. The temperature was raised to 180 ° C. The imidization reaction was carried out for 5 hours while distilling the produced water out of the system to obtain a polyimide resin solution having a resin concentration of about 20% by weight. The viscosity immediately after synthesis of the polyimide solution was 2.6 Pa · s, and the viscosity after storage for 1 month was 2.8 Pa · s. The obtained polyimide resin had an acid value of 4.3 mgKOH / g, Mn = 21,100, Mw = 48,900, and a glass transition temperature of 25 ° C.

Synthesis example 5
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 69 g, NMP 69 g, xylene 16 g, (A) component (A1) TMEG 21.7 g (0.053 mol) And (A2) DSDA 19.0 g (0.053 mol), and (B1) BAPP 24.6 g (0.060 mol) and (B2) XTJ-542 40.3 g (0.040 mol) as component (B). The temperature was raised to 180 ° C. while stirring and stirring under a nitrogen stream. The imidization reaction was carried out for 5 hours while distilling the produced water out of the system to obtain a polyimide resin solution having a resin concentration of about 40% by weight. The viscosity immediately after synthesis of the polyimide solution was 23.5 Pa · s, and the viscosity after storage for 1 month was 24.8 Pa · s. The obtained polyimide resin had an acid value of 19.3 mgKOH / g, Mn = 11,400, Mw = 24,000, and a glass transition temperature of 44 ° C.

Synthesis Example 6 (Comparative product: lacking component (A1))
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 135 g, NMP 135 g, xylene 30 g, (A) component, DSDA 36.3 g (0.102 mol), (B ) As a component, 24.6 g (0.060 mol) of BAPP and 16.0 g (0.040 mol) of D-400 were charged, and the temperature was raised to 180 ° C. while stirring under a nitrogen stream. The imidization reaction was carried out for 5 hours while distilling the produced water out of the system to obtain a polyimide resin solution having a resin concentration of about 20% by weight. The obtained polyimide resin had an acid value of 3.6 mgKOH / g, Mn = 25,200, Mw = 60,300, and a glass transition temperature of 174 ° C.

Synthesis Example 7 (Comparative product: (B) component is excessive)
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 135 g, NMP 135 g, xylene 30 g, (A) component, TMEG 20.5 g (0.050 mol), and DSDA 17.8 g (0.050 mol), as component (B), 25.4 g (0.062 mol) of BAPP and 16.0 g (0.040 mol) of D-400 were charged and stirred at 180 ° C. under a nitrogen stream. The temperature was raised to. The imidization reaction was carried out for 5 hours while distilling the produced water out of the system to obtain a polyimide resin solution having a resin concentration of about 20% by weight. The viscosity immediately after synthesis of the polyimide solution was 11.9 Pa · s, and the viscosity after 1 month storage was 16.6 Pa · s. The obtained polyimide resin had an acid value of 0.1 mgKOH / g or less, Mn = 22,300, Mw = 50,000, and a glass transition temperature of 87 ° C.

Examples 1-30 and Comparative Examples 1-3
<Manufacture of thermosetting resin composition>
The polyimide resin solution prepared in the above synthesis example and the components shown in Table 1 are kneaded with a ceramic three roll (manufactured by Inoue Seisakusho, "HHC-178X356"), and thermosetting the composition shown in Table 1 A functional resin composition was prepared. In addition, the polyimide resin, epoxy resin, hardening | curing agent, and filler in Table 1 are as follows.

Polyimide 1: Polyimide resin obtained in Synthesis Example 1 Polyimide 2: Polyimide resin obtained in Synthesis Example 2 Polyimide 3: Polyimide resin obtained in Synthesis Example 3 Polyimide 4: Polyimide resin obtained in Synthesis Example 4 Polyimide 5 : Polyimide resin obtained in Synthesis Example 5 Polyimide 6: Polyimide resin obtained in Synthesis Example 6 Polyimide 7: Polyimide resin obtained in Synthesis Example 7.

