JP5021337B2 - Resin composition containing thermal base generator - Google Patents

Description

  The present invention relates to a resin composition suitable for a coverlay of a flexible printed wiring board and a flexible printed wiring board using the same.

In recent years, in a flexible printed wiring board (hereinafter abbreviated as FPC) that is remarkably elongated, a material excellent in flexibility and flexibility is required as a base material and a coverlay.
For FPC coverlays, a dry film that can be laminated is desired because of the superiority of the process. Furthermore, the dry film is desired to have photosensitivity.
When manufacturing an FPC using a dry film having no photosensitivity, the dry film is mechanically punched into a predetermined outer shape pattern, aligned with the circuit board, and then dried with the circuit board. The film was pasted together. Once dry film sensitization is realized, the dry film can be patterned into a desired pattern by photolithography after the circuit board and dry film are bonded together, so mechanical pattern punching, alignment with the circuit board, etc. Is no longer necessary.

As such a photosensitive dry film, there is a proposal of using a polyamic acid excellent in alkali developability. For example, a photosensitive resin composition containing a (meth) acrylate compound, polyamic acid, and a photopolymerization initiator has been proposed. Such a photosensitive resin composition forms a pattern through exposure and development processes. Then, it is necessary to perform imidization at a high temperature of 200 ° C. or higher (for example, Patent Document 1).
However, high temperature heating during imidization damages the FPC. Although the heating temperature can be lowered by using an imidization catalyst, there is a concern that when the imidization catalyst is added as it is, the reaction gradually proceeds and the stability of the composition deteriorates. Therefore, it has been studied to use a thermal imidizing agent that generates an imidization catalyst by heating.

  The thermal imidizing agent generates an imidization catalyst by the heat generated by heating the pattern formed by photolithography after forming the cover layer of the photosensitive resin composition on the substrate with wiring. And imidization is performed. If it is a thermal imidizing agent that generates an imidization catalyst at a low temperature, the imidization catalyst is generated at the temperature at which the film is formed, that is, at the time of varnish drying or thermal lamination. As described above, if an imidization catalyst is generated before the pattern formation process by photolithography, imidization proceeds in both the exposed and unexposed areas. Therefore, it becomes difficult to form a pattern.

For this reason, it is desired that the thermal imidizing agent used for the FPC coverlay should be imidized at a heat treatment temperature that does not damage the FPC substrate as well as excellent thermal stability.
Examples of known thermal imidizing agents include carbamate compounds and quaternary ammonium salts (for example, Non-Patent Document 1 and Patent Document 2). The carbamate compound generates not only an imidization catalyst but also carbon dioxide gas by heat. When gas is generated in the film, there is a concern that the surface of the film is rough and voids due to foaming are generated, which is not preferable as an FPC coverlay. Further, a compound containing an ionic salt such as a quaternary ammonium salt is not preferable because there is a concern that the insulation reliability is impaired when an FPC coverlay is formed.
JP 2005-91399 A JP 05-197148 A Chemistry Letters Vol.34, No.10 (2005)

  This invention is made | formed in view of this point, and is excellent in thermal stability, and was excellent in the thermal stability which was difficult in the conventional resin composition by using the thermal base generator which does not generate | occur | produce a gas component. Another object of the present invention is to provide a resin composition that can be patterned by alkali development, that does not cause surface roughness, and that is imidized at a heat treatment temperature that does not damage the FPC substrate.

The resin composition of the present invention, a resin containing thermal base generator which generates a compound with an amine having the lactone ring and (A), the resin (B) having the moiety capable of causing ring closure reaction the amine as a catalyst, the In the composition, a site capable of causing a ring-closing reaction of the resin (B) is an organic group represented by the formula (1), and the thermal base generator (A) is represented by the formula (4a) or the formula (5a). It is at least one of the compounds represented by

(In Formula (1), R ¹ is a tetravalent organic group, and R ² is a divalent organic group.)

In the resin composition of this invention, it is preferable to contain a quinonediazide compound (C).
In the resin composition of this invention, it is preferable to contain the photoinitiator (D) and the compound (E) which has a double bond.
The film of the present invention is characterized by being composed of the above resin composition.
The laminated film of the present invention comprises a carrier film and the film provided on the carrier film.

