KR102277203B1 - Photosensitive thermosetting resin composition and flexible printed circuit board - Google Patents

Abstract

The present invention provides a photosensitive thermosetting resin composition that is excellent in reliability such as impact resistance and flexibility, processing precision, and workability, and is suitable for the batch formation process of an insulating film of a flexible printed wiring board, particularly a bent part (bent part) and a mounting part (non-bend part). to provide. The present invention is a photosensitive thermosetting resin composition comprising an alkali-soluble resin having an imide ring, an alkali-soluble resin other than the alkali-soluble resin having an imide ring, a photobase generator, and a thermosetting component. It is preferable that the other alkali-soluble resin of this invention has any 1 or more types of a urethane bond, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, and a biphenyl skeleton in a structure.

Description

A photosensitive thermosetting resin composition and a flexible printed wiring board TECHNICAL FIELD

The present invention relates to a photosensitive thermosetting resin composition and a flexible printed wiring board, and more particularly, it can develop with alkali, has excellent heat resistance and flexibility, and is easy to manage temperature and time during heat curing after light irradiation It is related with the flexible printed wiring board provided with the photosensitive thermosetting resin composition and the hardened|cured material of the said photosensitive thermosetting resin composition.

In recent years, the spread of smart phones or tablet terminals and the improvement of performance are progressing rapidly. The information equipment terminals represented by these have high consumer demands for downsizing and thinning, and in order to meet the demands, high density and space saving of circuit boards inside products are required. Therefore, the use of the flexible printed wiring board which can be bent and accommodated and which can raise the freedom degree of circuit arrangement is expanding, and it is calculated|required that the reliability with respect to a flexible printed wiring board is also much higher.

Currently, as an insulating film for securing insulation reliability of flexible printed wiring boards, a polyimide-based coverlay is used for the bent portion (bent portion), and a mixed process using a photosensitive resin composition is widely used for the mounting portion (non-bend portion). It has been adopted (refer to Patent Documents 1 and 2). Polyimide is excellent in mechanical properties such as heat resistance and flexibility, and on the other hand, the photosensitive resin composition used for the mounting part is excellent in electrical insulation, solder heat resistance, etc., and has a characteristic that microfabrication is possible.

In the conventional coverlay based on polyimide, since processing by die punching is required, it is unsuitable for fine wiring. Therefore, using together the photosensitive resin composition (solder resist) of the alkali development type in which the process by photolithography is possible is performed for the chip mounting part which requires fine wiring partially. In the case of partial use of such a resin composition in the manufacture of a flexible printed wiring board, there was a problem that the cost and workability were inferior by passing through two steps of a step of bonding a coverlay and a step of forming a solder resist. .

Japanese Patent Laid-Open No. 62-263692 Japanese Patent Laid-Open No. 63-110224

Therefore, conventionally, examination of the insulating film of the flexible printed wiring board which does not follow a mixed process is made|formed. For example, although applying the photosensitive resin composition for soldering resists as a coverlay of a flexible printed wiring board is examined, with the resin composition for soldering resists, reliability, such as impact resistance and flexibility as a coverlay, is inadequate. In the resin composition for soldering resists, since cure shrinkage by acrylic photopolymerization was also accompanied, there existed a subject also in dimensional stability, such as curvature of a flexible wiring board.

In addition, as a photosensitive polyimide compatible with alkali solubility and mechanical properties, a method of thermal ring closure after patterning using a polyimide precursor has been proposed, but there was a problem in workability such as requiring high-temperature treatment.

Therefore, it is an object of the present invention to have excellent reliability, processing precision, and workability such as impact resistance and flexibility, and photosensitivity suitable for the batch formation process of an insulating film of a flexible printed wiring board, in particular, a bent portion (bent portion) and a mounting portion (non-bend portion) To provide a thermosetting resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the resin composition containing alkali-soluble resin which has an imide ring, a photobase generator, and a thermosetting component could solve the said subject, as a result of earnestly examining in order to solve the said subject.

That is, the photobase generator is activated by light irradiation, and the alkali-soluble resin and thermosetting component having an imide ring are reacted with an alkali-soluble resin having an imide ring using the generated base as a catalyst, and only the unexposed portion is removed with an alkali solution. was found to be possible. Thereby, while microfabrication by alkali development is attained, it is expectable to obtain the hardened|cured material excellent in reliability.

On the other hand, in the heat curing reaction after light irradiation, if the width of heating temperature and heating time can be widened, since it becomes a resin composition excellent in workability, the present inventors found the following as a result of further studies Thus, the present invention was completed. That is, by setting the photosensitive thermosetting resin composition comprising an alkali-soluble resin having an imide ring, a photobase generator, and a thermosetting component, and an alkali-soluble resin other than an alkali-soluble resin having an imide ring, in addition to the above properties, more A photosensitive thermosetting resin composition excellent in workability can be obtained.

The present invention is the following [1] to [7].

[1] A photosensitive thermosetting resin composition comprising an alkali-soluble resin having an imide ring, an alkali-soluble resin other than the alkali-soluble resin having an imide ring, a photobase generator, and a thermosetting component.

[2] The photosensitive thermosetting resin composition of [1], wherein the other alkali-soluble resin has any one or more of a urethane bond, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, and a biphenyl skeleton in the structure.

