TW201527429A - Photosensitive heat-curable resin composition and flexible printed wiring board - Google Patents

Abstract

Provided are the following: a photosensitive heat-curable resin composition having excellent flame-retardance, insulation reliability, and bending resistance properties; a dry film; and a flexible printed wiring board provided with a cured product of the photosensitive heat-curable resin composition. The present invention is a photosensitive heat-curable resin composition characterized by comprising (A) a polyimide resin having an imide ring and a carboxyl group, (B) a photobase generator, (C) a thermal curing component, and (D) a flame retardant. Preferably, the invention comprises substantially no (meth)acrylate monomer.

Description

Photosensitive thermosetting resin composition and flexible printed wiring board

The present invention relates to a photosensitive thermosetting resin composition and a flexible printed wiring board, and more particularly to a photosensitive thermosetting resin composition which is excellent in flame retardancy and folding resistance by alkali development. And a flexible printed wiring board including the cured product of the photosensitive thermosetting resin composition.

In recent years, the popularity and performance of smart phones or tablet terminals have increased rapidly. Consumers have high requirements for miniaturization and thinning of the information equipment terminals represented by these, and it is necessary to increase the density and space of the circuit board inside the product in accordance with the requirements. Therefore, the use of a flexible printed wiring board which can be bent and accommodated and which can improve the degree of freedom in circuit arrangement is being expanded, and the reliability of the flexible printed wiring board is also required to be higher than the above.

At present, as an insulating film for ensuring the insulation reliability of a flexible printed wiring board, a protective film mainly composed of polyimide is used in a bent portion (flexure portion) at a mounting portion (non-deflection) Part) A mixing process using a photosensitive resin composition (see Patent Documents 1 and 2). Polyimine is excellent in mechanical properties such as heat resistance and flexibility, and is attached to the mounting unit. The photosensitive resin composition used has excellent microfabrication properties such as electrical insulating properties and solder heat resistance.

The printed wiring board, in particular, the flexible printed wiring board (hereinafter referred to as FPC) is required to have high flame retardancy, and the insulating film which is one of the main constituent elements is also required to have excellent flame retardancy. In comparison with a printed wiring board of a glass epoxy substrate, an FPC using a polyimide substrate or the like as a substrate is a film. On the other hand, since the thickness of the insulating film required is the same for both the printed wiring board and the FPC, the burden on the insulating film is relatively large when the film is FPC.

Therefore, various proposals have been made for the flame retardation of the insulating film. For example, it has been carried out in a curable resin composition for obtaining an insulating film, and the phosphorus-containing compound imparting flame retardancy to the resin composition is excellent in heat resistance. Epoxy resin. For example, Patent Document 3 discloses a flame-retardant photosensitive resin composition for FPC comprising (a) a binder polymer such as an epoxy resin, (b) a halogenated aromatic ring having a bromophenyl group or the like in the molecule, and a photopolymerizable compound of a polymerizable ethylenically unsaturated bond such as a (meth)acrylinyl group, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and (e) a phosphorus atom in the molecule Phosphorus compound.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 62-263692

Patent Document 2: Japanese Laid-Open Patent Publication No. SHO 63-110224

Patent Document 3: Japanese Patent Laid-Open Publication No. 2007-10794

In the photosensitive resin composition of the prior art, a (meth) acrylate monomer is blended in order to adjust the viscosity, improve the physical properties of the cured coating film, and improve the sensitivity. The (meth) acrylate monomer is relatively flammable, and the flame retardancy of the photosensitive resin composition is impaired. Therefore, in order to compensate for this disadvantage, it is necessary to prepare a large amount of a flame retardant such as a phosphorus-containing compound.

However, when a phosphorus-containing compound is blended in the photosensitive resin composition, the folding resistance is deteriorated, and cracks may occur in the cured coating film during the cutting process of the wiring board or during the thermal shock test. Further, many of the phosphorus-containing compounds have a phosphate skeleton, and the ionic impurities are increased by blending these, and the insulating reliability of the photosensitive resin composition is also lowered.

Therefore, an object of the present invention is to provide a photosensitive thermosetting resin composition excellent in flame retardancy and folding resistance, and a flexible printed wiring board including the cured product of the photosensitive thermosetting resin composition.

The present inventors have found a photosensitive thermosetting resin containing a polyimine resin having a quinone ring and a carboxyl group, a photobase generator, a thermosetting component, and a flame retardant in order to solve the above problems. The object can solve the above problems.

That is, it was found that the photobase generator was activated by light irradiation to produce a base as a catalyst, and a polyimine resin having a carboxyl group and a thermosetting component were obtained. The addition reaction is carried out by heating, whereby only the unexposed portion can be removed by the alkali solution. Therefore, it is expected to obtain a cured product which can be microfabricated by alkali development and which is excellent in reliability. Further, even if the (meth) acrylate monomer is not blended, sufficient cured physical properties can be obtained, and the resin having the quinone ring is excellent in flame retardancy, so that it is not necessary to add a large amount of flame retardant, and the cause can be avoided. Deterioration of the folding resistance and insulation reliability caused by the flame retardant.

The present invention is the following [1] to [8].

[1] A photosensitive thermosetting resin composition comprising (A) a polyimine resin having a quinone ring and a carboxyl group, (B) a photobase generator, (C) a thermosetting component, and (D) Flame retardant.

[2] The photosensitive thermosetting resin composition according to [1], wherein the (D) flame retardant is a phosphorus compound.

[3] The photosensitive thermosetting resin composition according to [1], wherein the (meth) acrylate monomer is substantially not contained.

[4] The photosensitive thermosetting resin composition according to [1], wherein the (A) polyimine resin having a quinone ring and a carboxyl group has a phenolic hydroxyl group.

[5] The photosensitive thermosetting resin composition according to [1], wherein the (C) thermosetting component is a cyclic ether compound.

[6] The photosensitive thermosetting resin composition according to [1], which is used for a flexible wiring board.

[7] A dry film characterized by having a resin layer composed of the photosensitive thermosetting resin composition of [1].

[8] A printed wiring board characterized by having a cured product, the hardening The system is formed using the photosensitive thermosetting resin composition of [1] or the dry film of [7].

