TW201908429A - Laminated structure, dry film and flexible printed wiring board - Google Patents

Abstract

Provided are: a multilayer structure which has higher bendability than ever before, in particular, excellent crack resistance to excessive seam folding; a dry film; and a flexible printed wiring board which comprises a cured product of the dry film as a protective film. A multilayer structure which comprises a resin layer (A) and a resin layer (B) that is laminated on a flexible printed wiring board, with the resin layer (A) being interposed therebetween. The resin layer (B) is formed from a photosensitive thermosetting resin composition that contains an alkali-soluble resin, a photopolymerization initiator, a thermally reactive compound and a block copolymer; and the resin layer (A) is formed from an alkali developable resin composition that contains an alkali-soluble resin and a thermally reactive compound.

Description

Laminated structure, dry film, and flexible printed wiring board

The present invention relates to a laminated structure useful as an insulating film for a flexible printed wiring board, a dry film, and a flexible printed wiring board (hereinafter, also simply referred to as "wiring board").

In recent years, the miniaturization and thinness of electronic devices promoted by the spread of smart phones and tablet terminals has made it necessary to reduce the space of circuit boards. Therefore, the use of the flexible printed wiring board which can be folded and stored is gradually expanding, and the flexible printed wiring board is required to have a high reliability so far.

In contrast, polyimide, which is excellent in mechanical properties such as heat resistance and bendability, is widely used as an insulating film for ensuring the reliability of insulation of flexible printed wiring boards. A hybrid coating process that is a coating layer of a substrate (see, for example, Patent Documents 1 and 2), and uses a photosensitive resin composition capable of fine processing, such as excellent electrical insulation and solder heat resistance, in a mounted portion (non-bent portion). .

That is, the coating layer based on polyimide must be processed by die stamping, so it is not suitable for fine wiring. Therefore, it is necessary to partially use an alkali-developing photosensitive resin composition (solder resist) capable of achieving processing by photolithography on a wafer mounting portion that requires fine wiring. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 62-263692 [Patent Document 2] Japanese Patent Laid-Open No. 63-110224

[Problems to be Solved by the Invention]

Therefore, in the past manufacturing steps of the flexible printed wiring board, a mixed loading process of a step of attaching the cladding layer and a step of forming a solder resist had to be adopted, so there were problems of poor cost and workability.

In contrast, the application of the insulating film as a solder resist or the insulating film as a clad layer to a solder resist and a clad layer of a flexible printed wiring board has been reviewed so far, but the requirements for reducing the space of the circuit board, Materials that can fully meet the performance requirements of both solder resist and cladding have not yet reached practicality.

Specifically, in order to reduce the space requirement of the circuit board, when the flexible printed wiring board is stored in the machine, the flexible printed wiring board with the mounted components is folded and stored. . Therefore, the flexible printed wiring board and its insulating film have been applied with a load in a folded state, but on this side, the actual situation is still not developed to fully meet the requirements of both the solder resist and the coating layer. Performance materials. Here, folding means folding the upper side of the flexible printed wiring board 180 °. Therefore, it is required for the flexible printed wiring board to have a high degree of flexibility so far, especially an insulating film suitable for a solder resist and a coating layer, which has excellent crack resistance even if it is excessively folded.

Therefore, the main object of the present invention is to provide a laminated structure that satisfies the performance required by both the solder resist and the cladding layer, and has a high bending property so far, especially a laminated structure that has excellent crack resistance even after being excessively folded. In addition, another object of the present invention is to provide an insulating film for a flexible printed wiring board, particularly a laminated structure suitable for forming a body of a bent portion (curved portion) and a mounted portion (non-curved portion). A film, and a flexible printed wiring board having a cured product thereof as a protective film, for example, a cladding layer or a solder resist. [Means to solve the problem]

The present inventors have completed the present invention as a result of careful research in order to solve the above-mentioned problems. That is, the laminated structure of the present invention is characterized by having a resin layer (A) and a resin layer (B) laminated on a flexible printed wiring board via the resin layer (A); The layer (B) is composed of a photosensitive thermosetting resin composition containing an alkali-soluble resin, a photopolymerization initiator, a thermally reactive compound, and a block copolymer, and the resin layer (A) is composed of An alkali-soluble resin and an alkali-developing resin composition of a heat-reactive compound.

In the laminated structure of the present invention, the block copolymer preferably has a structure represented by the following formula (I), and the mass average molecular weight (Mw) of the block copolymer is preferably 20,000 to 400,000. XYX (I) (In the formula (I), X is a polymer unit having a glass transition temperature Tg of 0 ° C or higher, and each may be the same or different. Y is a polymer unit having a glass transition temperature Tg of less than 0 ° C. .)

In the laminated structure of the present invention, it is preferable that the photopolymerization initiator contains the photobase generator as the photopolymerization initiator of the resin layer (B). Still further, in the laminated structure of the present invention, the resin layer (A) is preferably composed of an alkali-developing resin composition containing no photopolymerization initiator.

The laminated structure of the present invention can be used in at least any one of a bent portion and a non-bent portion of a flexible printed wiring board, and can be used in a coating layer and a solder resist of a flexible printed wiring board. And at least one of the interlayer insulation materials.

In addition, the dry film of the present invention is characterized by being supported or protected by at least one side of the laminated film of the present invention.

Furthermore, the flexible printed wiring board of the present invention is characterized by having an insulating film using the laminated structure of the present invention.

Here, the flexible printed wiring board of the present invention may be a layer having a layered structure of the present invention formed on the flexible printed wiring board, patterned by light irradiation, and once in a developing solution. Insulation film formed by pattern. In addition, instead of using the laminated structure of the present invention, a resin layer (A) and a resin layer (B) may be sequentially formed on a flexible printed wiring board, and then patterned by light irradiation. A patterned insulating film is formed in the developing solution at one time. Furthermore, the "pattern" in the present invention refers to a pattern-shaped hardened material, that is, an insulating film. [Effect of the invention]

According to the present invention, it is possible to provide a laminated structure that satisfies the performance required by both the solder resist and the cladding layer, and has high bending properties so far, and particularly has excellent crack resistance even if it is excessively folded. In addition, it becomes possible to realize an insulating film suitable for a flexible printed wiring board, especially a laminated structure, a dry film, and a one-time forming process of a bent portion (bent portion) and a mounted portion (non-bent portion), A flexible printed wiring board having a hardened material as a protective film, for example, a cladding layer or a solder resist.

Hereinafter, embodiments of the present invention will be described in detail. (Laminated Structure) The laminated structure of the present invention has a resin layer (A) and a resin layer (B) laminated on a flexible printed wiring board with the resin layer (A) interposed therebetween. Here, in the laminated structure of the present invention, the resin layer (A) and the resin layer (B) function substantially as an adhesive layer and a protective layer, respectively. The laminated structure of the present invention has a resin layer (B) which is photosensitive with an alkali-soluble resin, a photopolymerization initiator, a thermally reactive compound, and a block copolymer (also referred to as "BCP"). The resin layer (A) is composed of a thermosetting resin composition, and the resin layer (A) is a characteristic point composed of an alkali-developing resin composition including an alkali-soluble resin and a thermoreactive compound.