[3] The photosensitive thermosetting resin composition according to [1] or [2], wherein the content of the other alkali-soluble resin is 10 to 70 parts by mass based on 100 parts by mass of the alkali-soluble resin having an imide ring.

[4] The photosensitive thermosetting resin composition according to any one of [1] to [3], wherein the thermosetting component is a compound having at least one of a cyclic ether group and a cyclic thioether group.

[5] A dry film formed by coating and drying the photosensitive thermosetting resin composition according to any one of [1] to [4].

[6] A cured coating film obtained by curing the photosensitive thermosetting resin composition according to any one of [1] to [4] or a dry film formed by coating and drying the composition.

[7] A printed wiring board having a cured coating film obtained by curing the photosensitive thermosetting resin composition according to any one of [1] to [4] or a dry film formed by coating and drying the composition.

According to the present invention, a photosensitive thermosetting resin composition capable of developing with alkali, excellent in heat resistance and flexibility, and easy temperature and time management during heat curing after light irradiation, and water containing the photosensitive thermosetting resin composition It becomes possible to provide the dry film which has a paper layer, and the flexible printed wiring board provided with the hardened|cured material of the said photosensitive thermosetting resin composition. The photosensitive thermosetting resin composition of this invention is suitable for the insulating film of a flexible printed wiring board, especially the batch formation process of a bending part (bending part) and a mounting part (non-bending part).

BRIEF DESCRIPTION OF THE DRAWINGS It is a process diagram which shows typically an example of the manufacturing method of the flexible printed wiring board of this invention.
2 is a DSC chart showing the results of Reference Examples 3 and 6.

The photosensitive thermosetting resin composition of this invention contains alkali-soluble resin which has an imide ring, another alkali-soluble resin, a photobase generator, and a thermosetting component, It is characterized by the above-mentioned.

The photosensitive thermosetting resin composition of the present invention uses a base generated from a photobase generator as a catalyst, and an alkali-soluble resin having an imide ring and a thermosetting component are subjected to an addition reaction by heating after exposure, and the unexposed portion is treated with an alkali solution. It is a resin composition from which image development becomes possible by removing by

As will be described later, alkali-soluble resins other than alkali-soluble resins having an imide ring, particularly alkali-soluble resins having at least one of a urethane bond, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, and a biphenyl skeleton exist If it does, compared with the case where it does not exist, at the time of the heat-hardening reaction after exposure (at the time of the following PEB process), the time until alkali resistance by addition reaction under the same heating temperature can be lengthened. In addition, it is possible to broaden the selection range of the heating temperature during the heat curing reaction (in the PEB process below). In this regard, the workability and handleability of the resin composition are improved. Generation|occurrence|production of the so-called cloudiness from which an unexposed part becomes alkali resistance can also be suppressed.

The photosensitive thermosetting resin composition of this invention is suitable for the resin insulating layer of a flexible printed wiring board, for example, a coverlay, and a soldering resist.

When forming the resin insulating layer of a flexible printed wiring board using the photosensitive thermosetting resin composition of this invention, a suitable manufacturing method becomes as follows. That is, a step of forming a resin layer containing the photosensitive thermosetting resin composition of the present invention on a flexible printed wiring board, a step of irradiating the resin layer with light in a pattern, a step of heating the resin layer (Post Exposure Bake) ; PEB), and alkali development of the resin layer to form a resin insulating layer having a pattern. If necessary, after alkali development, further light irradiation or heat curing (post-curing) is performed, the resin composition is completely cured, and a highly reliable resin insulating layer is obtained.

As described above, in the photosensitive thermosetting resin composition of the present invention, suitably, a carboxyl group and a thermosetting component are addition-reacted by heat treatment after selective light irradiation, whereby negative pattern formation by alkali development is possible.

Since the obtained cured product is excellent in heat resistance and flexibility and can be fine-processed by alkali development, it is not necessary to partially use an alkali-developable photosensitive resin composition with respect to polyimide, and the bent part of a flexible printed wiring board It can be used in both (bent part) and mounting part (non-bend part), so it is suitable for the batch forming process of bent part (bend part) and mounting part (non-bend part).

Hereinafter, each component is demonstrated in detail.

[Alkali-soluble resin having an imide ring]

In this invention, alkali-soluble resin which has an imide ring has alkali-soluble groups, such as a carboxyl group and an acid anhydride group, and an imide ring, and is resin soluble in an alkali solution in an uncured state.

It is preferable that alkali-soluble resin which has an imide ring has a partial structure represented by following formula (1) as an imide ring. In formula (1), it is preferable that R contains an aromatic ring.

It is more preferable that the partial structure represented by said Formula (1) is a thing represented by following formula (2) or (3).

The position of the carboxyl group is not particularly limited. A carboxyl group may exist as a substituent of the said imide ring or group couple|bonded with it, and a carboxyl group may be introduce|transduced into polyimide resin by synthesize|combining using what has a carboxyl group as an amine component or an isocyanate component.

A well-known and usual method can be used for the synthesis|combination of the alkali-soluble resin which has an imide ring. For example, resin obtained by making a carboxylic anhydride component, an amine component, and/or an isocyanate component react is mentioned. Imidization may be performed by thermal imidization, may be performed by chemical imidation, and may be manufactured using these together.