Epoxy 1: a dicyclopentadiene type epoxy resin having an epoxy equivalent of 258 (manufactured by Dainippon Ink & Chemicals, trade name “HP-7200”)
Epoxy 2: modified novolak type epoxy resin having an epoxy equivalent of 275 (glycolyl etherified product of novolak type resin obtained by condensation of dimethylolbiphenyl and phenol, in general formula (7), Ar ² = 1 hydroxyl group from phenol and hydrogen atom Residue obtained by removing one, epoxy resin having Ar ³ = biphenylene group: “NC-3000” manufactured by Nippon Kayaku Co., Ltd.)
Epoxy 3: novolak type epoxy resin having an epoxy equivalent of 230 (glycidyl etherified product of novolak type resin obtained from hydroxynaphthalene and cresol and formaldehyde, in general formula (6), Ar ¹ = 1 hydroxyl group and 1 hydrogen atom from cresol Epoxy resin which is a residue obtained by removing or a hydroxynaphthalene residue: “NC-7000L” manufactured by Nippon Kayaku Co., Ltd.)
Epoxy 4: novolak type epoxy resin having an epoxy equivalent of 215 (cresol novolak type, “Epicron N-680” manufactured by Dainippon Ink & Chemicals, Inc.)
Epoxy 5: Bisphenol type epoxy resin having an epoxy equivalent of 2800 (“YD-019” manufactured by Tohto Kasei Co., Ltd.)
Epoxy 6: Brominated bisphenol type epoxy resin having an epoxy equivalent of 400 (“YDB-400” manufactured by Tohto Kasei Co., Ltd.).

Curing agent 1: “Amicure PN-23” manufactured by Ajinomoto Fine Techno Co., Ltd.
Hardener 2: “Adeka Hardener EH-4342S” manufactured by Asahi Denka Kogyo Co., Ltd.
Curing agent 3: “Adeka Hardener EH-3366S” manufactured by Asahi Denka Kogyo Co., Ltd.
Curing agent 4: “Phenolite TD-2131” manufactured by Dainippon Ink & Chemicals, Inc.

Filler 1: Barium sulfate (average particle size 0.4 μm, Sakai Chemical Co., Ltd. barium sulfate B-32)
Filler 2: Talc (average particle size 4.8 μm, LMS-300 manufactured by Fuji Talc)
Filler 3: Dry silica (average particle diameter 10 nm, Leorosil QS-20 manufactured by Tokuyama Corporation).

  The average particle size of the fillers 1 and 2 is determined by using a laser diffraction scattering method particle size distribution measuring device (Microtrac particle size distribution device HRA, manufactured by Microtrac Co., Ltd.) and using a nonionic surfactant (Triton X- 100) is a value measured after dispersing the filler in water and ultrasonically dispersing the filler for 3 minutes.

  The average particle diameter of the filler 3 is a value obtained by analyzing with image analysis software (IP-1000C manufactured by Asahi Engineering Co., Ltd.) using a transmission electron microscope (JEM200CX manufactured by JEOL Ltd.). is there.

Flame retardant 1: Triphenyl phosphate (trade name “TPP”, manufactured by Daihachi Chemical Co., Ltd.)
Flame retardant 2: Melamine cyanurate (trade name “MC-860”, manufactured by Nissan Chemical Co., Ltd.)
Flame retardant 3: Antimony pentoxide (trade name “Sampoc NA-1030”, manufactured by Nissan Chemical Co., Ltd.).

  Using the thermosetting resin composition thus obtained, a film of the thermosetting resin composition was prepared and evaluated in accordance with the following method. In the accompanying drawings, like parts are indicated by like reference numerals.

< Evaluation of printed wiring board >
(1) Creation of circuit board A A non-adhesive copper-clad laminate (trade name “Iupicel N” manufactured by Ube Industries, Ltd .; film thickness 25 μm, electrolytic copper thickness 8 μm) is coated with photoresist, exposed, developed, As shown in FIG. 1, after etching and peeling, conductor portions 11 and 11 ′ (10 on the left side and 9 on the right side) having a line width of 50 μm and a space width of 50 μm and electrically connecting these conductor portions A circuit board having a comb-shaped pattern portion 10 provided with terminal portions 12 and 12 ′ was produced.

  After screen-printing each thermosetting resin composition described in Tables 1 to 4 over almost the entire surface of the comb-shaped pattern portion 10 of the circuit board, it is processed under the drying and curing conditions described in Tables 5 to 8. A circuit board A having a cured film 13 of a thermosetting resin composition having a thickness of 10 μm was prepared.