The laminated film of the present invention preferably includes a cover film formed on the film.
The flexible printed wiring board of the present invention comprises: a base material having wiring; and a cover lay formed on the base material so as to cover the wiring and configured using the film or the laminated film. And

  By containing a compound having a lactone ring, a thermal base generator (A) for generating an amine, and a resin (B) having a site capable of causing a ring-closing reaction using the amine as a catalyst, A resin composition that is excellent in stability, can be patterned by alkali development, does not cause surface roughness, and is imidized at a heat treatment temperature that does not damage the FPC substrate can be realized.

The present inventors include a thermal base generator (A) that generates a compound having a lactone ring and an amine, and a resin (B) having a site capable of causing a ring-closing reaction using the amine as a catalyst. Provided a resin composition that is imidized at a heat treatment temperature that is difficult in the past, has excellent thermal stability, can be patterned by alkali development, does not cause surface roughness, and does not damage the FPC board. To do.
Hereinafter, embodiments of the present invention will be described in detail.
First, the thermal base generator (A) will be described.
The thermal base generator (A) according to the present invention is decomposed by heat to generate a compound having a lactone ring and an amine. The amine may be either a primary amine or a secondary amine, but in the resin composition of the present invention, a secondary amine is preferable because it is used as an imidization catalyst.

The thermal base generator (A) according to the present invention is decomposed by heat and generates a compound having a lactone ring and an amine, but does not generate a gas component such as carbon dioxide. It is preferable not to generate a gas component from the viewpoint of preventing roughness due to degassing of the film surface.
Examples of the amine generated from the thermal base generator (A) according to the present invention include an amine having an alkyl group and a cyclic amine.
Examples of the secondary amine having an alkyl group include diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-s-butylamine, dipentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine. , Didecylamine, and the like. These secondary amines having an alkyl group may have aromatic or other substituents. Examples of the secondary amine having an aromatic group include N-methylaniline, N-ethylaniline, diphenylamine, and N-benzylisopropylamine. Examples of the amine having another substituent include diethanolamine, N-methylethanolamine, and N-ethylethanolamine.

Examples of the cyclic secondary amine include pyrrolidine, piperidine, morpholine, hexamethyleneimine, heptamethyleneimine, and octamethyleneimine.
The cyclic secondary amine may have a substituent in the ring. In the case of having a substituent of a methyl group or an ethyl group, the basicity becomes slightly stronger due to the electron donating property of the substituent, so that it can be used when adjusting the basicity. Examples of such cyclic secondary amines include dimethylpiperidine and diethylpiperidine.
The cyclic secondary amine may contain an oxygen atom in the ring. Since the cyclic secondary amine containing an oxygen atom becomes slightly weak in basicity, it can be used when adjusting the basicity. Examples of such a cyclic secondary amine include morpholine.

The cyclic secondary amine may have a double bond in the ring. Such cyclic secondary amines include pyrrole.
The cyclic secondary amine may have two cyclic secondary amines in one molecule. Examples of such cyclic secondary amines include piperazine and homopiperazine.
Among these secondary amines, cyclic secondary amines having low steric hindrance in the vicinity of amine protons are preferable. From the viewpoint of ring stability, a 5-membered to 9-membered ring is preferable, and a 5-membered to 7-membered cyclic secondary amine is more preferable. Examples of such a compound include compounds represented by formula (2) or formula (3). Among these, the compound represented by the formula (6) is particularly preferable from the viewpoint of imidation catalyst ability.

(In the formula (2), n is 4 to 8, and R ³ is a monovalent organic group selected from hydrogen, a methyl group, and an ethyl group. A plurality of R ³ may be the same or different. .)

(In formula (3), k and m are each 1 or more, and the sum of k and m is 4 to 8. R ³ has the same meaning as above. Plural R ^{3 s} are the same or different. May be.)

(In formula (6), R ³ has the same meaning as described above. Plural R ^{3 s} may be the same or different. R ⁴ is oxygen or a methylene group.)
In addition, the compound that is eliminated when the thermal base generator (A) generates an amine has a lactone ring, which is caused by a ring-closing reaction that occurs when the thermal base generator is heated. Any compound having a lactone ring may be used, but a 4-membered to 6-membered ring is preferable from the viewpoint of ring stability.
Examples of the compound having a 4-membered to 6-membered lactone ring include β-propiolactone, γ-butyrolactone, and δ-valerolactone. The compound having a lactone ring may have an aromatic ring. Examples of the compound having an aromatic ring include phthalide and 4-chromanone. Of these, γ-butyrolactone having excellent ring stability is preferable.