Examples of the carboxylic acid anhydride component include tetracarboxylic anhydride and tricarboxylic acid anhydride, but it is not limited to these acid anhydrides, and if it is a compound having an acid anhydride group and a carboxyl group that react with an amino group or an isocyanate group, it It can be used by including a derivative. In addition, these carboxylic acid anhydride components may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the tetracarboxylic anhydride include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, and 3,6-bis(trifluoromethyl). Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-ox Cydiphthalic 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(trifluoromethyl) Rhomethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5'-tetrakis(trifluoromethyl)-3,3',4,4 '-biphenyltetracarboxylic dianhydride, 2,2',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5 ,5',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride and 2,2',5,5',6,6 '-Hexakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3" ,4,4"-Terphenyltetracarboxylic dianhydride, 3,3'",4,4'"-Quarterphenyltetracarboxylic dianhydride, 3,3"",4,4""-quinquiphenyl Tetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-di Phthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-di phthalic 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 dianhydride, 1,1 ,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3-hexafluoro-1,3-trimethylene-4, 4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,1,2 ,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl -4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis(3,4- Dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3) ,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy) Phenyl]methane dianhydride, 2,2-bis[3-(3,4-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)- 1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4 ,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2 ,3,4-Butanetetracarboxylic dianhydride, 1,2,3,4-cyclo Butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid Dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene- 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2 -dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-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 Water, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 3,3'-difluorooxy-4,4'-diphthalic dianhydride, 5,5 '-difluorooxy-4,4'-diphthalic dianhydride, 6,6'-difluorooxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6 '-hexafluorooxy-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoro Rhomethyl)oxy-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5,5'-tetra Kis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5 ,5',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoro methyl)oxy-4,4'-diphthalic dianhydride, 3,3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4' -diphthalic dianhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic dianhydride, 3,3', 5,5',6,6'-hexafluorosulfonyl-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride , 5,5'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride , 3,3',5,5'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl) Sulfonyl-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',5 ,5',6,6'-hexakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3'-difluoro-2,2-perfluoropropylidene-4 ,4'-diphthalic dianhydride, 5,5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2 -Perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluoro-2,2-perfluoropropylidene-4,4' -diphthalic dianhydride, 3,3'-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl) )-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride , 3,3',5,5'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',6,6'- tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-2, 2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)-2,2-perfluoropropyl Liden-4,4'-diphthalic dianhydride, 9-phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis(trifluoro) Rhomethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracar Acid dianhydride, 9,9-bis[4-(3,4-dicarboxy)phenyl]fluorene dianhydride, 9,9-bis[4-(2,3-dicarboxy)phenyl]fluorene dianhydride , Ethylene glycol bistrimellitate dianhydride, 1,2-(ethylene)bis(trimellitate anhydride), 1,3-(trimethylene)bis(trimellitate anhydride), 1,4-(tetramethylene)bis (trimellitate anhydride), 1,5-(pentamethylene)bis(trimellitate anhydride), 1,6-(hexamethylene)bis(trimellitate anhydride), 1,7-(heptamethylene)bis(tri melitate anhydride), 1,8-(octamethylene)bis(trimellitate anhydride), 1,9-(nonamethylene)bis(trimellitate anhydride), 1,10-(decamethylene)bis(trimellitate) anhydride), 1,12-(dodecamethylene)bis(trimellitate anhydride), 1,16-(hexadecamethylene)bis(trimellitate anhydride), 1,18-(octadecamethylene)bis(trimelli tate anhydride) and the like.

As tricarboxylic acid anhydride, trimellitic acid anhydride, nuclear hydrogenation trimellitic acid anhydride, etc. are mentioned, for example.

As an amine component, although diamine, such as an aliphatic diamine and aromatic diamine, polyhydric amines, such as an aliphatic polyether amine, can be used, It is not limited to these amines. In addition, you may use these amine components individually or in combination.

Examples of the diamine include diamines having one benzene nucleus, such as p-phenylenediamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, and 2,6-toluenediamine. , 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and diaminodiphenyl ethers such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodi Phenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)- 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Methane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (o-tolidine), 2,2'-dimethyl Benzidine (m-tolidine), 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'- Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4' -Dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1, 3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide two benzene nuclei such as seed, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, and 3,3'-dicarboxy-4,4'-diaminodiphenylmethane Diamine, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-amino) Phenyl) 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'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-amino phenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)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, etc. diamine with three benzene nuclei, 3,3'-bis(3) -Aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-amino Phenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether , bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4- (3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-amino) Phenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy) )phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone; Bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-( 4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2, 2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane; 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-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- Aromatic diamines such as diamines having four benzene nuclei such as hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane , 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 ,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane Aliphatic diamines, such as these, are mentioned, As an aliphatic polyether amine, ethylene glycol and/or a propylene glycol polyhydric amine, etc. are mentioned.