According to the present invention, it is possible to provide a photosensitive thermosetting resin composition which is excellent in flame retardancy and folding resistance by alkali development, and a flexible printed wiring board including the cured product of the photosensitive thermosetting resin composition. . The photosensitive thermosetting resin composition of the present invention is suitable for an insulating film of a flexible printed wiring board, and in particular, a forming process of a bent portion (bending portion) and a mounting portion (non-bending portion). Moreover, the photosensitive thermosetting resin composition of the present invention is also suitable as a resin composition for a protective layer of a protective layer of a multilayer structure. Here, the protective layer refers to a resin layer having a protective layer of a laminated structure of two or more layers which is not adjacent to the flexible printed circuit board.

1‧‧‧Flexible printed wiring substrate

2‧‧‧Bronze circuit

3‧‧‧ resin layer

4‧‧‧ resin layer

5‧‧‧ mask

Fig. 1 is a schematic view showing an example of a method of manufacturing a flexible printed wiring board of the present invention.

The photosensitive thermosetting resin composition of the present invention is characterized by (A) a polyimine resin having a quinone ring and a carboxyl group, (B) a photobase generator, (C) a thermosetting component, and (D) ) Flame retardant. The photosensitive thermosetting resin composition of the present invention preferably contains substantially no (meth) acrylate monomer.

In the photosensitive thermosetting resin composition of the present invention, a base produced by a photobase generator is used as a catalyst, and a polyimine resin having a carboxyl group is reacted with a thermosetting component by heating after exposure, and A resin composition which is developed by removing an unexposed portion by an alkali solution. Thereby, it is not necessary to mix the (meth) acrylate monomer which is required in the photosensitive resin composition which utilizes the polymerization reaction of the radical generate|occur|produced by photo-radical-polymerization initiator from the past.

Herein, the substantially no (meth) acrylate single system is not actively formulated as a constituent component, but it is not excluded that a small amount is contained within a range that does not impair the effects of the present invention. For example, the (meth) acrylate monomer is usually formulated in an amount of 20 to 50 parts by mass based on 100 parts by mass of the photosensitive resin in order to obtain a compounding effect. However, in the photosensitive thermosetting resin composition of the present invention, 100 parts by mass of the polyimine resin having a quinone imine ring and a carboxyl group of the component A) is preferably 15 parts by mass or less, more preferably 10 parts by mass or less. Of course, as described above, the composition of the (meth) acrylate monomer may not be contained. The (meth) acrylate monomer is described below.

The (meth) acrylate monomer is flammable, and by substantially containing no such monomer, the flame retardancy of the photosensitive thermosetting resin composition can be prevented from decreasing. Therefore, it is not necessary to mix a large amount of a flame retardant represented by a phosphorus-containing compound, and it is possible to suppress a decrease in folding endurance due to a phosphorus-containing compound and a decrease in insulation reliability.

The above-mentioned (meth) acrylate single system is used as a photosensitive monomer in the photosensitive resin composition for forming an insulating film, in order to adjust the viscosity, promote photocurability, or improve development (meth) Acrylate monomers, listed as polyester (meth) acrylate, polyether (meth) acrylate Ester, urethane (meth) acrylate, carboxylic acid ester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate. Specific compounds are hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. N,N-dimethyl methacrylamide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide, etc.; acrylamide; N,N-dimethylamine Aminoalkyl acrylates such as ethyl acrylate, N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, cis-hydroxyethyl isocyanide a polyhydric acrylate such as a uric acid ester or such an ethylene oxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct; a phenoxy acrylate, a bisphenol A diacrylate a polybasic acrylate such as an ester, an oxirane adduct of the phenols or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane a polyacrylate of a glycidyl ether such as triglycidyl ether or triglycidyl isocyanurate; not limited to the above, and also includes a polyether a acrylate or a melamine acrylate which is directly acrylated with a polyol such as an alcohol, a polycarbonate diol, a hydroxyl terminated polybutadiene or a polyester polyol, or a urethane acrylated by a diisocyanate, and It corresponds to at least any one of the methacrylates of the above acrylate.

The photosensitive thermosetting resin composition of the present invention can be suitably used for a resin insulating layer of a flexible printed wiring board, such as a protective layer or a solder resist.

When the photosensitive insulating layer of the flexible printed wiring board is formed using the photosensitive thermosetting resin composition of the present invention, a preferred production method is as follows. also In other words, the method includes the steps of: forming a resin layer formed of the photosensitive thermosetting resin composition of the present invention on a flexible printed wiring board; and irradiating the resin layer with light of a pattern; The step of heating the resin layer (Post Exposure Bake: also referred to as PEB) and the step of causing the resin layer to perform alkali development to form a resin insulating layer having a pattern. Further, after alkali development, light irradiation or heat curing (post-hardening) is carried out to completely cure the resin composition to obtain a highly reliable resin insulating layer.

According to this, the photosensitive thermosetting resin composition of the present invention is preferably subjected to an addition treatment of a carboxyl group and a thermosetting component by heat treatment after selective light irradiation, whereby negative alkali formation can be used to form a negative Type pattern.

Since the obtained cured product is excellent in heat resistance and flexibility, and can be microfabricated by alkali imaging, it is not necessary to use a photosensitive resin composition of a base-developing type in combination with a polyimine. Any of the bent portion (flexed portion) and the attached portion (non-flexed portion) of the flexible printed wiring board is applied to a primary forming process of the bent portion (flexed portion) and the attached portion (non-flexed portion).

Hereinafter, each component will be described in detail.

[(A) Polyimine resin with quinone ring and carboxyl group]

In the present invention, (A) a polyimine resin having a quinone ring and a carboxyl group is a resin having a carboxyl group and a quinone ring.

The polyimine resin of the component (A) preferably has a partial structure represented by the following formula (1) as a quinone ring. In the formula (1), R is preferably an aromatic ring-containing one.

The partial structure represented by the above formula (1) is more preferably represented by the following formula (2) or (3).

The position of the carboxyl group is not particularly limited. A carboxyl group may be present as a substituent of the above-mentioned quinone ring or a group bonded thereto, and a carboxyl group may be synthesized by using a carboxyl group as an amine component or an isocyanate component, and a carboxyl group may be introduced into the polyimide resin.

Further, the polyimine resin of the above component (A) preferably has a phenolic hydroxyl group. When a phenolic hydroxyl group is present, the time from the addition reaction to the alkali resistance at the same heating temperature at the time of the heat hardening reaction after exposure (hereinafter referred to as the PEB step) is increased as compared with the case where it is not present. Moreover, the heating temperature of the heat hardening reaction (hereinafter referred to as the PEB step) can be increased. Choose the range. Based on this, the workability and workability of the resin composition are improved. The unexposed portion is resistant to alkali, and so-called excessive photoreception can be suppressed.