  As the thermal base generator (A) for generating a compound having a lactone ring and an amine, for example, compounds represented by formula (4) or formula (5) are preferable. Among these, the formula (4) is preferable because of excellent thermal stability.

(In Formula (4), R ³ has the same meaning as described above. Plural R ^{3 s} may be the same or different. R ⁴ is an oxygen or methylene group. A is 2-4. )

(In Formula (5), R ³ has the same meaning as described above. Plural R ^{3 s} may be the same or different. R ⁴ is an oxygen or methylene group. B is 0-2. )
Next, resin (B) (hereinafter referred to as resin (B)) having a site capable of causing a ring-closing reaction using the amine according to the present invention as a catalyst will be described.
The resin (B) is a resin having a site capable of causing a ring closure reaction using the amine generated from the thermal base generator (A) as a catalyst. The resin (B) is characterized in that properties such as alkali solubility, glass transition point, elongation, and elastic modulus are changed by causing a ring-closing reaction. As such a resin, there is a resin having an organic group represented by the formula (7) or the formula (1), but a resin having an organic group represented by the formula (1) is preferable from the viewpoint of a ring-closing reaction with an amine. .

(In Formula (1), R ¹ is a tetravalent organic group, and R ² is a divalent organic group.)
Examples of the resin having an organic group represented by the formula (1) include polyamide, polyimide, and polybenzoxazole.
When the resin (B) is a polyamide, a polyamic acid may be formed with the organic group represented by the formula (1) as shown in the formula (8).

(In Formula (8), R ¹ is a tetravalent organic group and R ² is a divalent organic group. X is 1 or more. Plural R ¹ and R ² are the same or different. May be.)
When the resin (B) is a polyimide, as shown in the formula (9), it can be used as a polymer obtained by partially imidizing polyamic acid.

(In Formula (9), R ¹ is a tetravalent organic group, R ² is a divalent organic group. X and y are 1 or more. A plurality of R ¹ and R ² may be the same. May be different.)
When the resin (B) is polyimide, from the viewpoint of alkali dissolution rate, the ratio of x / (x + y) in formula (9) is preferably 0.5 or more, and more preferably 0.7 or more.
When the resin (B) is polybenzoxazole, as shown in the formula (10), it can be used as a polymer in which a polybenzoxazole skeleton is introduced into polyamide.

(In Formula (10), R ¹ is a tetravalent organic group, R ² is a divalent organic group, and R ⁵ is a divalent organic group. X and z are 1 or more. R ¹ and R ² and R ⁵ may be the same or different.)
When the resin (B) is polybenzoxazole, the ratio of x / (x + z) in the formula (10) is preferably 0.5 or more from the viewpoint of the alkali dissolution rate.
The resin (B) is preferably polyamide or polyimide represented by the formula (8) or the formula (9) from the viewpoint of mechanical properties such as flexibility.
The polymer represented by the formula (8) or the formula (9) is synthesized from diamine and tetracarboxylic dianhydride, and as the raw material, for example, the following can be used.

Examples of diamines that can be used include aromatic diamines, aliphatic diamines, and alicyclic diamines.
Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 3,3 ′. -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3, , 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diamino Diphenyl ketone, , 4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] Bisaniline, 3,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methyl) Tylidene)] bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- ( 4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) heptane That.

Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane.
Examples of the alicyclic diamine include a compound represented by the formula (11).

Further, for the purpose of introducing a carboxyl group and / or a hydroxyl group, a diamine having a carboxyl group or a diamine having a hydroxyl group can be used. Introduction of a carboxyl group and / or a hydroxyl group is preferred from the viewpoint of alkali solubility of polyamide or polyimide.
Examples of the diamine having a carboxyl group include a compound represented by the formula (12).