Moreover, as follows, the amine which has a carboxyl group can also be used. Examples of the amine having a carboxyl group include diaminobenzoic acids such as 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid and 3,4-diaminobenzoic acid; 3,5-bis(3-aminophenoxy)benzoic acid; Aminophenoxybenzoic acids such as 3,5-bis(4-aminophenoxy)benzoic acid, 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-3,3 carboxyl such as '-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, 4,4'-diamino-2,2',5,5'-tetracarboxybiphenyl Biphenyl compounds, 3,3'-diamino-4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,2-bis[3 -Amino-4-carboxyphenyl]propane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 2,2-bis[3-amino-4-carboxyphenyl]hexafluoropropane, 4,4 Carboxydiphenyl alkanes such as carboxydiphenylmethane such as '-diamino-2,2',5,5'-tetracarboxydiphenylmethane, 3,3'-diamino-4,4'-dicarboxydi Phenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2 Carboxydiphenyl ether compounds such as 2',5,5'-tetracarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenylsulfone, 4,4'-diamino-3 ,3'-dicarboxydiphenylsulfone, 4,4'-diamino-2,2'-dicarboxydiphenylsulfone, 4,4'-diamino-2,2',5,5'-tetracarboxydi Diphenylsulfone compounds such as phenylsulfone, bis[(carboxyphenyl)phenyl]alkane compounds such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis Bis[(carboxyphenoxy)phenyl]sulfone compounds, such as [4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, etc. are mentioned.

As the isocyanate component, diisocyanates such as aromatic diisocyanate, isomers and multimers thereof, aliphatic diisocyanates, alicyclic diisocyanates and isomers thereof, and other general-purpose diisocyanates can be used. no. In addition, you may use these isocyanate components individually or in combination.

As diisocyanate, For example, aromatics, such as 4,4'- diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenyl sulfone diisocyanate, diphenyl ether diisocyanate, etc. aliphatic diisocyanates such as diisocyanate and its isomers, multimers, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate, or alicyclic diisocyanates and isomers obtained by hydrogenating the aromatic diisocyanate, or In addition, general-purpose diisocyanate is mentioned.

Alkali-soluble resin which has an imide ring may have an amide bond. The amide bond obtained by making isocyanate and carboxylic acid react may be sufficient as this, and what is based on reaction other than that may be sufficient as it. Moreover, you may have a bond containing other addition and condensation.

For the synthesis of alkali-soluble resins having an imide ring, known and usual alkali-soluble polymers, oligomers, and monomers having a carboxyl group and/or acid anhydride group may be used, for example, these known and usual alkali-soluble resins are used alone or as described above. In combination with a carboxylic acid anhydride component, resin obtained by making it react with the said amine/isocyanate may be sufficient.

In order that alkali-soluble resin which has an imide ring respond|corresponds to an alkali developing process, it is preferable that the acid value is 20-200 mgKOH/g, It is preferable that it is 60-150 mgKOH/g more suitably. When this acid value is 20 mgKOH/g or more, solubility with respect to alkali increases, developability becomes favorable, Furthermore, since the crosslinking degree with the thermosetting component after light irradiation becomes high, sufficient image development contrast can be obtained. Moreover, when this acid value is 200 mgKOH/g or less, so-called thermal cloudiness in the PEB process after light irradiation mentioned later can be suppressed, and a process margin becomes large.

Moreover, when developability and cured coating-film characteristic are considered, 1,000-100,000 are preferable and, as for the molecular weight of alkali-soluble resin which has an imide ring, 2,000-50,000 are more preferable.

When this molecular weight is 1,000 or more, sufficient develop resistance and hardened|cured material property can be acquired after exposure and PEB. Moreover, when molecular weight is 100,000 or less, alkali solubility increases and developability improves.

[Other alkali-soluble resins]

In this invention, other alkali-soluble resin is alkali-soluble resin other than alkali-soluble resin which has the said imide ring. Alkali-soluble resin has alkali-soluble groups, such as a carboxyl group and an acid-anhydride group, and is resin soluble in an alkali solution in a non-hardened state. Preferably, it has any 1 or more types of a urethane bond, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, and a biphenyl skeleton in a structure. Alkali-soluble resins other than those having an imide ring have lower reactivity with a carboxyl group than alkali-soluble resins having an imide ring, and the addition reaction with a thermosetting component proceeds relatively slowly, and alkali-soluble resins having these bonds or skeletons are alkali-soluble resins other than those having an imide ring. When is present, it is possible to take a longer heating time at the time of the PEB process compared to the case where it does not exist, and it becomes possible to widen the selection range of the heating temperature at the time of the PEB process.

Moreover, it is preferable that other alkali-soluble resins have an ethylenically unsaturated double bond in a molecule|numerator from a viewpoint of the improvement of the prevention effect of sagging at the time of heating. As an ethylenically unsaturated double bond, the thing derived from (meth)acrylic acid or a (meth)acrylic acid derivative is preferable. By having an ethylenically unsaturated double bond, when the photosensitive thermosetting resin composition of the present invention is heat-cured after development after light irradiation, the resin melts by heating and the pattern formed by development collapses, so-called sagging occurs. can be suppressed.

Another alkali-soluble resin according to the present invention has an alkali-soluble resin, a bisphenol A-type epoxy resin having an epoxy equivalent of 190 g/eq, and a composition comprising an oxime ester-based photobase generator, the reaction initiation temperature at the time of unexposed It is preferable that it is 75 degreeC or more. Specifically, the alkali-soluble resin and the epoxy equivalent of about 190 g / eq (184 to 194 g / eq) of the bisphenol A epoxy resin is contained so that the carboxyl group and the epoxy group are in an equivalent ratio of 1:1, with respect to 100 parts by mass of the alkali-soluble resin It is preferable that the reaction initiation temperature at the time of unexposed of the composition containing 10 mass parts of oxime ester type photobase generators is 75 degreeC or more.