(2) Preparation of circuit board B-1 and circuit board B-2 After sputtering a nickel alloy on polyimide tape (trade name “Upilex S” manufactured by Ube Industries, Ltd .; film thickness 25 μm), a photoresist is applied, Exposure and development. Subsequently, copper plating is applied to the circuit pattern portion, etching is performed to obtain a circuit portion, and further, tin plating is applied to the circuit portion, so that the conductor thickness is 8 μm, the line width is 10 μm, and the space width is 15 μm, as shown in FIG. Comb pattern portion 20 having conductor portions 21 and 21 'and terminal portions 22 and 22' for electrically connecting these conductor portions (the left conductor portion 21 is 10 pieces and the right conductor portion 21 'is 9 pieces) A circuit board having

  Each thermosetting resin composition described in Tables 1 to 4 is screen-printed on one half surface of the comb-shaped pattern portion 20 of the circuit board, and heat-cured by treatment under the drying and curing conditions described in Tables 5 to 8. Circuit board B-1 which has the cured film 23 of a conductive resin composition was created.

  Moreover, as shown in FIG. 3, each thermosetting resin composition described in Tables 1 to 4 is screen-printed on almost the entire surface of the comb-shaped pattern portion 20 of the circuit board, and the drying described in Tables 5 to 8, A circuit board B-2 having a cured film 24 of a thermosetting resin composition was produced by treatment under curing conditions.

(3) Preparation of substrate C Each thermosetting resin composition described in Tables 1 to 4 is screen-printed on almost the entire surface of polyimide tape (trade name “Iupilex S” manufactured by Ube Industries, Ltd.). The board | substrate C which processed on the drying and hardening conditions of 8 and formed the cured film of the thermosetting resin composition with a film thickness of 9-12 micrometers was created.

(4) Evaluation method The following (a)-(l) was evaluated about the board | substrate which has the cured film obtained by the method of said (1), (2) or (3).

(A) The screen printed portion of the warped substrate C was cut to a width of 35 mm and a length of 35 mm, and the height of the warp from the surface plate when the convex surface was faced down and placed on a horizontal surface plate was measured. .

(B) Pencil Hardness The pencil strength of the cured film of the thermosetting resin composition formed on the substrate C is JIS K-5600-5-4-1999 using Mitsubishi High Uni (trade name, manufactured by Mitsubishi Pencil Co., Ltd.). It measured according to.

(C) Adhesion According to JIS D-0202-1988, 100 crosscuts are put in a grid pattern on the cured film of the thermosetting resin composition of the substrate C, and then a peeling test using a cellophane adhesive tape is performed. went. The state of peeling of the cured film was visually observed and judged according to the following criteria:
A: No peeling at all O: Peeling occurred at one place Δ: Peeling occurred at 2 to 10 places X: Peeling occurred at 11 or more places.

(D) Solder heat resistance (whitening)
A flux (“LONCO 3355-11” manufactured by London Chemical Co., Ltd.) was applied to the circuit board A, and then immersed in a molten solder bath at 260 ° C. for 5 seconds, and then washed with water. The degree of whitening of the cured film after 5 cycles of this cycle was observed. The evaluation of whitening of the cured film is as follows:
A: No whitening occurred. B: Whitening occurred slightly. Δ: Whitening was observed. X: Whitening occurred remarkably.

(E) Solder heat resistance (adhesion)
Evaluation of the adhesion of the cured film in the same manner as the adhesion of (c) above, using the circuit board A which has been dipped in the solder bath and washed once with the same method as the solder heat-resistant whitening test of (d) above. Went. The evaluation of adhesion is as follows:
A: No peeling occurred. O: A slight peeling occurred. Δ: A peeling occurred in a considerable part. X: A bulging or peeling of the cured film had occurred before the peeling test.

(F) The solvent resistant substrate C was immersed in 2-propanol at room temperature for 1 hour, and the state of the cured film was visually observed. The substrate C was immersed in acetone for 1 hour at room temperature, and the state of the cured film was visually observed. The evaluation of solvent resistance is as follows:
A: No change was caused by any solvent. Δ: Slight changes such as swelling of the cured film were observed. X: The cured film was peeled off.

(G) The state of the cured film after immersing the acid-resistant circuit board A in 10% by weight of hydrochloric acid at room temperature for 1 hour was observed. The acid resistance is evaluated as follows:
A: No abnormality occurred. Δ: A slight change such as swelling of the cured film occurred. X: The cured film peeled off.