  Examples of the diamine having a hydroxyl group include 1,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino-4-hydroxybenzene, 1,4-diamino-6-hydroxy. Benzene, 1,5-diamino-6-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, 1,2-diamino-3,5-dihydroxybenzene, 4- (3,5-diaminophenoxy) phenol 3- (3,5-diaminophenoxy) phenol, 2- (3,5-diaminophenoxy) phenol, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-diamino-4,4 '-Dihydroxybiphenyl, 2,2-bis (4-hydroxy-3-aminophenyl) propane, 2,2-bis (4 Hydroxy-3-aminophenyl) hexafluoropropane, bis (4-hydroxy-3-aminophenyl) ketone, 2,2-bis (4-hydroxy-3-aminophenyl) sulfide, 2,2-bis (4-hydroxy) -3-aminophenyl) ether, 2,2-bis (4-hydroxy-3-aminophenyl) sulfone, 2,2-bis (4-hydroxy-3-aminophenyl) methane, 4-[(2,4- Diamino-5-pyrimidinyl) methyl] phenol, p- (3,6-diamino-s-triazin-2-yl) phenol, 2,2-bis (4-hydroxy-3-aminophenyl) difluoromethane, 2,2 -Bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoro Lopan, bis (4-amino-3-hydroxyphenyl) ketone, 2,2-bis (4-amino-3-hydroxyphenyl) sulfide, 2,2-bis (4-amino-3-hydroxyphenyl) ether, 2 , 2-bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) difluoromethane Is mentioned.

Moreover, diaminosiloxane can be used for the purpose of introducing a siloxane skeleton.
The introduction of a siloxane skeleton is preferable from the viewpoint of elongation when formed into a film. Examples of the diaminosiloxane include a compound represented by the formula (13).

(In Formula (13), R ⁶ is a divalent organic group, and k is an integer of 1 to 10.)
Examples of the divalent organic group represented by R ⁶ include a hydrocarbon group and an aromatic group. The hydrocarbon group is an ethylene group, a propylene group, a butylene group, or the like. The aromatic group is a phenylene group or the like.
These diamines can be used alone or in combination.
Examples of tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, tetracarboxylic dianhydrides having ester groups, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides. It is done.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3′4,4′-biphenyltetracarboxylic dianhydride, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid. Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3 -Dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis ( 2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10 -Perylenete Lacarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride Thing, 2, 3, , 7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethyl Silane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxy) Phenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester Acid anhydride), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarbo. Xylphenoxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) And diphenyl sulfide dianhydride.

  Examples of tetracarboxylic dianhydrides having ester groups include 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydride) and 1,3-bis (2-hydroxyhexafluoroisopropyl). Benzene bis (trimellitic anhydride), 1,2- (ethylene) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride) 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (Octamethylene) bis (trimellitate anhydride), 1,9- (nonamethylene) bis ( Rimerimate anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitic anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride).

  Examples of the alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,5- Cyclooctadiene-1,2,5,6-tetracarboxylic dianhydride, 5-carboxymethylbicyclo [2.2.1] heptane-2,3,6-tricarboxylic acid-2,3: 5,6- Dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6: 3,5-dianhydride, bicyclo [2.2.2] oct-7-ene-2,3 5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3 4,5-tetracar Acid dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, decahydronaphthalene-1,4 5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane -1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (Exo-bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride) sulfone.

These tetracarboxylic dianhydrides can be used alone or in combination.
The polymer represented by the formula (8) can be obtained by, for example, mixing the diamine and tetracarboxylic dianhydride in a suitable solvent to synthesize a polyamic acid that is a polyimide precursor. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl. Ketones, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, dimethyl carbonate, diethyl malonate, diethyl ether, isopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran can be used. These solvents may be used alone or in combination of two or more.

  Moreover, the polymer shown by Formula (9) can be obtained by partially imidating the polyamic acid obtained by making it above, for example. The imidization may be performed only by heating in an appropriate solvent, or may be performed by adding a catalyst and heating. As a solvent, the same thing as the synthesis | combination of a polyamic acid may be used, and a different thing may be used. Hexane, heptane, octane, benzene, toluene, xylene and the like can be used in addition to the above-described synthetic solvents for polyamic acid. These solvents may be used alone or in combination of two or more. As the catalyst, for example, acid anhydrides, lactones, and bases can be used. Examples of the acid anhydride include acetic anhydride. The lactone is preferably γ-valerolactone, and the base is preferably pyridine and / or methylmorpholine. The catalyst used for partially imidizing the polyamic acid is preferably removed after synthesis. The catalyst can be removed, for example, by adding a solvent azeotroped with water such as toluene or xylene to the synthesis solvent to azeotrope with water generated during imidization.