In the present invention, in the laminated structure obtained by laminating two resin layers, the resin layer (B) on the upper layer side contains a block copolymer, thereby achieving a high degree of bending with good balance so far. Properties, especially excellent crack resistance to excessive folding, and excellent heat resistance.

Moreover, such a laminated structure of the present invention may be a flexible printed wiring board having a copper circuit formed on a flexible substrate, which has a resin layer (A) and a resin layer (B) in this order, and the upper layer side The resin layer (B) is a photosensitive thermosetting resin composition that can be patterned by light irradiation, and the resin layer (A) on the lower layer side does not contain a photopolymerization initiator, and the resin layer ( B) and the resin layer (A) can also be patterned at one time by developing.

The reason for this is that the resin layer (A) on the printed wiring board side does not contain a photopolymerization initiator. Generally, this resin layer (A) cannot be patterned as a single layer. However, in the present invention, In the laminated structure, active species such as radicals generated from the photopolymerization initiator contained in the resin layer (B) above it diffuse to the resin layer (A) directly below during exposure. Therefore, it becomes possible to pattern the two layers at the same time.

[Resin layer (A)] (Alkali-developing resin composition) As the alkali-developing resin composition constituting the resin layer (A), as long as it contains one or more functional groups among phenolic hydroxyl groups and carboxyl groups, and An alkali-soluble resin developed by an alkali solution and a composition of a thermally reactive compound may be used. Preferable examples include a resin composition containing a compound having a phenolic hydroxyl group, a compound having a carboxyl group, and a compound having a phenolic hydroxyl group and a carboxyl group, and known ones can be used.

Examples of the resin composition include a resin composition containing a carboxyl group-containing resin or a carboxyl group-containing photosensitive resin, a compound having an ethylenically unsaturated bond, and a thermally reactive compound that have been conventionally used as a solder resist composition.

Here, as the carboxyl group-containing resin or the carboxyl group-containing photosensitive resin, and a compound having an ethylenically unsaturated bond, known and commonly used compounds can be used. In addition, as the thermally reactive compound, a known and commonly used compound having a functional group capable of hardening and reacting with heat such as a cyclic (thio) ether group and the like as the thermally reactive compound used in the resin layer (B) can be used.

Such a resin layer (A) may or may not contain a photopolymerization initiator. Examples of the photopolymerization initiator used when a photopolymerization initiator is included include those used in the resin layer (B). The photopolymerization initiator is the same.

In the present invention, the resin layer (B) must contain a block copolymer. However, the resin layer (A) can also be used to the extent that it does not affect the effects of the present invention, that is, the required performance of both the solder resist and the coating layer. ) Contains a block copolymer. As the block copolymer at this time, the same as the block copolymer used in the resin layer (B) can be used. The blending amount of the block copolymer in the resin layer (A) is preferably 15 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably the resin layer (A) with respect to 100 parts by mass of the alkali-soluble resin. ) Does not contain a block copolymer, and only the resin layer (B) contains a block copolymer. If the blending amount of the block copolymer is 15 parts by mass or less, it will not affect the developability, bendability, crack resistance, and heat resistance.

[Resin layer (B)] (Photosensitive thermosetting resin composition) 之 The photosensitive thermosetting resin composition constituting the resin layer (B) contains an alkali-soluble resin, a photopolymerization initiator, and a thermally reactive compound. And block copolymers.

(Alkali-soluble resin) As the alkali-soluble resin, the same well-known and conventional ones as the resin layer (A) can be used, and a fluorene-imide structure having excellent properties such as bending resistance and heat resistance can be suitably used. Carboxyl-containing resin of at least any one of amidine structures. Examples of the carboxyl group-containing resin having at least one of a fluorenimine structure and a fluorenimine structure include (1) a carboxyl group-containing resin having a fluorenimine structure and a fluorenamine structure, and (2) a fluorinated imine structure. However, carboxyl-containing resins having no fluorene structure and (3) carboxyl-containing resins having fluorene structure but no fluorinimine structure; these resins can be used alone or as a mixture of two or more. In the present invention, among carboxyl group-containing resins having at least one of a fluorene imine structure and a fluorene structure, it is preferable to use a carboxyl group resin having a fluorene imine structure and a fluorene structure. Furthermore, the carboxyl group-containing resin having at least one of a fluorene imine structure and a fluorene structure may further have a phenolic hydroxyl group.

(1) Carboxyl-containing resin having a fluorene imine structure and a fluorene structure A diamine of an amine is reacted with an anhydride (a1) containing an anhydride having at least 3 carboxyl groups and 2 of these are anhydrides to obtain a sulfonium imide, and then the obtained sulfonium imide and a diisocyanate compound are obtained. It is obtained by reacting the reaction raw materials. As described later, it is preferable that the reaction raw material contains an anhydride (a2) having at least 3 carboxyl groups and 2 of which are anhydrous, in addition to the sulfonium imide and the diisocyanate compound.

Here, the diamine used in the synthesis of the polyamidoamine imine resin includes at least a carboxyl group-containing diamine, and a diamine having an ether bond is preferably used in combination. Examples of the carboxyl group-containing diamine include diaminobenzoic acids such as 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, and the like. Aminophenoxybenzoic acids such as 5-bis (3-aminophenoxy) benzoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, 3,3'-methylenebis (6-aminobenzoic acid), carboxybiphenyl compounds such as 3,3'-diamino-4,4'-dicarboxybiphenyl, 3,3'-diamino-4,4'-di Carboxydiphenylmethanes such as carboxydiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3'-diamino-4,4'-di A carboxydiphenyl ether compound such as a carboxydiphenyl ether and the like may be used alone or in a suitable combination.

Examples of the diamine having an ether bond include polyoxyethylene diamine and polyoxypropylene diamine. Other examples include polyoxyalkylene groups containing oxyalkylene groups having different carbon chain numbers. Diamine, etc. The molecular weight of the diamine having an ether bond is preferably 200 to 3,000, and more preferably 400 to 2,000. Examples of the polyoxyalkylene diamines include polyoxyethylene diamines such as Jeffamine ED-600, ED-900, ED-2003, EDR-148, HK-511, etc. manufactured by Huntsman, USA, or Jeffamine D -230, D-400, D-2000, D-4000 and other polyoxypropylene diamines, or Jeffamine XTJ-542, XTJ533, XTJ536 and others with polytetramethylene ethylene. As the diamine having an ether bond, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane can also be used.

As such a diamine, a diamine other than the diamine may be used in combination. As other diamines that can be used in combination, general-purpose aliphatic diamines, aromatic diamines, and the like can be used alone or in a suitable combination. Specifically, examples of the other diamine include p-phenylene diamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, diamine with one benzene nucleus, 4,4'-diaminodiphenyl ethers, 3,3'-diaminodiphenyl ethers, 3,4'-diaminodiphenyl ethers and other diamine diphenyl ethers, 4 , 4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminodiamine Benzene, 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl Phenyl] benzene, 1,4-bis [2- (3-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-aminophenoxy) phenyl] Ethers, aromatic diamines such as 3,3'-diamino-4,4'-dihydroxydiphenylphosphonium, 1,2-diaminoethane, 1,3-diaminopropane, 1, 4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamine The aliphatic diamine octane.