The measurement of the reaction initiation temperature is collected in a DSC (Differential Scanning Calorimeter) measuring container so as not to photosensitize the composition containing the alkali-soluble resin, the epoxy resin and the photobase generator as described above, and DSC from 25°C to 200°C It carries out by measuring the heat of reaction in (temperature increase conditions 5 degreeC/min). In the DSC chart obtained by measuring in this way, the temperature at which the differential scanning heat becomes the minimum value is called the reaction initiation temperature.

In the unexposed state, when the reaction initiation temperature of the carboxyl group and the functional group reacting with the carboxyl group in the thermosetting component is 75° C. or higher, the alkali solubility of the unexposed part in the PEB process described later can be sufficiently maintained, and in the PEB process A large selection range of heating temperature can be taken.

Specific examples of the other alkali-soluble resin include compounds (any of oligomers and polymers) enumerated as (1) to (11) below.

(1) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols and polyethers Carboxyl groups by polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups Containing urethane resin.

(2) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin A photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth)acrylate or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(3) During the synthesis of the resin of (1) or (2), a compound having one hydroxyl group and one or more (meth)acryl group is added in a molecule such as hydroxyalkyl (meth)acrylate, and the terminal (meth) ) Acrylated photosensitive carboxyl group-containing urethane resin.

(4) During the synthesis of the resin of (1) or (2), a compound having one isocyanate group and one or more (meth)acrylic groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate The photosensitive carboxyl group containing urethane resin which added and carried out the terminal (meth)acrylated.

(5) Carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate or isobutylene.

(6) A photosensitive carboxyl group-containing resin in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, and dibasic acid anhydride is added to a hydroxyl group present in a side chain.

(7) A photosensitive carboxyl group-containing resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and dibasic acid anhydride is added to the generated hydroxyl group .

(8) A polyester resin containing a carboxyl group in which a dicarboxylic acid is reacted with a bifunctional oxetane resin, and a dibasic acid anhydride is added to a primary hydroxyl group generated.

(9) A compound having a plurality of phenolic hydroxyl groups in one molecule is reacted with an alkylene oxide such as ethylene oxide or propylene oxide and/or a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, Carboxyl group-containing photosensitive resin obtained by partially esterifying the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.

(10) A compound having a plurality of phenolic hydroxyl groups in one molecule is reacted with an alkylene oxide such as ethylene oxide and propylene oxide and/or a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, Carboxyl group-containing resin obtained by making a polybasic acid anhydride react with the reaction product obtained.

(11) A photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth)acryl group in one molecule to the resin of the above (5) to (10).

It is preferable that the acid value of other alkali-soluble resin is 20-200 mgKOH/g, More preferably, it is 40-150 mgKOH/g. Alkali solubility is favorable that an acid value is in said range, and patterning by alkali image development becomes easy.

Moreover, 1,000-100,000 are preferable and, as for the mass average molecular weight of other alkali-soluble resin, 3,000-50,000 are more preferable. When molecular weight is in said range, alkali solubility is favorable and patterning by alkali image development becomes easy.

It is preferable that content of other alkali-soluble resin is 10-70 mass parts with respect to 100 mass parts of alkali-soluble resins which have an imide ring. By the content in the above range, the heating time can be sufficiently long at the time of the PEB process, and it becomes possible to sufficiently widen the selection range of the heating temperature at the time of the PEB process.

[Photobase Generator]

The photobase generator used in the present invention can function as a catalyst for the addition reaction of a carboxyl group and a thermosetting component to be described later by changing the molecular structure or cleaving the molecule by irradiation with light such as ultraviolet or visible light. A compound that produces one or more basic substances. As a basic substance, a secondary amine and a tertiary amine are mentioned, for example.

When the resin composition of the present invention has an ethylenically unsaturated group in the system, the polymerization reaction of the ethylenically unsaturated group by light irradiation can be initiated. It is preferable to function also as an optical radical polymerization initiator to generate|generate.

As the photobase generator, for example, α-aminoacetophenone compound, oxime ester compound, acyloxyimino group, N-formylated aromatic amino group, N-acylated aromatic amino group, nitrobenzylcarbamate group, alkoxybenzylcar The compound etc. which have substituents, such as a barmate group, are mentioned. Especially, an oxime ester compound and (alpha)-aminoacetophenone compound are preferable. As the α-aminoacetophenone compound, it is particularly preferable to have two or more nitrogen atoms.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethylN,N'-diethylcarbamate), WPBG-027 (trade name: (E)-1-[3-(2-hyde) Roxyphenyl)-2-propenoyl]piperidine), WPBG-082 (trade name: guanidinium 2-(3-benzoylphenyl)propionate), WPBG-140 (trade name: 1-(anthraquinone-2) -yl) ethyl imidazole carboxylate) etc. can also be used.

The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs in the molecule to form a basic substance (amine) that exhibits a curing catalytic action. Specific examples of the α-aminoacetophenone compound include (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan) and 4-(methylthiobenzoyl)- 1-methyl-1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-) A commercially available compound such as morpholinyl)phenyl]-1-butanone (Irgacure 379, trade name, manufactured by BASF Japan) or a solution thereof can be used.