Next, the (photosensitive) resin composition according to the present invention will be described.
The resin composition of the present invention can be a photosensitive resin composition. In this case, the thermal base generator (A) and the resin (B) may contain a quinonediazide compound (C), a photopolymerization initiator (D), a compound having a double bond (E), or the like.
When the resin composition according to the present invention is used as a positive photosensitive resin composition capable of alkali development, a quinonediazide compound (C) may be contained.
Examples of the quinone diazide compound include 1,2-benzoquinone diazide sulfonic acid esters, 1,2-benzoquinone diazide sulfonic acid amides, 1,2-naphthoquinone diazide sulfonic acid esters, 1,2-naphthoquinone diazide sulfonic acid amides. Is mentioned.

1,2-naphthoquinone diazide sulfonic acid esters include trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, 1,2-naphthoquinone diazide sulfonate esters of (polyhydroxyphenyl) alkanes And the like.
Examples of 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester etc. are mentioned.

  Examples of 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones include 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 , 2 ′, 4,3′-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzopheno -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2′-tetra Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3 4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

Examples of 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones include 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3 , 4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.
Examples of 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like.

  Examples of 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,4 -Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane- 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p -Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-s Phosphonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3 , 4-Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2 -Naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3- Phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1, 2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide— 5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxy) Phenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4- Sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide— 5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 Examples include ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester.

  Among these, 1,2-naphthoquinonediazide sulfonic acid esters are preferable from the viewpoint of dissolution inhibiting ability. As 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester at the 4-position of the sulfonic acid group and 1,2-naphthoquinone diazide-5-sulfonic acid ester at the 5-position Any of these may be used. 1,2-naphthoquinonediazide sulfonic acid ester can be obtained by esterifying with sulfonic acid using a compound having a phenolic hydroxyl group as a raw material. For example, 1,2-naphthoquinonediazide-4-sulfonic acid or its acid chloride or its sulfonate, or 1,2-naphthoquinonediazide-5-sulfonic acid at the 5-position with respect to 1 mol of the functional group of the phenolic hydroxyl group Alternatively, the acid chloride or sulfonate thereof can be obtained by mixing in a suitable solvent such as acetone. At this time, a basic catalyst such as triethylamine may be used. The esterification rate with sulfonic acid is preferably 0.60 or more and 0.98 or less from the viewpoint of dissolution inhibiting ability and alkali solubility after exposure.

When the resin composition according to the present invention is used as a negative photosensitive resin composition capable of alkali development, it contains a photopolymerization initiator (D) and a compound (E) having a double bond. Good. In this case, since the compound having a double bond starts to be polymerized by the photopolymerization initiator in the exposed area, the IPN structure (interpenetrating polymer network structure) is formed, so that the exposed area can be dissolved in an alkaline developer. descend. Thereby, the solubility difference of an exposed part and an unexposed part can be increased, and it can be used as a negative photosensitive resin composition.
Examples of the photopolymerization initiator (D) include benzophenone, Michler's ketone, benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-phenylacetophenone, 2- Hydroxy-2-methylpropiophenone, 2-hydroxy-4-isopropyl-2-methylpropiophenone, 2-ethylanthraquinone, 2-t-butylanthraquinone, diethylthioxanthone, chlorothioxanthone, benzyl, benzyldimethyl ketal, 1- Hydroxycyclohexyl phenyl ketone, benzoylbenzoic acid, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzo Le diphenylphosphine oxide. Furthermore, equimolar adducts of benzoin and ethylene oxide, 2- to 4-fold molar adducts, equimolar adducts of benzoin and propylene oxide, 2- to 4-fold molar adducts, α-allylbenzoin, 1-hydroxycyclohexyl phenyl ketone And ethylene oxide equimolar adduct, 2 to 4 times mole adduct, 1-hydroxycyclohexyl phenyl ketone and propylene oxide equimolar adduct, 2 to 4 times mole adduct, benzoylbenzoic acid and ethylene oxide, etc. Reactant, 2 to 4 times mole adduct, benzoylbenzoic acid and propylene oxide equimolar reaction, 2 to 4 times mole adduct, hydroxybenzophenone and ethylene oxide equimolar reactant, 2 to 4 times mole adduct, Equimolar reaction product of hydroxybenzophenone and propylene oxide, 2 to 4 times Adduct, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 4- (2-acryloxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 4 Equimolar reaction product of 2- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone and ethylene oxide, 2- to 4-fold molar adduct, 4- (2-hydroxyethoxy) -phenyl- (2 -Hydroxy-2-propyl) ketone and propylene oxide equimolar reactant, 2- to 4-fold molar adduct, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- ( 4-decylphenyl) -2-hydroxy-2-methylpropan-1-one and the like. These can be used 1 type or in mixture of 2 or more types.