The anhydride (a1) used in the synthesis of the polyamidoamine imine resin includes an anhydride having at least 3 carboxyl groups and 2 of which are anhydrous. Examples of the acid anhydride include at least one of an aromatic ring and an aliphatic ring. Examples of the acid anhydride include anhydrous trimellitic acid (trimellitic anhydride) (benzene- 1,2,4-tricarboxylic acid (1,2-anhydrous, TMA), 4,4'-oxydiphthalic anhydride, and the like, as those having an aliphatic ring, hydrogenated trimellitic anhydride (cyclohexyl) Alkane-1,2,4-tricarboxylic acid-1,2-anhydrous, H-TMA) and the like. These acid anhydrides may be used alone or in combination of two or more. Also, a carboxylic dianhydride may be used in combination. Examples of the carboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, and the like, and tetracarboxylic anhydride.

As the diisocyanate compound used in the synthesis of the above-mentioned polyamidoamine imine resin, for example, aromatic diisocyanate and its isomers or polymers, aliphatic diisocyanates, alicyclic diisocyanates, and the like may be used. Structures such as diisocyanates, or other commonly used diisocyanates, but not limited to them. These diisocyanate compounds may be used alone or in combination.

As described above, the polyfluorenimide imide resin can be obtained by reacting a reaction raw material containing a sulfonium imide and a diisocyanate compound, and can also contain an acid anhydride used in obtaining the sulfonimide as The same acid anhydride (a2). As this acid anhydride (a2), the same thing as the said acid anhydride (a1) can be used, and the thing which is different can also be used. The content of the acid anhydride (a2) in the reaction raw material at this time is not particularly limited.

As described above, the polyamidoamine imine resin has the viewpoint of improving alkali solubility and improving developability, especially based on the use of a carboxyl-containing diamine and diamine having an ether bond, and an alicyclic trimellitic acid That is, H-TMA is preferred. For the same reason, it is preferable to use an aliphatic diisocyanate compound in the second-stage reaction of such a polyamidamine / imide resin. Thereby, by effectively introducing a fatty chain or alicyclic structure into the structure, it becomes possible to improve alkali solubility without significantly reducing characteristics.

In addition, as the carboxyl group-containing resin having a fluorene imine structure and a fluoramine structure, a polyfluorene amine imine resin having a structure shown by the following general formula (1) and a structure shown by the following general formula (2) can be used. .

Here, X ₁ is a residue of an aliphatic diamine (a) derived from a dimer acid having 24 to 48 carbon atoms. X ₂ is a residue of an aromatic diamine (b) having a carboxyl group. Y systems are each independently a cyclohexane ring or an aromatic ring.

Specifically, as a polyamidofluorine imine resin which has such a structure, what is shown by following General formula (3) is mentioned.

In the above general formula (3), X is each independently a diamine residue, Y is each independently an aromatic ring or a cyclohexane ring, and Z is a residue of a diisocyanate compound. n is a natural number.

(2) Carboxyl-containing resin having a fluorene imine structure but not having a fluorene structure A carboxyl group resin having a fluorene imine structure but not having a fluoramine structure is not particularly limited as long as it is a resin having a carboxyl group and a fluorene imine ring. For the synthesis system of a carboxyl group-containing resin having a fluorenimine structure but not having a fluorenimine structure, a known conventional method of introducing a fluorinimide ring into a carboxyl group-containing resin can be used. Examples thereof include resins obtained by reacting a carboxylic acid anhydride component with an amine component and / or an isocyanate component. The fluorene imidization may be thermal fluoridation, chemical fluoridation, or a combination thereof.

Here, examples of the carboxylic acid anhydride component include tetracarboxylic acid anhydride and tricarboxylic acid anhydride, but they are not limited to these acid anhydrides, as long as they are compounds having an acid anhydride group and a carboxyl group which react with an amine group or an isocyanate group. It is also possible to use derivatives including them. These carboxylic anhydride components may be used alone or in combination.

Examples of the tetracarboxylic anhydride include pyromellitic dianhydride, 3-fluoro pyromellitic dianhydride, 3,6-difluoro pyromellitic dianhydride, and 3,6-bis (trifluoromethyl ) Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4 '-Oxydiphthalic dianhydride, 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'-hexafluoro-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 (trifluoro (Methyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5 '-(trifluoromethyl) -3,3', 4,4 ' -Biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-di (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 5,5 ', 6,6'-(trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 2,2', 5,5 ', 6,6'- Lu (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic acid di Anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ”, 4,4” -terphenyltetracarboxylic dianhydride, 3,3 '”, 4,4'”-quad Phenyltetracarboxylic dianhydride, 3,3 "", 4,4 ""-p-Pentaphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1- Ethynyl-4,4'-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylidene-4,4'-diphthalic acid Dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene -4,4'-Diphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, difluoromethylene -4,4'-diphthalic acid dianhydride, 1,1,2,2-tetrafluoro-1,2-ethyl-4,4'-diphthalic acid 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 acid dianhydride, thio-4,4'-diphthalic acid dianhydride, sulfo-4,4'-diphthalic acid dianhydride, 1,3-bis (3,4-dicarboxyl (Phenyl) -1,1,3,3-tetramethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) phthalic anhydride, 1,4-bis (3,4- Carboxyphenyl) phthalic anhydride, 1,3-bis (3,4-dicarboxyphenoxy) phthalic anhydride, 1,4-bis (3,4-dicarboxyphenoxy) phthalic anhydride, 1, 3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] phthalic anhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] Phthalic anhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2, 2-bis [3- (3,4-dicarboxyphenoxy) 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) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy Group) -1,1,3,3-tetramethyldisiladian dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride , 3,4,9,10-fluorenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2, 3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic 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-ethylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1- Ethynyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene group-4,4'-bis (cyclohexane-1,2-di (Carboxylic 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 acid dianhydride, 5, 5'-difluorooxy-4,4'-diphthalic acid dianhydride, 6,6'-difluorooxy-4,4'-diphthalic acid dianhydride, 3,3 ', 5,5', 6,6'-hexafluorooxy-4,4'-diphthalic acid dianhydride, 3,3'-bis (trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 5,5 '-Bis (trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 6,6'-bis (trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 3 , 3 ', 5,5'-Di (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 3,3', 6,6'-Di ( Trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 5,5 ', 6,6'-di (trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 3,3 ', 5,5', 6,6'-Lu (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 3,3'-difluorosulfonyl-4,4 '-Diphthalic acid dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic acid dianhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic acid Anhydride, 3,3 ', 5,5', 6,6'-hexafluorosulfonyl-4,4'-diphthalic dianhydride, 3,3'-bis (trifluoromethyl) sulfonyl- 4,4'-diphthalic acid dianhydride, 5,5'-bis (trifluoromethyl) sulfofluorenyl-4,4'-diphthalic acid dianhydride, 6,6'-bis (trifluoromethyl) Sulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 5,5'-(trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 6,6'-Di (trifluoromethyl) sulfofluorenyl-4,4'-diphthalic dianhydride, 5,5', 6,6'-Di (trifluoromethyl) sulfofluorenyl- 4,4'-Diphthalic acid dianhydride, 3,3 ', 5,5', 6,6'-L (trifluoromethyl) sulfofluorenyl-4,4'-diphthalic acid dianhydride, 3, 3'-difluoro-2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 5,5'-difluoro-2,2-perfluoropropylene-4,4'- Diphthalic acid dianhydride, 6,6'-difluoro-2,2-perfluoropropylene-4,4'-diphthalic acid Dianhydride, 3,3 ', 5,5', 6,6'-hexafluoro-2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 3,3'-bis (tris (Fluoromethyl) -2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 5,5'-bis (trifluoromethyl) -2,2-perfluoropropylene-4 , 4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 3,3 ', 5,5'- (Trifluoromethyl) -2,2-perfluoropropylene-4,4'-diphthalic dianhydride, 3,3 ', 6,6'-(trifluoromethyl) -2,2- Perfluoropropylene-4,4'-diphthalic dianhydride, 5,5 ', 6,6'-(trifluoromethyl) -2,2-perfluoropropylene-4,4'- Diphthalic acid dianhydride, 3,3 ', 5,5', 6,6'-Lu (trifluoromethyl) -2,2-perfluoropropylene-4,4'-diphthalic acid dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3,6, 7-tetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 9,9-bis [4- (3,4-di Carboxy) phenyl] fluorenic dianhydride, 9,9-bis [4- (2,3-dicarboxy) phenyl] fluorenic dianhydride, ethylene glycol bistrimellitic dianhydride, 1,2- (extend Ethyl) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (meta Trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7 -(Heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (ninemethylene) bis (partial Trimellitic anhydride), 1,10- (decylmethylene) bis (trimellitic anhydride), 1,12- (dodecylmethylene) bis (trimellitic anhydride), 1, 16- (hexadecanemethylene) bis (trimellitic anhydride), 1,18- (octadecylmethylene) bis (trimellitic anhydride) and the like. Examples of the tricarboxylic anhydride include trimellitic anhydride, nuclear hydrogenated trimellitic anhydride, and the like.