As an oxime ester compound, if it is a compound which produces|generates a basic substance by light irradiation, any can be used. As such an oxime ester compound, CGI-325 by BASF Japan, Irgacure-OXE01, Irgacure-OXE02, N-1919 by ADEKA Corporation, NCI-831 etc. are mentioned as a commercial item. Moreover, the compound which has two oxime ester groups in a molecule|numerator described in Unexamined-Japanese-Patent No. 4344400 can also be used suitably.

In addition, Japanese Patent Laid-Open No. 2004-359639, Japanese Patent Laid-Open No. 2005-097141, Japanese Patent Laid-Open No. 2005-220097, Japanese Patent Laid-Open No. 2006-160634, and Japanese Patent Laid-Open No. 2008-094770 The carbazole oxime ester compound of Unexamined-Japanese-Patent No. 2008-509967, Unexamined-Japanese-Patent No. 2009-040762, and Unexamined-Japanese-Patent No. 2011-80036, etc. are mentioned.

These photobase generators may be used individually by 1 type, and may be used in combination of 2 or more type. The compounding quantity of the photobase generator in the resin composition of this invention becomes like this. Preferably it is 0.1-40 mass parts with respect to 100 mass parts of thermosetting components, More preferably, it is 0.1-30 mass parts. When it is 0.1 mass part or more, the contrast of the developability of a light irradiated part/unirradiated part can be obtained favorably. Moreover, when it is 40 mass parts or less, hardened|cured material property improves.

[thermosetting component]

A thermosetting component has a functional group in which addition reaction with a carboxyl group is possible by heat|fever. As a thermosetting component, the compound which has a cyclic (thio) ether group is preferable, for example, and an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned.

The said epoxy resin is resin which has an epoxy group, Any well-known thing can be used. The bifunctional epoxy resin which has two epoxy groups in a molecule|numerator, the polyfunctional epoxy resin which has many epoxy groups in a molecule|numerator, etc. are mentioned. Moreover, the hydrogenated bifunctional epoxy compound may be sufficient.

Examples of the epoxy compound include bisphenol A epoxy resin, brominated epoxy resin, novolak epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, glycidylamine epoxy resin, hydantoin epoxy resin, alicyclic Formula epoxy resins, trihydroxyphenylmethane type epoxy resins, bixylenol type or biphenol type epoxy resins, or mixtures thereof; Bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, dicy An epoxy resin having a chloropentadiene skeleton, a glycidyl methacrylate copolymerized epoxy resin, a copolymerized epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, and a CTBN-modified epoxy resin may be mentioned.

As other liquid bifunctional epoxy resins, vinylcyclohexene diepoxide, (3',4'-epoxycyclohexylmethyl)-3,4-epoxycyclohexanecarboxylate, (3',4'-epoxy- and alicyclic epoxy resins such as 6'-methylcyclohexylmethyl)-3,4-epoxy-6-methylcyclohexanecarboxylate. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

Moreover, as a thermosetting component, you may mix|blend well-known and common compounds, such as a maleimide compound, a block isocyanate compound, an amino resin, a benzoxazine resin, carbodiimide resin, a cyclocarbonate compound, and an episulfide resin.

As a compounding quantity of a thermosetting component, it is preferable that the equivalence ratio (carboxyl group:heat-reactive group, such as an epoxy group) of the alkali-soluble resin which has the said imide ring and the said other alkali-soluble resin is 1:0.1 - 1:10. By setting it as the range of such a compounding ratio, image development becomes favorable and a fine pattern can be formed easily. The equivalent ratio is more preferably 1:0.2 to 1:5.

(radical photopolymerization initiator)

The photosensitive thermosetting resin composition of this invention may contain the radical photopolymerization initiator other than the said photobase generator. As an optical radical polymerization initiator, the well-known radical optical polymerization initiator which produces|generates a radical by light irradiation can be used. For example, alkylphenone-based photopolymerization initiators other than α-aminoacetophenone-based photopolymerization initiators that can function as the photobase generator described above, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, and the like are mentioned.

(polymer resin)

A commonly known polymer resin can be blended with the photosensitive thermosetting resin composition of the present invention for the purpose of improving the flexibility and dryness to the touch of the resulting cured product. Examples of the polymer resin include cellulose-based, polyester-based, phenoxy resin-based polymers, polyvinylacetal-based, polyvinylbutyral-based, polyamide-based, polyamideimide-based binder polymers, block copolymers, and elastomers. The said polymer resin may be used individually by 1 type, and may use 2 or more types together.

(inorganic filler)

An inorganic filler can be mix|blended with the photosensitive thermosetting resin composition of this invention. An inorganic filler is used in order to suppress cure shrinkage of the hardened|cured material of a resin composition, and to improve characteristics, such as adhesiveness and hardness. Examples of the inorganic filler include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, Neuburg diatomaceous earth, and the like. have. The said inorganic filler may be used individually by 1 type, and may use 2 or more types together.

(coloring agent)

A coloring agent can further be mix|blended with the photosensitive thermosetting resin composition of this invention. As the colorant, commonly known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes and dyes may be used.

(organic solvent)

An organic solvent can be used for the photosensitive thermosetting resin composition of this invention for manufacture of a resin composition, or for viscosity adjustment for apply|coating to a base material or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. These organic solvents may be used individually by 1 type, and may be used as 2 or more types of mixture.