(H) Bleeding In the circuit board B-1 obtained in the above (FIG. 2), as shown in FIG. 4 which is an enlarged view of the portion E in FIG. The printed thermosetting resin composition oozes out into the space portion 21s between the conductor portion 21 and the conductor portion 21 'by the capillary phenomenon during the drying and curing process, and is cured to form the oozing portion 25. Is done. The length d of the bleed portion 25, that is, the distance between the end 23e of the cured film 23 of the thermoplastic resin composition in the line portion and the tip 25e of the bleed portion 25 oozing into the space portion was measured. . The results were evaluated according to the following criteria:
◎: The length of the oozing part is less than 50 μm ◯: The length of the oozing part is 50 μm or more and less than 100 μm △: The length of the oozing part is 100 μm or more and less than 200 μm ×: The length of the oozing part is 200 μm or more.

(I) Gold plating solution resistance Commercially available plating catalyst bath (catalyst solution: “Metal plate activator 350” manufactured by Meltex), commercially available electroless nickel plating bath (nickel plating bath: “Melplate Ni manufactured by Meltex”) -865M ") and a commercially available electroless gold plating bath (gold plating solution:" Ourolectroles UP "manufactured by Meltex, Inc.), the circuit board A is immersed in a catalyst bath at 30 ° C for 3 minutes, followed by After being immersed in an electrolytic nickel plating bath at 55 ° C. for 20 minutes, further immersed in an electroless gold plating bath at 95 ° C. for 10 minutes to give a nickel plating thickness of 0.5 μm and a gold plating thickness of 0.03 μm.

  As a result, the cured film 13 of the thermosetting resin composition shown in FIG. 1 is not plated, while the circuit portions exposed without being covered with the cured film 13, that is, the conductors 11, 11 ′ and the terminal portions 12. , 12 'was plated only.

  Thereafter, the appearance of the cured film 13 was visually observed to observe the appearance, particularly the penetration of plating at the end of the cured film 13 and the lifting of the cured film 13 from the substrate.

Subsequently, the adhesion test of the cured film was performed in the same manner as the evaluation of the adhesion (c), and the resistance to gold plating solution was evaluated according to the following criteria:
◎: No change in appearance of cured film after plating, and no peeling occurred even in adhesion test ○: No change in appearance of cured film after plating, and no peeling occurred in adhesion test, but end of cured film Slight plating penetration was observed in the part. Δ: The appearance of the cured film was not changed after plating, but peeling occurred at two or more places in the adhesion test. X: The cured film was floating from the substrate after plating. In the adhesion test, peeling occurred at two or more locations.

(J) Instead of a gold plating bath resistant to tin plating, tin plating is performed at 70 ° C. for 5 minutes using an electroless tin plating solution (tin plating solution: “Tinposit LT-34” manufactured by Rohm and Haas). The evaluation was performed in the same manner as in the above (i) except that it was performed.

(K) A bias voltage of DC 60 V was applied to the comb-shaped electrode pattern of the electric corrosion resistant circuit board B-2, and the plate was left for 1000 hours under the conditions of 85 ° C. and 85% RH. The insulation resistance value was measured using an evaluation system AEI-103.
In addition, the evaluation of electric corrosion resistance is as follows:
A: The insulation resistance value of the film after 1000 hours was 10 ⁸ Ω or more. ○: The insulation resistance value of the film after 1000 hours was 10 ⁷ Ω or more. Δ: The insulation resistance of the film after 1000 hours. The value was 10 ⁵ or more and less than 10 ⁷ Ω x: The insulation resistance value after 1000 hours was less than 10 ⁵ Ω.

(L) The flexible substrate C was folded so that the cured film of the thermosetting resin composition was on the outside, and the cured film at the bent part was observed with a 50 × optical microscope to confirm the presence or absence of cracks. Flexibility was determined according to the following criteria:
◎: No crack at all ○: Slight cracks are observed ×: Many cracks are observed.

(M) The flame retardant substrate C was cut to a size of 13 mm width × 125 mm length, and the obtained test piece was subjected to a flame retardant test in accordance with the flame retardant test standard UL94 of a plastic material. . Flame retardancy was evaluated according to the following criteria:
(Double-circle): The flame retardance of V-0 was shown.

  X: The flame retardancy of V-0 was not shown.