Examples of the amine component include diamines such as aliphatic diamines and aromatic diamines, polyvalent amines such as aliphatic polyetheramines, diamines having carboxylic acids, and diamines having phenolic hydroxyl groups. Restricted by these amines. These amine components may be used alone or in combination.

Examples of the diamine include p-phenylene diamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, and 2,6-toluene Diamine, such as a diamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether Diamino diphenyl ethers, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di Methyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4 '-Diaminodiphenylmethane, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4 , 4'-Diaminobenzidine aniline, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (o-benzidine), 2,2'-dimethylbenzidine (m-benzidine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4 , 4'-diaminodiphenyl sulfide, 3,3'- Aminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminobenzophenone, 3,3 ' -Diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenyl Methane, 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-aminophenylbenzene) ) -1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylsulfenyl, 3,4'-diaminodiphenylsulfenyl, 4,4 '-Diaminodiphenylsulfene, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2 benzene diamines, 1,3-bis (3-amine Phenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene , 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1 , 3-bis (3-aminophenoxy) -4-trifluoromethylbenzene, 3,3'-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3 '-Diamino-4,4'-bis (4- Phenylphenoxy) benzophenone, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis (4-aminophenylsulfide) benzene, 1,4-bis ( 4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylphosphonium) benzene, 1,3-bis (4-aminophenylphosphonium) benzene, 1,4-bis (4 -Aminophenylhydrazone) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl ] Benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene and other three benzene nuclei diamine, 3,3'-bis (3-aminophenoxy) Benzene, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenylbenzene Oxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-amine Phenylphenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] one, bis [4- (3-aminophenoxy) phenyl] one, bis [4- (4-aminophenoxy) phenyl] one, Bis [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] fluorene, bis [3- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) benzene Yl] fluorene, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenylbenzene Oxy) 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-amine Phenylphenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) benzene Group] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [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-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, etc. 4 aromatic benzene diamines, aromatic diamines, etc. Aminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamine Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1 Aliphatic diamines such as 1,11-diaminoundecane, 1,12-diaminododecane, and 1,2-diaminocyclohexane. Examples of aliphatic polyetheramines include ethyl Polyvalent amines such as diols and / or propylene glycols.

Examples of the amine having a carboxyl group include diaminobenzoic acids such as 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, and 3,5 -Aminophenoxybenzoic acids such as bis (3-aminophenoxy) benzoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, 3,3'-diamino-4 4,4'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, 4,4 Carboxybiphenyl compounds such as '-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-amine Methyl-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4'-diamino-2,2 ', 5,5'- Carboxydiphenylalkanes such as carboxydiphenylmethane, tetracarboxydiphenylmethane, etc., 3,3'-diamino-4,4'-dicarboxydiphenyl ethers, 4,4'-diamine -3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2,2 ', 5 , 5'- Carboxydiphenyl ether compounds such as tetracarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenylphosphonium, 4,4'-diamino-3,3'- Dicarboxydiphenylphosphonium, 4,4'-diamino-2,2'-dicarboxydiphenylphosphonium, 4,4'-diamino-2,2 ', 5,5'-tetracarboxydi Diphenylphosphonium compounds such as phenylphosphonium, and bis [(carboxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane Bis [(carboxyphenoxy) phenyl] fluorene compounds and the like, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] fluorene and the like.

As the isocyanate component, diisocyanates such as aromatic diisocyanate and its isomers or polymers, aliphatic diisocyanates, alicyclic diisocyanates and its isomers, or other commonly used diisocyanates can be used. , But not limited to those isocyanates. These isocyanate components may be used alone or in combination.

Examples of the diisocyanate include 4,4'-diphenylmethane diisocyanate, methylenephenyl diisocyanate, naphthalene diisocyanate, succinic diisocyanate, biphenyldiisocyanate, and diphenylphosphonium diisocyanate. , Diphenyl ether diisocyanate and other aromatic diisocyanates and its isomers, polymers, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate and other aliphatic diisocyanates , Or alicyclic diisocyanates and isomers of the aforementioned aromatic diisocyanates to be hydrogenated, or other commonly used diisocyanates.

(3) A carboxyl group-containing resin having a fluorene structure but not having a fluorinimine structure. A carboxyl group containing resin having a fluorene structure but not having a fluorimine structure is not particularly limited as long as it is a resin having a carboxyl group and a fluoramine bond.

As described above, the carboxyl group-containing resin suitable for use as the alkali-soluble resin of the present invention has an acid value of preferably 20 to 200 mgKOH / g, and more preferably 60 to 150 mgKOH / g in order to correspond to the photolithography step. When the acid value is 20 mgKOH / g or more, the solubility in alkali increases and the developability becomes good, and since the degree of cross-linking with the heat-hardening component after light irradiation becomes high, sufficient contrast can be obtained. On the other hand, when the acid value is 200 mgKOH / g or less, it becomes easy to draw a correct pattern, and in particular, the so-called thermal blur in the PEB (POST EXPOSURE BAKE) step after light irradiation described below can be suppressed, and the process tolerance can be made. Get bigger.