(Other optional ingredients)

Components, such as a photosensitive monomer, a mercapto compound, an adhesion promoter, antioxidant, and a ultraviolet absorber, can be further mix|blended with the photosensitive thermosetting resin composition of this invention as needed. For these, a well-known substance can be used in the field|area of an electronic material. In addition, in the resin composition, well-known and usual thickeners such as finely divided silica, hydrotalcite, organic bentonite, and montmorillonite; Additives can be blended.

[Dry Film]

The dry film of this invention has a resin layer containing the photosensitive thermosetting resin composition of this invention, It is characterized by the above-mentioned. The dry film of the multilayer structure which also has a layer containing resin compositions other than the photosensitive thermosetting resin composition of this invention may be sufficient.

In dry film formation, for example, the photosensitive thermosetting resin composition of the present invention is diluted with an organic solvent, adjusted to an appropriate viscosity, and applied to a uniform thickness on a carrier film by a known method such as a comma coater. Then, it dries for 1 to 30 minutes at the temperature of 50-130 degreeC normally, and forms a resin layer on a carrier film.

As the carrier film, a plastic film is used. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers. After forming a resin layer on a carrier film, you may laminate|stack the cover film which can be peeled further on the surface of a resin layer.

[Flexible printed wiring board and manufacturing method thereof]

The flexible printed wiring board of this invention has a hardened|cured material containing the resin layer of a photosensitive thermosetting resin composition or a dry film, It is characterized by the above-mentioned.

The manufacturing method of the flexible printed wiring board of this invention includes the process of forming the resin layer containing the photosensitive thermosetting resin composition on a flexible printed wiring board, the process of irradiating light to the resin layer in pattern shape, the process of heating a resin layer, and water and alkali-developing the layer to form at least one of a coverlay and a solder resist.

[resin layer forming process]

At this process, at least one resin layer containing a photosensitive thermosetting resin composition is formed on a flexible printed wiring board.

A coating method and a lamination method are mentioned as a formation method of a resin layer.

In the case of the coating method, the photosensitive thermosetting resin composition is apply|coated on a flexible printed wiring board by methods, such as screen printing, and a resin layer is formed by drying.

In the case of the lamination method, first, the photosensitive thermosetting resin composition is diluted with the organic solvent, it adjusts to an appropriate viscosity, it apply|coats and dries on a carrier film, and the dry film which has a resin layer is produced. Next, after bonding so that a resin layer may contact with a flexible printed wiring board with a laminator etc., a carrier film is peeled.

In addition, another layer can be laminated|stacked on the resin layer. It is preferable that another layer contains an alkali developing type photosensitive resin composition. As an alkali developing type photosensitive resin composition, a well-known composition can be used, For example, the well-known composition for coverlays or for soldering resists can be used. Thus, by setting it as the laminated structure which included other layers, the hardened|cured material which was further excellent in impact resistance and flexibility can be obtained.

[Light irradiation process]

At this process, the photobase generator contained in a resin layer is activated by light irradiation in a negative pattern shape, and a light irradiation part is hardened. At this process, a photobase generator destabilizes with the base which generate|occur|produced in the light irradiation part, and when a base proliferates chemically, it can fully harden|cure to the deep part of a resin layer.

As the light irradiator, a direct drawing device, a light irradiator equipped with a metal halide lamp, etc. can be used. The pattern-shaped mask for light irradiation is a negative mask.

As an active energy ray used for light irradiation, it is preferable to use the laser beam or scattered light whose maximum wavelength is in the range of 350-450 nm. By making a maximum wavelength into this range, a photobase generator can be activated efficiently. As long as the laser beam of this range is used, either a gas laser or a solid-state laser may be used. In addition, although the amount of light irradiation varies depending on the film thickness, etc., it can be generally 100-1500 mJ/cm<2>.

[Heating process]

In this process, a light irradiation part is hardened by heating a resin layer after light irradiation. According to this process, it can harden|cure to a deep part with the base which generate|occur|produced in the light irradiation process. After the resin layer is pattern-exposed, alkali solubility is expressed by addition-reacting many carboxyl groups of the exposed part with the thermally reactive functional group of the thermosetting component, and most of the carboxyl groups of the unexposed part do not react with the thermally reactive functional group of the thermosetting component. , the heating temperature is set on the condition that alkali solubility can be maintained by remaining. From such a viewpoint, the heating temperature is preferably 80 to 140°C. From the point of industrial mass productivity and process control, 10 to 100 minutes are preferable and, as for heating time, the range of 10 minutes to 60 minutes is more preferable.

Since hardening of the photosensitive thermosetting resin composition in this invention is a ring-opening reaction of the epoxy resin by a thermal reaction, for example, compared with the case where hardening advances by a photoradical reaction, distortion and cure shrinkage can be suppressed.

[Development process]

In a developing process, an unirradiated part is removed by alkali development, and the insulating film on a negative pattern shape, especially a coverlay, and a soldering resist are formed.

As a developing method, it can follow well-known methods, such as dipping. Moreover, as a developing solution, imidazoles, such as sodium carbonate, potassium carbonate, potassium hydroxide, amines, 2-methylimidazole, aqueous alkali solutions, such as tetramethylammonium hydroxide aqueous solution (TMAH), or these mixtures can be used.