The compound (E) having a double bond is preferably an acrylate compound or a methacrylate compound having two or more double bonds in one molecule from the viewpoint of reactivity.
Examples of such acrylate compounds include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. , Tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate Polypropylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy 1-acryloxy 3-meta Cloxypropane, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4- (acryloxy-polyethoxy) phenyl] propane, 2, 2-bis [4- (acryloxy-polypropoxy) phenyl] propane, 2,4-diethyl-1,5-pentanediol diacrylate, ethoxylated totimethylolpropane triacrylate, propoxylated totimethylol group Pan triacrylate, isocyanuric acid EO modified triacrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate, ditrimethylolpropane tetrale Acrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, 1,3,5-triacryloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, 5,5-diallylbarbituric acid, diallylamine, diallyldimethylsilane, diallyldisulfide, diallylether, diallylsiale Salts, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4′-isopropylidene diphenol diacrylate.

  Examples of the methacrylate compound include 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, Tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl Methacrylate, steer Lyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol di Methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2 , 2-bis [4- (methacryloxy polyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, polypropylene glycol dimethacrylate, 1, -Butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol di Examples include methacrylate, 1,4-cyclohexanedimethanol dimethacrylate, glycidyl methacrylate, and 4,4′-isopropylidene diphenol dimethacrylate.

  The resin composition according to the present invention may further contain a photosensitizer. There is no restriction | limiting in particular as a photosensitizer, A well-known photosensitizer can be used. For example, aromatic azides such as azidoanthraquinone and azidobenzalacetophenone; coumarin compounds such as coumarin, ketocoumarin, 3,3′-carbonylbis (diethylaminocoumarin), and 3-ketocoumarin; benzanthrone of aromatic ketones, Phenontolenquinone, benzyl, benzophenone, p, p′-tetramethyldiaminobenzophenone, etc .; aromatic amines N-phenyldiethanolamine, N-phenylglycine, p-nitroaniline, 2,4-dinitroaniline, 2-chloro- 4-nitroaniline 2,6-dinitro-4-nitroaniline, Michler's ketone, etc .; thioxanthone compounds such as thioxanthone, diethylthioxanthone, isopropylthioxanthone; aromatic hydrocarbons anthracene, naphthalene Diphenyl, p- nitro diphenyl; is quinones anthraquinone, naphthoquinone, benzoquinone, etc.. In addition, for example, coumarin compounds having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335; 3-ketocoumarin compounds described in JP-A-63-221110; JP-A-4-221958 Xanthene dyes described in JP-A-4-219756; pyromethene dyes described in JP-A-6-19240; JP-A-47-2528; JP-A-54-155292; (P-dialkylaminobenzylidene) ketone and styryl dye described in JP-A-56-166154 and JP-A-59-56403; sensitizing dye having a julolidyl group described in JP-A-6-295061; The diaminobenzene compound described in 11-326624 gazette can be mentioned. Of these, compounds having absorption in the vicinity of 300 to 450 nm are preferable, and specifically, coumarin compounds, thioxanthone compounds, and aromatic ketones are preferable.

A known additive can be added to the resin composition according to the present invention, if necessary, within a quantitative and qualitative range that does not depart from the effects of the present invention. Specifically, adhesion improvers, surfactants, antioxidants, UV inhibitors, light stabilizers, plasticizers, waxes, fillers, pigments, dyes, foaming agents, antifoaming agents, dehydrating agents, charging Examples thereof include an inhibitor, an antibacterial agent, an antifungal agent, a leveling agent, and a dispersant.
The resin composition according to the present invention comprises a thermal base generator (A) and a resin (B) and, if necessary, a quinonediazide compound (C) or a photopolymerization initiator (D) and a compound having a double bond (E ), And are mixed in an arbitrary solvent. The solution obtained by mixing can be used as a coating solution. Solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone , Cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, dimethyl carbonate, diethyl malonate, diethyl ether, isopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and the like.