In addition, when the molecular weight of such a carboxyl group-containing resin is taken into consideration, the mass average molecular weight Mw is preferably 100,000 or less, more preferably 1,000 to 100,000, and even more preferably 2,000 to 50,000. When the molecular weight is 100,000 or less, the alkali solubility of the unexposed portion is increased and the developability is improved. On the other hand, when the molecular weight is 1,000 or more, sufficient exposure resistance and hardened properties can be obtained in the exposed portion after exposure and PEB.

(Photopolymerization initiator) As a photopolymerization initiator used in the resin layer (B), a conventionally known one can be used, and in particular, when used in a PEB step after light irradiation described later, it is preferable to have a photobase generation as well. Photopolymerization initiator function of the agent. Moreover, in this PEB step, a photopolymerization initiator and a photobase generator may be used together.

A photopolymerization initiator that also has a function as a photobase generator is a compound that changes a molecular structure by irradiation with light such as ultraviolet rays or visible light, or generates a functional function by molecular cleavage as described later. One or more basic substances that are catalysts for the polymerization reaction of thermally reactive compounds. Examples of the basic substance include a secondary amine and a tertiary amine. Examples of such a photopolymerization initiator that also has a function as a photobase generator include, for example, an α-aminoacetophenone compound, an oxime ester compound, or an oxyoxyimino group and N-formamidine Compounds such as a substituent of an aromatic amine group, an N-halide aromatic amine group, a nitrobenzylcarbamate group, an alkoxybenzylcarbamate group, and the like. Among them, oxime ester compounds and α-aminoacetophenone compounds are also preferable, and oxime ester compounds are more preferable. The α-aminoacetophenone compound is particularly preferably one having two or more nitrogen atoms.

The α-aminoacetophenone compound is only required to be an alkaline substance (amine) that has a benzoin ether bond in the molecule and causes cracking in the molecule when exposed to light to achieve a hardening catalyst action.

As the oxime ester compound, any compound that generates a basic substance upon irradiation with light can be used arbitrarily.

Such a photopolymerization initiator system may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the photopolymerization initiator in the resin composition is preferably 0.1 to 40 parts by mass, and more preferably 0.3 to 15 parts by mass, relative to 100 parts by mass of the alkali-soluble resin. In the case of 0.1 parts by mass or more, the contrast of the development resistance of the light-irradiated portion / non-irradiated portion can be well obtained. Moreover, when it is 40 mass parts or less, hardened | cured material characteristics will improve.

(Thermally Reactive Compound) As the heat-reactive compound, known and commonly used compounds having a functional group capable of curing reaction by heat such as a cyclic (thio) ether group, such as an epoxy compound, can be used. Examples of the epoxy compound include bisphenol A epoxy resin, brominated epoxy resin, phenolic epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, and propylene oxide. Amine-type epoxy resin, hydantoin-type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane-type epoxy resin, biphenol-type or biphenol-type epoxy resin, or a mixture thereof; Bisphenol S epoxy resin, bisphenol A phenolic epoxy resin, tetraphenol based ethane epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraepoxy Propylxylylene ethane resin, naphthyl-containing epoxy resin, epoxy resin with dicyclopentadiene skeleton, epoxy propyl methacrylate copolymer epoxy resin, cyclohexyl malein Copolymerized epoxy resin of imine and epoxy methacrylate, CTBN modified epoxy resin, etc.

The blending amount of the thermally reactive compound is preferably 1: 0.1 to 1:10 in an equivalent ratio with an alkali-soluble resin (alkali-soluble group such as carboxyl group: thermally reactive group such as epoxy group). By making the range of such a blending ratio, development becomes good, and it becomes a person who can form a fine pattern easily. The above equivalent ratio is preferably 1: 0.2 ~ 1: 5.

(Block copolymers) In order to achieve a good balance of the bendability up to now, especially excellent crack resistance against excessive folding, and excellent heat resistance, the block copolymer is included in the resin layer constituting the laminated structure of the present invention. (B) The most characteristic component. As this block copolymer, it generally means a copolymer of two or more kinds of polymer with different properties that are linked by a covalent bond to form a long-chain molecular structure. In the present invention, known blockers can be used as the block copolymer. X-Y or X-Y-X block copolymers are preferred, and X-Y-X block copolymers are preferred. X in the X-Y-X block copolymer may be the same or different.

Among X-Y or X-Y-X block copolymers, X is preferably a polymer unit having a glass transition temperature Tg of 0 ° C or higher. Preferably, X is a polymer unit having a glass transition temperature Tg of 50 ° C or higher. In addition, Y is preferably a polymer unit having a glass transition temperature Tg of less than 0 ° C, and more preferably a polymer unit having a glass transition temperature Tg of -20 ° C or lower. The glass transition temperature Tg can be measured by differential scanning calorimetry (DSC).

The block copolymer is more preferably a solid at 20-30 ° C. In this case, as long as it is a solid in this range, it may be a solid at a temperature outside this range. By being solid in the above-mentioned temperature range, it becomes excellent in tackiness after being dried into a film or after being temporarily dried after being applied to a substrate.

Among the X-Y-X type block copolymers, X is preferably one having a high compatibility with a thermally reactive compound, and Y is preferably one having a low compatibility with a thermally reactive compound. Therefore, it is considered that by forming a block phase in which the block phases at both ends are dissolved in the matrix, and the block copolymer in the center is incompatible with the matrix, the specific structure becomes easy to appear in the matrix.

As the polymer unit X, polymethyl methacrylate (PMMA), polystyrene (PS), etc. are preferred, and as the polymer unit Y, poly n-butyl (meth) acrylate (PBA), Polybutadiene (PB) and the like are preferred. In addition, a part of the polymer unit X is introduced with hydrophilicity such as styrene units, hydroxyl-containing units, carboxyl-containing units, epoxy-containing units, N-substituted acrylamide units, and the like, which have excellent compatibility with alkali-soluble resins. Sexual unit, it can become more compatible. It is particularly preferable to introduce an epoxy group-containing unit into a part of the polymer unit X. Among the above, the polymer unit X is also substituted with polystyrene, polyglycidyl methacrylate, or N for polypropylene amidamine, polymeth (meth) acrylate, or a carboxylic acid modified product or hydrophilic group thereof. Denaturants are preferred. The Y system is preferably a poly-n-butyl (meth) acrylate, polybutadiene, or the like. X and Y may be each composed of one type of polymer unit, or may be composed of two or more types of polymer units.

Examples of the method for producing the block copolymer include the methods described in Japanese Patent Application No. 2005-515281 and Japanese Patent Application No. 2007-516326.

Examples of commercially available X-Y-X type block copolymers include propylene fluorene-based triblock copolymers produced by living polymerization produced by Arkema Corporation. As this specific example, an XXY-type block copolymer (e.g., M51, M52, M53, M22) represented by polymethylmethacrylate-polybutylacrylate-polymethmethacrylate is exemplified. Etc.), and XXY-type block copolymers (for example, SM4032XM10, etc.) denatured with carboxylic acids, or XXY-type block copolymers (for example, M52N, M22N, M65N, etc.) that have been denatured with hydrophilic groups.