The synthesis of the polyimine resin of the component (A) can be carried out by a conventional method. For example, a resin obtained by reacting a carboxylic anhydride component with an amine component and/or an isocyanate component is exemplified. The ruthenium imidization can be carried out by thermal imidization, or by chemical imidization, or by using these.

The carboxylic anhydride component is exemplified by a tetracarboxylic anhydride or a tricarboxylic anhydride, but is not limited thereto. When it is a compound having an acid anhydride group and a carboxyl group which react with an amine group or an isocyanate group, a derivative thereof may be used. In addition, these carboxylic anhydride components may be used alone or in combination of two or more.

The tetracarboxylic anhydride is exemplified by, for example, pyromellitic dianhydride, 3-fluoropyrenetetracarboxylic dianhydride, 3,6-difluoro pyromellitic dianhydride, and 3,6-bis(trifluoromethyl)pyrene Acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxygen Phthalic anhydride, 2,2'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'-difluoro-3,3',4,4'- Biphenyltetracarboxylic dianhydride, 6,6'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5',6,6'-hexa Fluorin-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride , 5,5'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 6,6'-bis(trifluoromethyl)-3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5'-fluorene (trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2 , 2',6,6'-fluorene (trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5',6,6'-fluorene (trifluoromethyl) -3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',5,5',6,6'-lu (trifluoromethyl)-3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3",4,4"-terphenyltetracarboxylic dianhydride, 3,3'",4,4'"-tetraphenyltetracarboxylic acid Acid dianhydride, 3,3"", 4,4""-quinacyl tetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-Asian Base-4,4'-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-extended ethyl-4,4'-diphenyl Formic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-five Methylene-4,4'-diphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, Difluoromethylene-4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-extended ethyl-4,4'-diphthalic dianhydride, 1 1,2,2,3,3-hexafluoro-1,3-trimethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4- Octafluoro-1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5 - pentamethylene-4,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1 ,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetra Methyl siloxane dianhydride, 1,3-bis(3,4-dicarboxyphenyl) phthalic anhydride, 1,4-bis(3,4-dicarboxyphenyl) phthalic anhydride, 1,3- Bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-di) Carboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4 -Dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-di Carboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[3-(3,4 -dicarboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl Propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethyl phthalane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)-1,1,3,3-tetramethyldioxanane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-nonanedicarboxylic dianhydride, 1, 2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentane IV Carboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4' - biscyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1,2-extended ethyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4 '-Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1 1,1,3,3,3-hexafluoro-2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4 '-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4, 4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 3,3'-difluorooxy-4,4'-diphthalic dianhydride, 5 , 5'-difluorooxy-4,4'-diphthalic dianhydride, 6,6'-difluorooxy-4,4'-diphthalic dianhydride, 3,3', 5, 5',6,6'-hexafluorooxy-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)oxy-4,4'-diphthalic acid Anhydride, 5,5'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)oxy-4,4'-di Phthalic anhydride, 3,3',5,5'-fluorene (trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',6,6'-fluorene ( Trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5,5',6,6'-fluorene (trifluoromethyl)oxy-4,4'-diphthalic acid Anhydride, 3,3',5,5',6,6'-lu (trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3'-difluorosulfonyl- 4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic dianhydride, 6,6'-difluoro Sulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluorosulfonyl-4,4'-diphthalic dianhydride, 3 , 3'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)sulfonyl-4,4'-diphenyl Dicarboxylic acid dianhydride, 6,6'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5'-fluorene (trifluoromethyl) Sulfonyl-4,4'-diphthalic dianhydride, 3,3',6,6'-fluorene (trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5 , 5',6,6'-肆(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-land (three Fluoromethyl)-sulfonyl-4,4'-diphthalic dianhydride, 3,3'-difluoro-2,2-perfluoropropylene-4,4'-diphthalic dianhydride , 5,5'-difluoro-2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylene-4 , 4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluoro-2,2-perfluoropropylene-4,4'-diphthalic dianhydride , 3,3'-bis(trifluoromethyl)-2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)-2 , 2-perfluoropropylene-4,4 -Dicarboxylic acid dianhydride, 6,6'-difluoro-2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 3,3',5,5'-oxime ( Trifluoromethyl)-2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 3,3',6,6'-fluorene (trifluoromethyl)-2,2- Perfluoropropylene-4,4'-diphthalic dianhydride, 5,5',6,6'-fluorene (trifluoromethyl)-2,2-perfluoropropylene-4,4' -diphthalic dianhydride, 3,3',5,5',6,6'-lu (trifluoromethyl)-2,2-perfluoropropylene-4,4'-diphthalic acid Dihydride, 9-phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis(trifluoromethyl)xanthene-2,3 6,6-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 9,9-bis[4-(3, 4-Dicarboxy)phenyl]ruthenic anhydride, 9,9-bis[4-(2,3-dicarboxy)phenyl]ruthenium anhydride, ethylene glycol trimellitic acid dianhydride, 1,2- (extended ethyl) bis (trimellitic anhydride), 1,3- (three Methylene) bis(trimellitic anhydride), 1,4-(tetramethylene)bis(trimellitic anhydride), 1,5-(pentamethylene)bis(trimellitic anhydride), 1,6-(hexamethylene) double (trimellitic anhydride), 1,7-(heptylene)bis(trimellitic anhydride), 1,8-(octamethylene)bis(trimellitic anhydride), 1,9-(nonamethylene)bis(trimellitic anhydride), 1 , 10-(decamethylene)bis(trimellitic anhydride), 1,12-(dodecyl)bis(trimellitic anhydride), 1,16-(hexamethylene)bis(trimellitic anhydride), 1,18- (octamethylidene) bis (trimellitic anhydride) and the like.

The tricarboxylic anhydride is exemplified by, for example, trimellitic anhydride or nuclear hydrogenated trimellitic anhydride.

As the amine component, a polyamine such as a diamine such as an aliphatic diamine or an aromatic diamine or an aliphatic polyether amine can be used, but it is not limited to these amines. Further, the amine components may be used singly or in combination.