Moreover, the (dry) film can be obtained by apply | coating the solution of the resin composition which concerns on this invention to a predetermined base material, and making it dry by arbitrary methods.
A circuit board can be produced using the resin composition according to the present invention. In the case of producing a circuit board, a positive or negative photosensitive resin composition layer is laminated on at least a substrate having wiring, and pattern exposure is performed on the photosensitive resin composition layer, and the pattern exposure is performed. The subsequent resin composition layer is developed using an alkaline aqueous solution. The base material having wiring refers to a material having wiring on an arbitrary base material such as a hard base material such as a glass epoxy substrate or a glass maleimide substrate or a flexible base material such as a polyimide film.

Especially, the resin composition concerning this invention can be used suitably as a coverlay of the flexible printed wiring board which has wiring on flexible base materials, such as a polyimide film. When the resin composition according to the present invention is used as a coverlay for a flexible printed wiring board, for example, it is applied in a dry film state onto a substrate having wiring.
When using a dry film composed of the resin composition of the present invention, the resin composition solution is applied on an arbitrary carrier film such as a polyethylene terephthalate film or a metal film by an arbitrary method, and then dried. Into a laminated film having a carrier film and a dry film.

Moreover, it is good also as a laminated film by providing at least one layer of arbitrary antifouling films, such as a low density polyethylene film, and a protective film on a dry film.
This dry film is laminated on a substrate having wiring by an arbitrary method such as a heat laminating method, a heat pressing method, a heat vacuum laminating method, or a heat vacuum pressing method. Thus, a base material having wiring, and a cover lay formed on the base material so as to cover the wiring and made of a substance obtained by exposing and developing the resin composition according to the present invention, The flexible printed wiring board to comprise can be produced.
Although there is no restriction | limiting in particular in the film thickness of the coverlay formed by these methods, From points, such as a circuit characteristic, it is preferable that they are 4 micrometers-50 micrometers, It is more preferable that they are 6 micrometers-40 micrometers, It is 10 micrometers-30 micrometers. It is particularly preferred.

The light source used for the exposure is not particularly limited, and examples thereof include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser.
The aqueous alkali solution used for development is not particularly limited, and examples thereof include an aqueous sodium carbonate solution, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution. Although there is no restriction | limiting in particular as a developing method, For example, immersion development, paddle development, and spray development are mentioned.
A film, a positive pattern, or a negative pattern obtained on the substrate by these methods can be subjected to a heat treatment as necessary. The heating temperature is preferably 100 ° C. or more and 200 ° C. or less from the viewpoint of generation of an imidation catalyst, activation thereof, and damage to the FPC. More preferably, it is 120 degreeC or more and 180 degrees C or less.

Due to the heat treatment in this temperature range, the resin composition according to the present invention causes a ring closure reaction in the resin (B) component when the thermal base generator (A) generates an amine. Chemical properties, flame retardancy, etc. can be expressed.
Heating may be performed in an air atmosphere or a nitrogen atmosphere. Moreover, there is no restriction | limiting in particular as a heating method, However, It can carry out using oven, a baking furnace, a hotplate, etc.
The present invention is not limited to the embodiment described above, and can be implemented with various modifications. It is not limited to this about the numerical value and component in the said embodiment, It is possible to change suitably and to implement. In addition, various modifications can be made without departing from the scope of the present invention.

  The resin composition of the present invention can be applied to a patterning process using photolithography capable of alkali development, and can be suitably used as an FPC coverlay.

Claims (7)

A resin composition comprising a compound having a lactone ring, a thermal base generator (A) for generating an amine, and a resin (B) having a site capable of causing a ring-closing reaction using the amine as a catalyst, The site capable of causing the ring closure reaction of (B) is an organic group represented by the formula (1), and the thermal base generator (A) is at least one of the compounds represented by the formula (4a) or the formula (5a). A resin composition characterized by being a seed .

(In Formula (1), R ¹ is a tetravalent organic group, and R ² is a divalent organic group.)

The resin composition according to claim 1, comprising a quinonediazide compound (C). The resin composition according to claim 1 or 2 , comprising a photopolymerization initiator (D) and a compound (E) having a double bond. A film comprising the resin composition according to any one of claims 1 to 3 . A laminated film comprising: a carrier film; and the film according to claim 4 provided on the carrier film. The laminated film according to claim 5 , further comprising a cover film formed on the film. A substrate having wiring, and a cover lay formed on the substrate so as to cover the wiring and configured using the film or laminated film according to any one of claims 4 to 6. A flexible printed wiring board characterized by that.