The mass average molecular weight (Mw) of the block copolymer is usually 20,000 to 400,000, and preferably a range of 30,000 to 300,000. The molecular weight distribution (Mw / Mn) is preferably 3 or less.

When the mass average molecular weight is 20,000 or more, it has mechanical properties such as softness and elasticity of the composition, and the adhesiveness does not become too high. The effect of improving the bending and crack resistance becomes good, and the viscosity also becomes good. On the other hand, when the mass average molecular weight is 400,000 or less, the viscosity of the composition does not become high, and printability and developability are not easily reduced.

The block copolymer may be used singly or in combination of two or more kinds. The blending amount of the block copolymer is preferably 1 to 60 parts by mass relative to 100 parts by mass of the alkali-soluble resin, more preferably 2 to 50 parts by mass, and particularly preferably 3 to 40 parts by mass. When the blending amount of the block copolymer is 1 part by mass or more, flexibility and heat resistance are improved, and when it is 60 parts by mass or less, the balance of flexibility and heat resistance becomes good.

To the resin composition used in the resin layer (A) and the resin layer (B) as described above, the following components can be blended as necessary.

(Polymer Resin) The polymer resin is used for improving the flexibility and touch-drying property of the obtained hardened product, and it can be used in combination with the well-known and conventional ones other than the above-mentioned block copolymer. Examples of such polymer resins include cellulose-based, polyester-based, phenoxy resin-based polymers, polyvinyl acetal-based, polyvinyl butyral-based, polyamide-based, and polyamide-based Amine-based adhesive polymers, elastomers, etc. This polymer resin can be used alone or in combination of two or more.

(Inorganic Filler) Inorganic fillers can be blended in order to suppress the hardening shrinkage of the cured product and improve the properties such as adhesion and hardness. Examples of such inorganic fillers include barium sulfate, amorphous silica, fused silica, spherical silica, talc, white clay, magnesium carbonate, calcium carbonate, acidified aluminum, aluminum hydroxide, and nitrogen. Silicon, aluminum nitride, boron nitride, Neuburg Silicious earth, etc.

(Colorant) As a colorant, well-known and commonly used coloring agents such as red, blue, green, yellow, white, and black can be blended, and any of pigments, dyes, and pigments can be used.

(Organic Solvent) 溶剂 Organic solvents are those that can be blended in order to prepare a resin composition, or to coat a substrate or a carrier film to adjust viscosity. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. Such an organic solvent may be used singly or as a mixture of two or more kinds.

(Other components) If necessary, components such as a mercapto compound, an adhesion promoter, an antioxidant, and an ultraviolet absorber may be blended. These systems may use well-known customaries. In addition, it can be used with well-known and commonly used thickeners such as micronized silica, hydrotalcite, organic bentonite, montmorillonite, etc., such as polysiloxane-based, fluorine-based, polymer-based defoamers and / or leveling agents. Additives, silane coupling agents, rust inhibitors, and other commonly used additives.

Since the laminated structure of the present invention is excellent in flexibility, it can be used in at least one of a bent portion and a non-bent portion of a flexible printed wiring board, and can also be used as a covering for a flexible printed wiring board. Use at least one of a layer, a solder resist, and an interlayer insulating material.

The laminated structure of the present invention configured as described above is preferably used as a dry film having at least one side supported or protected by the film.

(Dry film) The dry film of the present invention can be produced, for example, by the following operations. That is, first, on a carrier film (supporting film), the composition constituting the resin layer (B) and the composition constituting the resin layer (A) are diluted with an organic solvent to adjust the viscosity to an appropriate viscosity. A known method such as a comma coater is applied sequentially. Thereafter, a dry film composed of the resin layer (B) and the resin layer (A) can be formed on the carrier film by generally drying at a temperature of 50 to 130 ° C for 1 to 30 minutes. A cover film (protective film) that can be peeled off can be further laminated on the dry film for the purpose of preventing dust from adhering to the surface of the film. As the carrier film and the cover film, a conventionally known plastic film can be suitably used. For the cover film, when the cover film is peeled off, the adhesive force between the resin layer and the carrier film is small. The thickness of the carrier film and the cover film is not particularly limited, and is generally appropriately selected within a range of 10 to 150 μm.

(Flexible printed wiring board) The flexible printed wiring board of the present invention is a layer having a laminated structure of the present invention formed on a flexible printed wiring substrate, and is patterned by light irradiation. The insulating film formed by patterning in the image liquid at one time.

(Manufacturing method of wiring board) The manufacturing of a flexible printed wiring board using the laminated structure of the present invention can be performed in accordance with the operation sequence shown in the step diagram of FIG. 1. That is, the manufacturing method includes a step of forming a layer of the laminated structure of the present invention (a lamination step) on a flexible wiring substrate on which a conductor circuit has been formed, and activating energy rays on the layer of the laminated structure. A step of irradiating a pattern (exposure step), and a step of developing a layer of the patterned layered structure in one step (imaging step) by subjecting the layer of the layered structure to alkali development. Further, if necessary, after the alkali development, further photo-hardening or thermal hardening (post-curing step) is performed to completely harden the layer of the laminated structure, and a highly reliable flexible printed wiring board can be obtained.

Moreover, the manufacturing of the flexible printed wiring board using the laminated structure of this invention can also be performed using the operation sequence shown in the step diagram of FIG. That is, the manufacturing method includes a step of forming a layer of the laminated structure of the present invention (a lamination step) on a flexible wiring substrate on which a conductor circuit has been formed, and activating energy rays on the layer of the laminated structure. A step of irradiating a pattern (exposure step), a step of heating a layer of the laminated structure (heating (PEB) step), and an alkali development of the layer of the laminated structure to form a warp pattern at one time The step of forming a layer of the structure (the developing step). Further, if necessary, after the alkali development, further light hardening or heat hardening (post-hardening step) is performed to completely harden the layer of the laminated structure, and a highly reliable flexible printed wiring board can be obtained. In particular, in the case of using a carboxyl group-containing resin having at least one of a fluorene imine structure and a fluorene structure in the resin layer (B), the operation sequence shown in the step diagram of FIG. 2 is preferably used.

Hereinafter, each step shown in FIG. 1 or FIG. 2 will be described in detail. [Lamination Step] In this step, a laminated structure is formed on the flexible printed wiring base material 1 of the conductor circuit 2. The laminated structure is formed of a resin layer 3 (resin layer (A)), and The resin layer 4 (resin layer (B)) is formed on the resin layer 3. The resin layer 3 is composed of an alkali-developing resin composition containing an alkali-soluble resin and the like. The resin layer 4 is composed of an alkali-containing resin. It consists of a photosensitive thermosetting resin composition, such as a soluble resin. Here, each of the resin layers constituting the laminated structure can be formed by, for example, sequentially applying the resin composition constituting the resin layers 3 and 4 to the wiring substrate 1 and drying the resin layers 3 and 4, or, It can be formed by laminating the resin composition constituting the resin layers 3 and 4 to the wiring substrate 1 in a dry film form having a two-layer structure.

The coating method for applying the resin composition to the wiring substrate may be a known method such as a blade coater, a lip coater, a comma coater, a film coater, and the like. In addition, the drying method is a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, etc., and a heat source having a heating method formed by steam. The method can be a method of contacting the hot air in the dryer countercurrently and using a nozzle Well-known methods, such as the method of blowing on a support body.