The diamine is exemplified by, for example, a benzene such as p-phenylenediamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine or 2,6-toluenediamine. Diaminodiphenyl such as diamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether or 3,4'-diaminodiphenyl ether Ethers, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl) sulfide, 4,4'-diaminobenzene Anthracene, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (o-tolidine), 2,2'-dimethylbenzidine (m-toluidine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-di Aminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylanthracene, 3 , 4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4 '-Dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane , 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1 ,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylarylene, 3,4'-diaminodiphenylarylene, 4,4'-diaminodiphenyl Two benzene nucleus diamines such as fluorene, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 1,3-bis(3-aminophenyl)benzene, 1, 3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-double (4 -aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-amine Phenoxy group) Fluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-bis(4-phenyl Phenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenyl sulfide)benzene, 1,4-bis(4) -aminophenyl sulfide) benzene, 1,3-bis(3-aminophenylphosphonium)benzene, 1,3-bis(4-aminophenylphosphonium)benzene, 1,4-bis(4- Aminophenyl hydrazine) benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl] Three benzene nuclear diamines such as benzene and 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy) Biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-amino) Phenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]one, bis[3-( 4-aminophenoxy)phenyl]one, bis[4-(3-aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl]one, double [3-(3-Aminophenoxy)phenyl] sulfide, bis[3-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy) Phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[3-(3-aminophenoxy)phenyl]indole, bis[3-(4- Aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[3 -(3-Aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane , bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-( 4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-dual [ 3-(4-Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-amino) An aromatic diamine such as a benzene nucleus diamine such as phenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,2-diaminoethane, 1,3 -diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1, The aliphatic diamine such as 2-diaminocyclohexane is exemplified by an ethylene glycol and/or a propylene glycol-based polyamine. Further, as described below, an amine having a carboxyl group can also be used.

The amine having a carboxyl group can be exemplified by 3,5-diaminobenzoic acid and 2,5-diamine. Diaminobenzoic acid such as benzoic acid, 3,4-diaminobenzoic acid, 3,5-bis(3-aminophenoxy)benzoic acid, 3,5-bis(4-aminophenoxyl) Aminophenoxybenzoic acid such as benzoic acid, 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxyl linkage Carboxybiphenyl compounds such as benzene, 4,4'-diamino-2,2'-dicarboxybiphenyl, 4,4'-diamino-2,2',5,5'-tetracarboxybiphenyl ,3,3'-diamino-4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,2-bis[3 -amino-4-carboxyphenyl]propane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 2,2-bis[3-amino-4-carboxyphenyl]hexafluoro a carboxydiphenylalkane such as a carboxydiphenylmethane such as propane or 4,4'-diamino-2,2',5,5'-tetracarboxydiphenylmethane, or a 3,3'-diamino group. -4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxyl a carboxydiphenyl ether compound such as diphenyl ether or 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl ether, 3,3'-diamino-4,4 '-Dicarboxydiphenylanthracene, 4,4'-di -3,3'-dicarboxydiphenylanthracene, 4,4'-diamino-2,2'-dicarboxydiphenylanthracene, 4,4'-diamino-2,2',5 , diphenyl hydrazine compound such as 5'-tetracarboxydiphenyl hydrazine, bis [(carboxyphenyl) such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane A phenyl] alkane compound, a bis[(carboxyphenoxy)phenyl]fluorene compound such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]anthracene or the like.

The introduction of a phenolic hydroxyl group into a polyimine resin can be carried out by combining a diamine having a phenolic hydroxyl group. The diamine having a phenolic hydroxyl group is exemplified by a diaminophenol such as 2,4-diaminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-di. Amino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2',5,5' -hydroxybiphenyl, etc. Hydroxybiphenyl compounds, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino-3,3'-dihydroxydiphenylmethane, 4, 4'-Diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis[3-amino-4-hydroxyphenyl]propane, 2,2-bis[4-amino-3 -hydroxyphenyl]propane, 2,2-bis[3-amino-4-hydroxyphenyl]hexafluoropropane, 4,4'-diamino-2,2',5,5'-tetrahydroxy a hydroxydiphenylalkane such as hydroxymethane or the like, 3,3'-diamino-4,4'-dihydroxydiphenyl ether or 4,4'-diamino-3, 3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 4,4'-diamino-2,2',5,5'- Hydroxydiphenyl ether compound such as tetrahydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 4,4'-diamino-3,3'-di Hydroxydiphenyl hydrazine, 4,4'-diamino-2,2'-dihydroxydiphenyl fluorene, 4,4'-diamino-2,2',5,5'-tetrahydroxydiphenyl Di-[(hydroxyphenyl)phenyl]alkane compounds such as diphenyl hydrazine compound, 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]propane, etc., 4 , 4'-bis(4-amino-3-hydroxybenzene Bis(hydroxyphenoxy)biphenyl compounds such as biphenyl, bis([hydroxyphenoxy] such as 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]indole a phenyl] anthracene compound, a carboxyl group such as 4,4'-diamino-3,3'-dihydroxydiphenylmethane or 4,4'-diamino-2,2'-dihydroxydiphenylmethane Diphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 4,4'-bis(4-amino-3-hydroxyphenoxy)biphenyl (hydroxyphenoxy)biphenyl compounds, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene Such as bis(hydroxyphenoxy)benzene compounds and the like.

As the isocyanate component, an aromatic diisocyanate and an isomer or polymer thereof, an aliphatic diisocyanate, or an alicyclic diisocyanate can be used. Diisocyanates such as esters and isomers thereof, or other widely used diisocyanates, but are not limited to such isocyanates. Further, the isocyanate components may be used singly or in combination.

The diisocyanate is exemplified by, for example, 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, biphenyl diisocyanate, diphenyl sulfonium diisocyanate, diphenyl ether diisocyanate and the like. An aliphatic diisocyanate such as a diisocyanate and an isomer thereof, a polymer, a hexamethylene diisocyanate, an isophorone diisocyanate or a dicyclohexylmethane diisocyanate, or a hydrogenated fat of the aforementioned aromatic diisocyanate Cyclic diisocyanates and isomers, or other widely used diisocyanates.

The polyimine resin of the component (A) may also have a guanamine bond. These may be those obtained by reacting an isocyanate with a carboxylic acid, or may be obtained by a reaction other than the reaction. Further, it may have a bond formed by other addition and condensation.

For the synthesis of the polyimine resin of the component (A), an alkali-soluble polymer, an oligomer, or a monomer having a carboxyl group and/or an acid anhydride group which is conventionally used may be used, and it may be, for example, a conventional one. A resin obtained by reacting an alkali-soluble resin alone or in combination with the above-described carboxylic anhydride component with the above amine/isocyanate.