  The composition of Examples 1-30 used for the above evaluation is shown in Tables 1-3, and the composition of the thermosetting resin composition of Comparative Examples 1-3 is shown in Table 4. Moreover, the drying and curing conditions and evaluation results in Examples 1 to 30 are shown in Tables 5 to 7, and the drying and curing conditions and evaluation results in Comparative Examples 1 to 3 are shown in Table 8.

  As can be seen from Tables 1 to 8, when polyimide 6 lacking the component (A1) is used (Comparative Example 1), adhesion, solder heat resistance, solvent resistance, plating solution resistance, and electrolytic corrosion resistance are inferior ( B) In the case where polyimide 7 having an excessive component is used (Comparative Example 2), the thermosetting resin composition is inferior in solder heat resistance, solvent resistance, acid resistance, plating solution resistance, and electric corrosion resistance and does not use an epoxy resin. When the product is used (Comparative Example 3), the solder heat resistance, solvent resistance, acid resistance, plating solution resistance, and electric corrosion resistance are poor.

  On the other hand, when the requirements of the present invention are satisfied (Examples 1 to 30), warpage, pencil hardness, adhesion, solder heat resistance, solvent resistance, acid resistance, oozing, plating solution resistance, electric corrosion resistance It is clear that it is excellent in all of flexibility and flexibility (flexibility), and is excellent as a cover coat for manufacturing a printed wiring board.

ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can form the uniform protective film excellent in heat resistance, a softness | flexibility, electrical insulation, and storage stability and excellent in adhesiveness can be provided. The thermosetting resin composition is industrially extremely useful as an electronic material, taking advantage of the excellent characteristics described above, and is particularly useful as a cover coat ink for producing a printed wiring board.

Claims (25)

A thermosetting resin composition comprising a polyimide resin, an epoxy resin, and an organic solvent, wherein the polyimide resin is
(A) component:
(A1) General formula (1)

[Wherein, X ¹ represents a linear or branched alkylene group having ^{1 to} 6 carbon atoms, a 1,3-phenylene group, or a 1,4-phenylene group. ]
And alkylene or phenylenebis (anhydrotrimellitate) represented by formula (2) and (A2)

A tetracarboxylic dianhydride mixture comprising diphenyl sulfone tetracarboxylic dianhydride represented by:
(B) component:
(B1) General formula (3)

[Wherein Y ¹ represents —O—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. ]
And (B2) general formula (4)

[Wherein, Z ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. h, i, and j each represent an integer of 0-50, and the sum of h + i + j is 2-50. ]
A polyimide obtained by subjecting to a diamine mixture containing a polyoxyalkylene diamine represented by the formula (A): component (B) charge molar ratio = 1.01-1.20: 1 and imidation reaction A thermosetting resin composition which is at least one kind of resin.   The thermosetting resin composition according to claim 1, wherein the molar ratio of the component (A1) to the component (A2) is (A1) :( A2) = 95: 5 to 40:60.   The thermosetting resin composition according to claim 1, wherein a molar ratio of the component (B1) to the component (B2) is (B1) :( B2) = 40: 60 to 90:10. The thermosetting resin composition according to claim ¹ , wherein X ¹ in the general formula (1) is an ethylene group.   2. The thermosetting resin composition according to claim 1, wherein, in the general formula (4), h, i, and j are each an integer of 0 to 35, and a total of h + i + j is 5 to 35. The thermosetting resin composition according to claim ¹ , wherein Z ¹ in the general formula (4) is a tetramethylene group. A thermosetting resin composition comprising a polyimide resin, an epoxy resin, and an organic solvent, wherein the polyimide resin is
(A) component:
(A1) General formula (1)

[Wherein, X ¹ represents a linear or branched alkylene group having ^{1 to} 6 carbon atoms, a 1,3-phenylene group, or a 1,4-phenylene group. ]
And alkylene or phenylenebis (anhydrotrimellitate) represented by formula (2) and (A2)

A tetracarboxylic dianhydride mixture containing diphenylsulfone tetracarboxylic dianhydride represented by: and component (B):
(B1) General formula (3)

[Wherein Y ¹ represents —O—, —SO ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —. ]
And (B2) general formula (4)