As a method of laminating a resin composition on a wiring substrate, it is preferable to perform lamination under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, even if the surface of the wiring substrate has unevenness, the dry film is closely adhered to the wiring substrate, so that air bubbles are not mixed, and the buried hole of the recessed portion on the surface of the wiring substrate is improved. . The pressing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120 ° C.

[Exposure Step] This step is to activate the photopolymerization initiator contained in the resin layer 4 into a negative pattern shape by irradiating active energy rays, and then harden the exposed portion. In the case of using a composition described later in the PEB step, a photopolymerization initiator or a photobase generator having a function as a photobase generator is activated into a negative pattern to generate alkali. As the exposure machine used in this step, a direct drawing device, an exposure machine equipped with a metal halide lamp, and the like can be used. The pattern-shaped exposure mask is a negative mask.

As the active energy ray used for exposure, it is preferable to use laser light or scattered light having a maximum wavelength in a range of 350 to 450 nm. By setting the maximum wavelength in this range, the photopolymerization initiator can be efficiently activated. The exposure amount varies depending on the film thickness, etc., but it is usually 100 to 1500 mJ / cm ² .

[PEB step] This step is to harden the exposed portion by heating the resin layer after exposure. With this step, an exposure step using a photopolymerization initiator having a function as a photobase generator or a resin layer (B) composed of a combination of a photopolymerization initiator and a photobase generator is used. The alkali generated in the resin can harden the resin layer (B) to a deep part. The heating temperature is, for example, 80 to 140 ° C. The heating time is, for example, 10 to 100 minutes. Since the hardening of the resin composition of the present invention is, for example, a ring-opening reaction of an epoxy resin due to a thermal reaction, it is possible to suppress distortion and hardening shrinkage compared to a case where hardening is caused by a photoradical reaction.

[Development step] This step is to remove the unexposed parts by alkali development to form a negative patterned insulating film, especially to form a coating layer and a solder resist. As a developing method, a known method such as dipping can be used. Further, as the developing solution, an aqueous alkali solution such as sodium carbonate, potassium carbonate, potassium hydroxide, amines, imidazoles such as 2-methylimidazole, tetramethylammonium hydroxide aqueous solution (TMAH), or the like can be used. And so on.

[Post-curing step] (1) This step is performed after the developing step, and the insulating film is completely thermally cured to obtain a highly reliable coating film. The heating temperature is, for example, 120 ° C to 180 ° C. The heating time is, for example, 5 minutes to 120 minutes. In addition, light irradiation may be applied to the insulating film before or after the post-hardening. [Example]

Hereinafter, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited by these examples and comparative examples.

<Synthesis example 1: Synthesis example of polyfluorene imine resin solution> 3Add a 3,3'-diamine-4,4 'to a detachable three-necked flask equipped with a stirrer, a nitrogen introduction tube, a fractionation ring, and a cooling ring. -22.4g of dihydroxydiphenylphosphonium, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane 8.2g, NMP 30g, γ-butyrolactone 30g, 4,4'- 27.9 g of oxydiphthalic anhydride and 3.8 g of trimellitic anhydride were stirred at 100 rpm for 4 hours at room temperature under a nitrogen environment. Next, 20 g of toluene was added, and toluene and water were distilled off at a silicon bath temperature of 180 ° C. and 150 rpm while stirring for 4 hours to obtain a polyimide resin solution (PI-1) having a phenolic hydroxyl group and a carboxyl group. The obtained resin (solid content) had an acid value of 18 mgKOH, a Mw of 10,000, and a hydroxyl equivalent of 390.

(Examples 1 to 6 and Comparative Examples 1 to 4) According to the component composition described in Tables 1 and 2, individually mix the materials described in Examples 1 to 6 and Comparative Examples 1 to 4, and premix them in a blender, then use 3 The roll mill is kneaded to prepare a resin composition that forms each resin layer. Where 値 in the table is not specifically defined, it is the mass part of solid content.

<Formation of Resin Layer (A)> A flexible printed wiring substrate having a copper thickness of 18 μm is prepared, and a pretreatment is performed using MEC CZ-8100. Thereafter, the resin composition constituting each resin layer (A) obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was applied to the flexibility of the pretreatment so that the film thickness after drying became 25 μm. Printed wiring substrate. Thereafter, the resin layer (A) was formed by drying in a hot-air circulation-type drying furnace at 90 ° C./30 minutes.

<Formation of Resin Layer (B)> (1) The resin composition constituting each resin layer (B) obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was applied to the above-mentioned layer so that the film thickness after drying became 10 μm. On the formed resin layer (A). Thereafter, the resin layer (B) was formed by drying in a hot-air circulation-type drying furnace at 90 ° C./30 minutes.

With this operation, an unhardened laminated structure composed of the resin layer (A) and the resin layer (B) described in Examples 1 to 6 and Comparative Examples 1 to 4 was formed on a flexible printed wiring substrate.

<Bendability> (Production of test piece) For an unhardened laminated structure on each flexible printed wiring substrate having the laminated structure formed by the above operation, an exposure apparatus equipped with a metal halide lamp was first used. (HMW-680-GW20), with full exposure at 500mJ / cm ² through a negative mask. Thereafter, the PEB step was performed at 90 ° C for 30 minutes, and then developed (30 ° C, 0.2MPa, 1% by mass Na ₂ CO ₃ aqueous solution) for 60 seconds, and then heat-cured at 150 ° C for 60 minutes to produce A flexible printed wiring board having a cured laminated structure. And this flexible printed wiring board was cut into about 15 mm x about 110 mm, and the test piece was produced.

(MIT test) Each obtained test piece was subjected to a MIT test in accordance with JIS P8115 using a MIT flex fatigue tester type D (manufactured by Toyo Seiki Seisakusho), and evaluated for bendability. Specifically, as shown in FIG. 3, the test piece 10 is mounted on the device, and the test piece 10 is vertically mounted on the holder 11 with a load F (0.5 kgf), and the bending angle α is 135. Bending was performed at a speed of 175 cpm, and the number of round trip bendings (times) until rupture was measured. The test environment was 25 ° C. The evaluation criteria are as follows. ◎: The hardened coating film at the bending place was not cracked more than 200 times. 〇: Bend 170 to 199 times without cracking. △: Bend 150 to 169 times without cracking. ×: The number of bends is 149 or less but cracks appear.

(Folding test) (1) Further, the bendability when each of the obtained test pieces was subjected to a folding test under the severe conditions shown below was evaluated. Specifically, as shown in FIG. 4, the applied load was sandwiched between two flat plates 12 in a state where the conductor circuit of the test piece 10 and the formation surface X of the cured coating film were made to be outside, and were bent to 180 °. G (1 kg of standard copper) was folded for 10 seconds, and then the operation of confirming whether cracks were generated on the hardened coating film portion 20 at the bending place using an optical microscope was regarded as one cycle, and the number of times before cracks occurred was recorded. The test environment was 25 ° C. The evaluation criteria are as follows. ◎: Bending was performed more than 10 times, and the hardened coating film at the bending place did not crack. 〇: Bend 6 to 9 times without cracking. △: Bending 3 to 5 times without cracking. ×: Cracking occurs when the number of bending is less than 2 times.合并 These evaluation results are combined and shown in Tables 1 and 2.