The polyimine resin of the component (A) preferably has an acid value of from 20 to 200 mgKOH/g, more preferably from 60 to 150 mgKOH/g, in order to correspond to the alkali development step. When the acid value is 20 mgKOH/g or more, the solubility to alkali is increased, the development property is improved, and further, the heat after irradiation with light is improved. The degree of crosslinking of the hardening component allows sufficient imaging contrast to be obtained. In addition, when the acid value is 200 mgKOH/g or less, the so-called thermal sensitization in the PEB step after the light irradiation described later can be suppressed, and the process margin can be increased.

Further, the molecular weight of the polyimine resin of the component (A) is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, in view of developability and film properties.

When the molecular weight is 1,000 or more, exposure is performed. After PEB, sufficient imageability and hardening properties can be obtained. Further, when the molecular weight is 100,000 or less, the alkali solubility is increased to improve the developability.

[(B) Photobase generator]

(B) The photobase generator is formed by changing the molecular structure by irradiation with light such as ultraviolet rays or visible light, or by cracking the molecule to form an addition reaction reaction as a polyimine resin having a carboxyl group and a thermosetting component. A compound of one or more basic substances having a function as a medium. The basic substance is exemplified by, for example, a secondary amine and a tertiary amine.

The photobase generator is exemplified by, for example, an α-aminoacetophenone compound, an oxime ester compound, or a decyloxyimine group, an N-methylated aromatic amine group, an N-deuterated aromatic amine group, and a nitrate. A compound such as a substituent such as a benzylamino acid group or an alkoxybenzyl urethane group. Among them, an oxime ester compound and an α-aminoacetophenone compound are preferred. As the α-aminoacetophenone compound, it is preferred to have two or more nitrogen atoms.

For other photobase generators, WPBG-018 (trade name: 9-fluorenylmethyl N,N'-diethylcarbamate), WPBG-027 (commercial product) can be used. Name: (E)-1-[3-(2-hydroxyphenyl)-2-propenyl]piperidinyl), WPBG-082 (trade name: 胍鎓2-(3-benzhydrylphenyl) Propionate), WPBG-140 (trade name: 1-(indol-2-yl)ethylimidazolium carboxylate), and the like.

The α-aminoacetophenone compound is a basic substance (amine) having a benzoin ether bond in a molecule and causing cracking by light irradiation in the molecule to form a hardening catalyst. As a specific example of the α-aminoacetophenone compound, (4-morpholinylbenzylidene)-1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Corporation, Japan) or 4-(methylthiobenzimidyl)-1-methyl-1-morpholinylethane (Irgacure 907, trade name, manufactured by BASF, Japan), 2-(dimethylamino)-2-[( Commercially available compounds such as 4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379, trade name, manufactured by BASF Corporation, Japan) or a solution thereof .

The oxime ester compound may be any compound as long as it is a compound which generates a basic substance by light irradiation. The oxime ester compound is preferably an oxime ester photobase generator having a group represented by the following formula (4).

(wherein R ¹ represents a hydrogen atom, an unsubstituted or phenyl group substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, an unsubstituted or substituted carbon group having 1 or more hydroxyl groups of 1 to 20; An alkyl group, the alkyl group interrupted by one or more oxygen atoms, an unsubstituted or substituted alkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group, unsubstituted or having a carbon number of 1 ~6 alkyl or phenyl substituted carbon 2 to 20 alkyl fluorenyl or benzhydryl group, R ² represents unsubstituted or substituted with a carbon number of 1 to 6 alkyl, phenyl or halogen atom An alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with one or more hydroxyl groups, an alkyl group interrupted by one or more oxygen atoms, an unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group a cycloalkyl group having 5 to 8 carbon atoms, an unsubstituted or alkylene group having 2 to 20 carbon atoms or a phenyl group substituted with a carbon number of 1 to 6 or a phenyl group).

Commercial products of the oxime ester-based photobase generator are CGI-325, Irgacure-OXE01, Irgacure-OXE02 manufactured by BASF Corporation of Japan, N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like. Further, a compound having two oxime ester groups in the molecule described in Japanese Patent No. 4344400 can also be used.

In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, An oxazolidine ester compound or the like described in JP-A-2008-80036, JP-A-2009-80036, and JP-A-2011-80036.

These photobase generators may be used alone or in combination of two or more. The amount of the photobase generator in the photosensitive thermosetting resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the thermosetting component. When the amount is 0.1 part by mass or more, the contrast resistance of the light-irradiating portion/non-irradiated portion can be favorably obtained. Further, when the amount is 40 parts by mass or less, the cured product property is improved.

[(C) Thermosetting component]

(C) The thermosetting component has a functional group capable of undergoing an addition reaction with a carboxyl group or a phenolic hydroxyl group by heat. The thermosetting component is preferably a compound having a cyclic (thio)ether group, and examples thereof include an epoxy resin and a polyfunctional oxetane compound.

The above epoxy resin is a resin having an epoxy group, and any of the conventional ones can be used. The invention is exemplified by a bifunctional epoxy resin having two epoxy groups in the molecule, a polyfunctional epoxy resin having a plurality of epoxy groups in the molecule, and the like. Further, it may be a hydrogenated bifunctional epoxy compound.

The above epoxy compounds are exemplified by bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin. Resin, hydantoin type epoxy resin, alicyclic epoxy resin, trishydroxyphenylmethane type epoxy resin, bisphenol type or biphenol type epoxy resin or a mixture thereof; Phenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetrahydroxyphenylethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl group Xylene decyl ethane resin, epoxy resin containing naphthyl group, epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymerized epoxy resin, cyclohexylmaleimide and nail A copolymerized epoxy resin of glycidyl acrylate, a CTBN modified epoxy resin, or the like.

Other liquid bifunctional epoxy resins are exemplified by vinylcyclohexene diepoxide, (3', 4'-epoxycyclohexylmethyl)-3,4-epoxycyclohexanecarboxylic acid. Ester, (3',4'-epoxy-6'-methylcyclohexylmethyl)-3,4- An alicyclic epoxy resin such as epoxy-6-methylcyclohexanecarboxylate. These epoxy resins may be used alone or in combination of two or more.

Further, a conventionally used compound such as a maleic imine compound, a blocked isocyanate compound, an amine resin, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound or a surface thiol resin may be blended as a compound. (C) Thermosetting component.

(C) The equivalent ratio of the amount of the thermosetting component to the polyimine resin of the component (A) (carboxy group: a thermally reactive group such as an epoxy group) is preferably from 1:0.1 to 1:10. By setting the range of the blending ratio, the developability can be improved, and the fine pattern can be easily formed. The above equivalent ratio is preferably from 1:0.2 to 1:5.