[Wherein, Z ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. h, i, and j each represent an integer of 0-50, and the sum of h + i + j is 2-50. ]
The molar ratio of the structural unit (AU) derived from the component (A) to the structural unit derived from the component (B) is obtained by subjecting the diamine mixture containing the polyoxyalkylenediamine represented by The thermosetting resin composition which is at least 1 sort (s) of the polyimide resin which is AU: BU = 1.01-1.20: 1. The thermosetting resin composition according to claim 7, wherein in the general formula (1), X ¹ is an ethylene group.   The thermosetting resin composition according to claim 7, wherein in general formula (4), h, i, and j are each an integer of 0 to 35, and the sum of h + i + j is 5 to 35. The thermosetting resin composition according to claim 7, wherein Z ¹ in the general formula (4) is a tetramethylene group.   The number average molecular weight of the polyimide resin is 5,000 to 100,000, the weight average molecular weight is 10,000 to 200,000, and the acid value is 1 to 50 mgKOH / g. The thermosetting resin composition as described.   The thermosetting resin composition according to any one of claims 1 to 10, wherein the epoxy resin is an epoxy resin having an epoxy equivalent of 100 to 10,000. The epoxy resin has the general formula (5)

[Wherein, R ⁴ represents a hydroxyl group or a glycidyloxy group. p represents 0 or an integer of 1 or more. When p is 2 or more, p R ^{4 s} may be the same or different. R ⁵ represents a halogen atom or an alkyl group having 1 to 5 carbon atoms. b represents an integer of 0 to 4. Z ² represents a single bond, —SO ₂ —, an alkylidene group having 1 to 6 carbon atoms, or a cycloalkylidene group having 3 to 8 carbon atoms. Further,-* and *-indicate that the upper structure and the lower structure are connected by a single bond. ]
Bisphenol type epoxy resin represented by
General formula (6)

[Wherein Ar ¹ is an aromatic group having 6 to 30 carbon atoms which may have 1 to 3 substituents selected from the group consisting of a halogen atom, a hydroxyl group and an alkyl group having 1 to 5 carbon atoms. Represents. q represents an integer of 1 or more. Further, (q + 1) Ar ¹ may be the same or different. ]
Novolac type epoxy resin represented by
General formula (7)

[Wherein Ar ² is an aromatic group having 6 to 30 carbon atoms which may have 1 to 3 substituents selected from the group consisting of a halogen atom, a hydroxyl group and an alkyl group having 1 to 5 carbon atoms. Represents. Ar ³ represents a phenylene group, a naphthalene group or a biphenylene group. r represents an integer of 1 or more. ]
Modified novolac-type epoxy resin represented by the general formula (8)

[In the formula, Ar ⁴ is an aromatic group having 6 to 30 carbon atoms which may have 1 to 3 substituents selected from the group consisting of a halogen atom, a hydroxyl group and an alkyl group having 1 to 5 carbon atoms. Represents. s represents an integer of 1 or more. ]
The thermosetting resin composition according to claim 1, which is at least one selected from the group consisting of dicyclopentadiene type epoxy resins represented by the formula:   The thermosetting resin composition of Claim 1 or 7 containing 10-200 weight part of epoxy resins with respect to 100 weight part of polyimide resins.   Furthermore, the thermosetting resin composition of Claim 1 or 7 containing an epoxy resin hardening | curing agent. Furthermore, the thermosetting resin composition of Claim 1 or 7 containing a flame retardant. The thermosetting according to claim 16, wherein the flame retardant is at least one selected from red phosphorus, phosphorus compounds, halogen compounds, siloxane compounds, nitrogen compounds, boron compounds, tin compounds, and antimony flame retardants. Resin composition.   Furthermore, the thermosetting resin composition of Claim 1 or 7 containing a filler.   The thermosetting resin composition according to claim 1 or 7, wherein the organic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone and γ-butyrolactone.   The thermosetting resin composition according to claim 1 or 7, wherein the total weight of the polyimide resin and the epoxy resin is 1 to 150 parts by weight with respect to 100 parts by weight of the organic solvent.   The thermosetting resin molding obtained by drying and hardening the thermosetting resin composition of Claim 1 or 7.   The thermosetting resin molding according to claim 21, which is in the form of a layer or a film.   The cover coat ink for printed wiring board manufacture containing the thermosetting resin composition of Claim 1 or 7.   The electronic component provided with the thermosetting resin molding in the form of the layer thru | or film | membrane of Claim 22.   25. The electronic component according to claim 24, which is a flexible printed wiring board, a TAB board, or a COF board provided with a thermosetting resin molded body in the form of a layer or a film according to claim 22 as a cover coat.

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