<Heat resistance> For an unhardened laminated structure on each flexible printed wiring substrate having the laminated structure formed by the above operation, an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp is first used. ), And exposed at 500 mJ / cm ² through a negative mask with an opening of about 2 mm to 5 mm in diameter formed on the copper. After that, the PEB step was performed at 90 ° C for 30 minutes, and then developed (30 ° C, 0.2MPa, 1% by mass Na ₂ CO ₃ aqueous solution) for 60 seconds, and then heat-cured at 150 ° C for 60 minutes to prepare A flexible printed wiring board (test substrate) having a cured laminated structure formed.

A rosin-based flux was applied to this test substrate, and it was immersed in a solder bath set to 260 ° C and 280 ° C in advance, and the occurrence of floating, swelling, and peeling of the cured coating film was evaluated. The evaluation criteria are as follows. ◎: Floating, swelling and peeling did not occur in any of the immersion at 260 ° C and 280 ° C. 〇: Although floating, swelling and peeling did not occur during immersion at 260 ° C, floating, swelling and peeling occurred during immersion at 280 ° C. ×: Floating and peeling occurred in any of immersion at 260 ° C and 280 ° C.合并 The evaluation results are combined and shown in Tables 1 and 2.

<Resolution> For the uncured laminated structure on each flexible printed wiring substrate on which the laminated structure is formed by the above operation, an exposure device (HMW-680-GW20) equipped with a metal halide lamp is first used. ), Through a negative mask, pattern exposure was performed at 500 mJ / cm ² and a 200 μm diameter opening was formed. Thereafter, after performing the PEB step at 90 ° C for 30 minutes, the pattern was drawn by performing development (30 ° C, 0.2MPa, 1% by mass Na ₂ CO ₃ aqueous solution) for 60 seconds, and heat was applied at 150 ° C × 60 minutes. It is hardened to form a flexible printed wiring board having a hardened laminated structure having an opening. The opening formed in the laminated structure of the obtained flexible printed wiring board was observed using an optical microscope adjusted 100 times, and the resolution was evaluated. The evaluation criteria are as follows. 〇: The opening is fully formed. ×: The opening was not formed. The evaluation results are combined and shown in Table 1 and Table 2.

＊ 1) Alkali-soluble resin 1: ZAR-1035: acid-denatured bisphenol A epoxy acrylate, acid value 98mgKOH / g (manufactured by Nippon Kayaku Co., Ltd.) * 2) polyimide resin: PI-1 : Synthesis Example 1 * 3) Photocurable monomer: BPE-500: ethoxylated bisphenol A dimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) * 4) epoxy resin: E828: bisphenol A Type epoxy resin, epoxy equivalent 190, mass average molecular weight 380 (manufactured by Mitsubishi Chemical Corporation) * 5) photopolymerization initiator: IRGACURE OXE02: oxime-based photopolymerization initiator (manufactured by BASF) * 6) Segment copolymer 1: M52N: XYX block copolymer having a mass average molecular weight (Mw) of about 100,000, manufactured by Arkema, NANOSTRENGTH (registered trademark) * 7) block copolymer 2: M65N: XXY block copolymer The weight-average molecular weight (Mw) is about 100,000 to 300,000, manufactured by Arkema, NANOSTRENGTH (registered trademark) * 8) alkali-soluble resin 2: P7-532: polyurethane acrylate, acid value 47mgKOH / g ( (Kyoeisha Chemical Co., Ltd.)

From the evaluation results shown in the above table, it is clear that in the laminated structure of each example, the resin layer (B) on the upper layer side contains the block copolymer, and the flexibility, heat resistance, and resolution Either of them can achieve excellent performance. On the other hand, in Comparative Examples 1 and 2 having a single-layer structure, the bendability, particularly the excellent crack resistance with excessive folding, is not sufficient. Even in the case of a laminated structure that does not contain a block copolymer, In Comparative Example 3, although good results were obtained in terms of heat resistance, the bendability, particularly the excellent crack resistance against excessive folding, was insufficient. In Comparative Example 4 in which only the resin layer (A) on the lower layer side of the laminated structure contained a block copolymer, good results were obtained in terms of heat resistance, but especially for the bendability, it was particularly excessively reduced. Excellent crack resistance and resolution are not sufficient. As described above, in the laminated structure obtained by laminating two resin layers, the photosensitive resin composition itself capable of maintaining resolution and the like can be maintained by including a block copolymer in the upper resin layer (B). Characteristics, and can improve the bending resistance, especially the excellent crack resistance and heat resistance to excessive folding.

1‧‧‧ Flexible printed wiring substrate

2‧‧‧ conductor circuit

3‧‧‧ resin layer

4‧‧‧ resin layer

5‧‧‧Mask

10‧‧‧ Test Strip

11‧‧‧ Fixture

12‧‧‧ tablet

20‧‧‧hardened coating

X‧‧‧Conductor circuit and forming surface of hardened coating film

[Fig. 1] A schematic diagram showing an example of a method for manufacturing a flexible printed wiring board of the present invention. [Fig. 2] A diagram schematically showing the steps of another example of the method for manufacturing a flexible printed wiring board of the present invention. [Fig. 3] A schematic explanatory diagram showing the MIT test of the example. [Fig. 4] A schematic explanatory diagram showing a folding test of an example.

Claims (9)

A laminated structure comprising: a resin layer (A); and a resin layer (B) laminated on a flexible printed wiring board with the resin layer (A) interposed therebetween; the aforementioned resin layer (B) It consists of a photosensitive thermosetting resin composition containing an alkali-soluble resin, a photopolymerization initiator, a thermally reactive compound, and a block copolymer, and the resin layer (A) is made of an alkali-soluble resin And thermally-reactive compound consisting of an alkali-developing resin composition. The laminated structure according to claim 1, wherein the aforementioned block copolymer has a structure represented by the following formula (I); XYX (I) In formula (I), X is a polymerization having a glass transition temperature Tg of 0 ° C or higher The physical units may be the same or different, and Y is a polymer unit whose glass transition temperature Tg is less than 0 ° C. For example, the laminated structure of claim 1 or 2, wherein the mass average molecular weight (Mw) of the aforementioned block copolymer is 20,000 to 400,000. The laminated structure according to any one of claims 1 to 3, which contains a photobase generator as the photopolymerization initiator of the resin layer (B). The laminated structure according to any one of claims 1 to 4, wherein the resin layer (A) is composed of an alkali-developing resin composition containing no photopolymerization initiator. The laminated structure according to any one of claims 1 to 5 is used in at least one of a bent portion and a non-bent portion of a flexible printed wiring board. The laminated structure according to any one of claims 1 to 6, which is used for at least any one of a coverlay, a solder resist, and an interlayer insulating material of a flexible printed wiring board. A dry film, characterized in that at least one side of the laminated structure according to any one of claims 1 to 7 is supported or protected by a film. A flexible printed wiring board characterized by having an insulating film using a laminated structure according to any one of claims 1 to 7.