[(D) flame retardant]

The photosensitive thermosetting resin composition of the present invention contains a flame retardant. The flame retardant is exemplified by a phosphate ester and a condensed phosphate ester, a phosphorus-containing element (meth) acrylate, a phenolic hydroxyl group-containing phosphorus compound, a cyclic phosphazene compound, a phosphazene oligomer, a phosphonic acid metal salt, and the like. a ruthenium compound such as a phosphorus compound, antimony trioxide or antimony pentoxide; a bromide such as pentabromodiphenyl ether or octabromodiphenyl ether; a metal hydroxide such as aluminum hydroxide or magnesium hydroxide; hydrotalcite; A layered double hydroxide such as a hydrotalcite-like compound. Based on the influence on the environmental surface or the flame retardant effect, it is preferably a phosphorus-containing compound, more preferably a phosphonic acid metal salt.

When a phosphorus-containing compound is blended in a large amount as described above, the cured product of the photosensitive thermosetting resin composition is deteriorated in folding resistance and insulation reliability, so the amount of blending is increased. The phosphorus content in the photosensitive thermosetting resin composition is preferably from 0.01 to 3.0%, more preferably from 0.01 to 2.5%.

Specific examples of the phosphonic acid constituting the phosphonic acid metal salt are exemplified by phosphonic acid, dimethylphosphonic acid, ethylmethylphosphonic acid, diethylphosphonic acid, methyl n-propylphosphonic acid, methane bis(methylphosphonic acid). ) Benzene-1,4-(dimethylphosphonic acid), methylphenylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, and mixtures thereof.

The metal component constituting the phosphonate is exemplified by, for example, calcium, magnesium, aluminum, zinc, barium, manganese, sodium, and potassium. Preferred are calcium, magnesium, aluminum and zinc.

Commercial products of the phosphonic acid metal salt are listed as EXOLIT OP 930, EXOLIT OP 935, etc. manufactured by CLARIANT.

(resin having phenolic hydroxyl group)

The photosensitive thermosetting resin composition of the present invention preferably contains a resin having a phenolic hydroxyl group. When a resin having a phenolic hydroxyl group is present, the time of the addition reaction to the alkali resistance at the same heating temperature during the heat-hardening reaction after exposure (hereinafter referred to as the PEB step) is increased as compared with the case where it is not present. . Further, the selection range of the heating temperature at the time of the heat hardening reaction (hereinafter referred to as the PEB step) can be increased. Based on this, the workability and workability of the resin composition are improved. The unexposed portion is alkali-resistant, and so-called excessive photo-sensing can be suppressed.

The resin having a phenolic hydroxyl group is not particularly limited as long as it has a phenolic hydroxyl group in the main chain or the side chain, that is, has a hydroxyl group bonded to the benzene ring. The phenolic hydroxyl group is also added to the thermosetting component in the same manner as the carboxyl group.

A compound having two or more phenolic hydroxyl groups in one molecule is preferred.

A compound having two or more phenolic hydroxyl groups in one molecule is exemplified by catechol, resorcin, hydroquinone, dihydroxytoluene, naphthalenediol, tert-butylcatechol, tert-butylhydroquinone, ortho Pyrogallol, pyrogallol, bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol, novolak type phenol resin, novolak type alkyl phenol resin, bisphenol A Novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, phenolic resin modified by terpene, polyvinyl phenol, condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, 1-naphthol Or a condensate of 2-naphthol and an aromatic aldehyde, etc., but it is not limited to these. These phenolic hydroxyl group-containing compounds may be used singly or in combination of two or more.

The above resin having a phenolic hydroxyl group preferably has a quinone ring. The quinone ring can be exemplified as the above. The resin having a quinone ring and a phenolic hydroxyl group is preferably a polyimine resin synthesized by using a diamine having a phenolic hydroxyl group as the carboxylic acid anhydride described above.

The molecular weight of a resin having a phenolic hydroxyl group, considering exposure. The mass average molecular weight after the PEB is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, in terms of developability, development resistance, and film properties.

(polymer resin)

In the photosensitive thermosetting resin composition of the present invention, in order to improve the flexibility and dryness of the obtained cured product, a conventional polymer resin can be blended. The polymer resin is exemplified by a cellulose-based, a polyester-based, a phenoxy resin-based polymer, a polyethylene acetal-based, a polyvinyl butyral-based, a polyamid-based, and a polyamidamine-based adhesive polymer. , block copolymer, elastomer Wait. These polymer resins may be used alone or in combination of two or more.

(inorganic filler)

An inorganic filler can be formulated in the photosensitive thermosetting resin composition of the present invention. The inorganic filler is used to suppress the curing shrinkage of the cured product of the photosensitive thermosetting resin composition, and to improve properties such as adhesion and hardness. Inorganic fillers are exemplified by, for example, barium sulfate, amorphous cerium oxide, molten cerium oxide, spherical cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, cerium nitride, aluminum nitride. , boron nitride, Neuburg Siliceous Earth, etc. The inorganic filler may be used singly or in combination of two or more.

(Colorant)

Further, a coloring agent can be formulated in the photosensitive thermosetting resin composition of the present invention. As the coloring agent, conventionally known coloring agents such as red, blue, green, yellow, white, and black may be used, and any of a pigment, a dye, and a coloring matter may be used.

(Organic solvents)

An organic solvent can be used in the photosensitive thermosetting resin composition of the present invention to prepare a resin composition, or to adjust the viscosity for application to a substrate or a carrier film.

Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. Wait. These organic solvents may be used singly or in combination of two or more.

(other optional ingredients)

In the photosensitive thermosetting resin composition of the present invention, components such as a thiol compound, an adhesion promoter, an antioxidant, and an ultraviolet absorber may be further blended as needed. These can be used by those skilled in the art of electronic materials. Further, the photosensitive thermosetting resin composition may be blended with conventionally used tackifiers such as fine powder of ceria, hydrotalcite, organic bentonite, and montmorillonite, polyfluorene, fluorine, and polymer. Conventional additives such as foaming agents and/or leveling agents, decane coupling agents, and rust inhibitors.

[dry film]

The dry film of the present invention is characterized by having a resin layer composed of the photosensitive thermosetting resin composition of the present invention.

In the case of dry film formation, for example, the photosensitive thermosetting resin composition of the present invention is diluted with an organic solvent to have an appropriate viscosity, and is applied to a carrier film to have a uniform thickness by a conventional method such as a notch wheel coater. Subsequently, it is usually dried at a temperature of 50 to 130 ° C for 1 to 30 minutes to form a resin layer on the carrier film.

As the carrier film, a plastic film can be used. The thickness of the carrier film is not particularly limited, but is generally selected in the range of 10 to 150 μm. After the resin layer is formed on the carrier film, a peelable protective film may be laminated on the surface of the resin layer.

[Flexible printed wiring board and method of manufacturing the same]

The flexible printed wiring board of the present invention is characterized in that it has a cured product of a photosensitive thermosetting resin composition or a resin layer of a dry film.

The method for producing a flexible printed wiring board according to the present invention comprises the steps of forming a resin layer made of a photosensitive thermosetting resin composition on a flexible printed wiring board, and irradiating a pattern on the resin layer. The step of light, the step of heating the resin layer, and the step of performing alkali development on the resin layer to form at least one of a protective layer and a solder resist.

[Resin layer forming step]

This step is to form at least one resin layer made of a photosensitive thermosetting resin composition on a flexible printed wiring board.

The method of forming the resin layer is exemplified by a coating method and a layering method.

In the coating method, the photosensitive thermosetting resin composition is applied onto a flexible printed wiring board by a method such as screen printing, and dried to form a resin layer.

In the case of layering, the photosensitive thermosetting resin composition is diluted with an organic solvent to adjust the viscosity to an appropriate viscosity, and is applied onto a carrier film and dried to prepare a dry film having a resin layer. Next, the resin film is bonded to the flexible printed wiring board by a laminator or the like, and then the carrier film is peeled off.

Further, another layer may be interposed between the resin layer and the flexible printed wiring board. The other layer is preferably an alkali-developing type photosensitive thermosetting resin group Made of things. As the alkali-developing type photosensitive thermosetting resin composition, a conventional composition can be used, and for example, a conventional composition for a protective layer or a solder resist can be used. By forming the laminated structure containing the other layers, a cured product excellent in impact resistance and flexibility can be obtained.

[Light irradiation step]

In this step, the photobase generator contained in the resin layer is activated by light irradiation to a negative pattern to harden the light-irradiating portion. In this step, the photobase generator is not stabilized by the alkali generated in the light irradiation portion, and the base is chemically proliferated to sufficiently harden to the deep portion of the resin layer.

As the light irradiation machine, a direct drawing device, a light irradiation machine equipped with a metal halide lamp, or the like can be used. The pattern-shaped light irradiation mask is a negative type mask.

The active energy line used for light irradiation preferably uses laser light or scattered light having a maximum wavelength in the range of 350 to 450 nm. By setting the maximum wavelength to this range, the photobase generator can be more effectively activated. If laser light of this range is used, either a gaseous laser or a solid-state laser can be used. Further, although the amount of light irradiation varies depending on the film thickness or the like, it is generally 100 to 1500 mJ/cm ² .

[heating step]

This step is to cure the light-irradiating portion by heating the resin layer after the light is irradiated. With this step, it can be hardened to the deep by the alkali generated in the light irradiation step. The heating temperature is, for example, 80 to 140 °C. The heating time is, for example, 10 to 100 minutes.

The hardening of the photosensitive thermosetting resin composition in the present invention For example, by the ring-opening reaction of the epoxy resin which is thermally reacted, deformation or hardening shrinkage can be suppressed as compared with the case of hardening by photo-radical reaction.

[development step]

The developing step removes the unirradiated portion by alkali development to form a negative-type pattern insulating film, particularly a protective film and a solder resist.

The developing method may be a conventional method such as dipping. Further, as the alkali developing solution, an alkaline aqueous solution such as potassium hydroxide, an amine or a tetramethylammonium hydroxide aqueous solution (TMAH) or a mixed solution of these may be used.

Further, after the development step, the insulating film may be further irradiated with light. Further, for example, it may be heated at 150 ° C or higher.

Next, an example of a method of producing the flexible printed wiring board of the present invention from the photosensitive thermosetting resin composition of the present invention will be described based on the step diagram of Fig. 1 . Further, Fig. 1 shows a case where the resin layer has a laminated structure, but it may be formed of only one layer.

In the laminating step of FIG. 1, a laminated structure composed of the resin layer 3 and the resin layer 4 is formed on the flexible printed wiring substrate 1 on which the copper circuit 2 is formed.

The resin layer 3 is made of an alkali-developing photosensitive resin composition containing a carboxyl group-containing resin or the like.

The resin layer 4 is formed on the resin layer 3, and is photosensitive by a polyimine resin having one or more quinone rings and one or more carboxyl groups in one molecule, a photobase generator, and a thermosetting component. A thermosetting resin composition is used.

In the light irradiation step of FIG. 1, the mask 5 is placed on the resin layer 4, and light is irradiated in a negative pattern to activate the photobase generator contained in the photosensitive thermosetting resin composition. A step of hardening the light irradiation portion. The heating step of Fig. 1 is a step of hardening the light-irradiating portion by heating the resin layer after the light irradiation step (PEB step). The developing step of Fig. 1 is a step of developing an alkaline aqueous solution, thereby removing the unirradiated portion to form a negative pattern layer.

Further, the second light irradiation step of Fig. 1 is a step of generating a base for activating the residual photobase generator, and the heat hardening step is a step for sufficiently thermally curing the pattern layer.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited by these Examples and Comparative Examples.

<Synthesis Example of Polyimine Resin Solution Containing Iridium Ring and Carboxyl Group>

Add 12.5 g of 3,5-diaminobenzoic acid, 8.2 g of 2,2'-bis[4-(4-amine) to a separable 3-neck flask equipped with a stirrer, a nitrogen inlet tube, a fractionation tube, and a cooling ring. Phenyloxy)phenyl]propane, 30 g of NMP, 30 g of γ-butyrolactone, 27.9 g of 4,4′-oxydiphthalic anhydride, 3.8 g of trimellitic anhydride, in a nitrogen atmosphere, in a chamber The temperature was stirred at 100 rpm for 4 hours. Then, 20 g of toluene was added, and the mixture was stirred for 4 hours while distilling off toluene and water at 180 ° C and 150 rpm in an oil bath temperature to obtain a polyimine resin solution (PI-1) having a quinone ring and a carboxyl group.

The obtained resin (solid content) had an acid value of 85 mgKOH/g and a weight average molecular weight (Mw) of 10,000.

<Synthesis Example of Polyimine Resin Resin Solution Containing Iridium Ring, Phenolic Hydroxy Group and Carboxyl Group>

22.4 g of 3,3'-diamino-4,4'-dihydroxydiphenylanthracene and 8.2 g of 2 were added to a separable 3-neck flask equipped with a stirrer, a nitrogen inlet tube, a fractionation tube and a cooling ring. 2'-bis[4-(4-aminophenoxy)phenyl]propane, 30 g of NMP, 30 g of γ-butyrolactone, 27.9 g of 4,4'-oxydiphthalic anhydride, 3.8 The trimellitic anhydride of g was stirred at 100 rpm for 4 hours at room temperature under a nitrogen atmosphere. Then, 20 g of toluene was added, and the mixture was stirred for 4 hours while distilling off toluene and water at 180 ° C and 150 rpm in an oil bath temperature to obtain an alkali-soluble resin solution (PI-2) having a quinone ring.

The obtained resin (solid content) had an acid value of 18 mgKOH/g, Mw of 10,000, and a hydroxyl equivalent of 390.

<Synthesis Example of Alkali Soluble Resin A-1>

A cresol novolac type epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd., "EPICLON" (registered trademark) N-680, epoxy equivalent: 210) 210 parts were fed into the four necks of a mixer and a circulation cooler. In the flask, 96.4 parts of carbitol acetate was added and dissolved by heating. Next, 0.46 parts of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was slowly added dropwise thereto for about 16 hours until the acid value became 3.0 mgKOH/g or less. The opposite The product was cooled to 80 to 90 ° C, and 76 parts of tetrahydrophthalic anhydride was added, and the reaction was carried out for 8 hours. After cooling, the reaction solution (paint) (taken as "A-1") was taken out. The photosensitive resin-based solid component thus obtained had an acid value of 78 mgKOH/g and a nonvolatile content of 65%.

<Preparation of Photosensitive Thermosetting Resin Composition>

The materials described in the examples were prepared according to the formulations described in the following Table 1, and premixed with a stirrer, and then kneaded by a 3-axis roll mill to prepare a photosensitive thermosetting resin composition. The values in the table are parts by mass unless otherwise specified.

<low warpage>

A sample prepared in the same manner as the sample for evaluation of flexibility (folding resistance) to be described later was cut into 50 mm × 50 mm, and warpage of four corners was measured, and an average value was obtained, and the evaluation was performed based on the following criteria.

○: Those whose warpage is less than 4 mm.

△: The warpage was 4 mm or more, and it was less than 8 mm.

×: The warpage is 8 mm or more.

<flammability>

The composition of each of the above examples and comparative examples was applied to a 25 μm, 12.5 μm thick polyimine film (KapTON 100H (25 μm), KAPTON 50H (12.5 μm), manufactured by Toray Dupont Co., Ltd.) by screen printing. After drying at 80 ° C for 30 minutes, it was allowed to cool to room temperature. Subsequently, the back surface was also coated on the entire surface by screen printing, dried at 80 ° C for 30 minutes, and allowed to cool to room temperature to obtain a double-coated substrate. Using the exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the resist was exposed on the entire surface of the obtained double-sided substrate at an optimum exposure amount, and 1 wt% of 30 ° C was applied under the conditions of a spray pressure of 2 kg/cm ² . The Na ₂ CO ₃ aqueous solution was developed for 60 seconds, and heat-hardened at 150 ° C for 60 minutes to prepare an evaluation sample. The sample for flame retardancy evaluation was subjected to a thin vertical burning test in accordance with the UL94 specification. As a result of the evaluation, the VTM-0 of the UL94 specification was rated as ○, the VTM-1 was rated as Δ, and the unqualified was rated as ×.

<Flexibility (Folding Resistance)>

The composition of each of the above examples and comparative examples was applied to a 25 μm-thick polyimine film (KAPTON 100H manufactured by Toray Dupont Co., Ltd.) by screen printing, dried at 80 ° C for 30 minutes, and allowed to cool to room. temperature. Using a metal halide lamp exposure apparatus (HMW-680-GW20), the resist was exposed to the obtained substrate at an optimum exposure amount, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C was exposed to a spray pressure of 0.2 MPa. Like 60 seconds, a resist pattern was obtained and the substrate was allowed to heat at 150 ° C for 60 minutes to harden.

The evaluation substrate obtained by crimping was subjected to 180° bending for several times, and the occurrence of cracks in the coating film at this time was observed by visual observation and a 200-fold optical microscope, and the number of times of bending until the occurrence of cracking was measured, and the following was used. Benchmarks are evaluated.

◎: The number of bending times is 6 or more.

○: The number of bending times is 4 to 5 times.

△: The number of bending times is 2 to 3 times.

×: The number of bending times is 0 to 1 time.

The results of the above various evaluation tests are shown in Table 1.

As understood from Table 1 above, Examples 1 to 4 of the present invention Although the resin composition has a small blending amount of the flame retardant, the flame retardancy is good, and the low warpage property and the folding endurance are also excellent. Further, in the resin composition of Example 5, since the amount of the acrylate monomer was large, the flame retardancy was slightly inferior. On the other hand, in the case of the component (A) of the present invention, Comparative Example 1 containing an acrylate monomer was inferior in flame retardancy and poor in low warpage, and Comparative Example 2 was inflammable by containing a large amount of flame retardant. It is getting better, but the folding resistance is getting worse.

Claims (8)

A photosensitive thermosetting resin composition comprising (A) a polyimine resin having a quinone ring and a carboxyl group, (B) a photobase generator, (C) a thermosetting component, and (D) Flame retardant. The photosensitive thermosetting resin composition of claim 1, wherein the (D) flame retardant is a phosphorus compound. The photosensitive thermosetting resin composition of claim 1, wherein substantially no (meth) acrylate monomer is contained. The photosensitive thermosetting resin composition of claim 1, wherein the (A) polyimine resin having a quinone ring and a carboxyl group has a phenolic hydroxyl group. The photosensitive thermosetting resin composition of claim 1, wherein the (C) thermosetting component is a cyclic ether compound. The photosensitive thermosetting resin composition of claim 1, which is used for a flexible wiring board. A dry film characterized by having a resin layer formed of the photosensitive thermosetting resin composition of claim 1. A printed wiring board characterized by comprising a cured product obtained by using the photosensitive thermosetting resin composition of claim 1 or the dry film of claim 7.