Moreover, you may light-irradiate an insulating film further after a developing process. Moreover, you may heat at 150 degreeC or more, for example.

Next, an example of the method of manufacturing the flexible printed wiring board of this invention from the resin composition of this invention is demonstrated based on the process diagram of FIG. In addition, although the case where the resin layer has a laminated structure is shown in FIG. 1, the case which consists of only one layer may be sufficient.

In the lamination process of FIG. 1, the laminated structure containing the resin layer 3 and the resin layer 4 is formed in the flexible printed wiring base material 1 in which the copper circuit 2 was formed.

The resin layer 3 contains the photosensitive resin composition of the alkali developing type containing carboxyl group-containing resin etc.

The resin layer 4 is formed on the resin layer 3 and contains the photosensitive thermosetting resin composition of the present invention comprising an alkali-soluble resin having an imide ring, another alkali-soluble resin, a photobase generator, and a thermosetting component. .

In the light irradiation step of FIG. 1 , the mask 5 is disposed on the resin layer 4 and light is irradiated in a negative pattern shape to activate the photobase generator contained in each resin layer to cure the light irradiation part. it is fair The heating process of FIG. 1 is a process (PEB process) of hardening a light irradiation part by heating a resin layer after a light irradiation process. The developing process of FIG. 1 is a process of developing with alkaline aqueous solution, an unirradiated part is removed, and is a process of forming a negative pattern layer.

In addition, the 2nd light irradiation process of FIG. 1 is a process for activating the remaining photobase generator as needed to generate a base, and a thermosetting process is a process for fully thermosetting a pattern layer, if necessary. to be.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited by these Examples and a comparative example.

<Synthesis example of alkali-soluble resin having an imide ring>

12.5 g of 3,5-diaminobenzoic acid, 2,2'-bis[4-(4-aminophenoxy)phenyl] in a separable three-necked flask equipped with a stirrer, nitrogen inlet tube, fractionation ring, and cooling ring 8.2 g of propane, 30 g of NMP, 30 g of γ-butyrolactone, 27.9 g of 4,4'-oxydiphthalic anhydride, and 3.8 g of trimellitic anhydride were added, and under a nitrogen atmosphere, room temperature, 100 rpm for 4 hours stirred. Then, 20 g of toluene was added, and it stirred for 4 hours, distilling toluene and water at 180 degreeC of silicone bath temperature, and 150 rpm, and the imide ring containing alkali-soluble resin solution was obtained.

<Measurement of reaction initiation temperature of other alkali-soluble resin>

Each alkali-soluble resin and the thermosetting component (bisphenol A type epoxy resin having an epoxy equivalent of about 190 g/eq, product name: E828, manufactured by Mitsubishi Chemical Co., Ltd.) were mixed so that the carboxyl group and the epoxy group had an equivalent ratio of 1:1, and added 10 parts by mass of a raw oxime ester-based photobase generator (Irgacure OXE-02, manufactured by BASF) was mixed with 100 parts by mass of alkali-soluble resin to obtain a sample. 5 mg of each sample is collected in a DSC measuring vessel (DSC6200 manufactured by Seiko Instruments) so as not to be photosensitized, and the heat of reaction at 25°C to 200°C (temperature increase 5°C/min) is measured, and heat generation due to reaction of carboxyl group and epoxy group The reaction initiation temperature was analyzed, and the minimum value of the differential scanning heat was set as the reaction initiation temperature. The results are shown in Table 1 below. In addition, about the measurement result of alkali-soluble resin 3 and alkali-soluble resin 6, a DSC chart is shown in FIG. In FIG. 2, the chart shown by the reference sign 6 shows the measurement result of alkali-soluble resin 3, The chart shown by the reference sign 7 shows the measurement result of the alkali-soluble resin 6, respectively.

※Alkali-soluble resin 1: carboxyl group-containing polyurethane (manufactured by Negami Kogyo Co., Ltd.), acid value 50 mgKOH/g

※Alkali-soluble resin 2: Polyurethane acrylate (manufactured by Kyoe Chemical Co., Ltd.), acid value 47 mgKOH/g

※Alkali-soluble resin 3: Bisphenol F-type acrylate resin (manufactured by Nippon Chemical Co., Ltd.), acid value 98 mgKOH/g

※Alkali-soluble resin 4: Bisphenol A type acrylate resin (manufactured by Nippon Chemical Co., Ltd.), acid value 98 mgKOH/g

※Alkali-soluble resin 5: Biphenyl type acrylate resin (manufactured by Nippon Chemical Co., Ltd.), acid value 98 mgKOH/g

※Alkali-soluble resin 6: Phenol novolac-type acrylate resin (manufactured by Nippon Kayaku Co., Ltd.), acid value 98 mgKOH/g

[Examples 1 to 7, Comparative Examples 1 to 3]

<Preparation of resin composition>

According to the formulations shown in Table 2 below, the materials described in Examples and Comparative Examples were each blended and premixed with a stirrer, and then kneaded with a triaxial roll mill to prepare a photosensitive photocurable thermosetting resin composition. The values in the table are solid content (parts by mass) unless otherwise specified.

<Formation process of resin layer>

The flexible printed wiring base material in which the circuit is formed by 18 micrometers of copper thickness was prepared, and it pre-processed using Mack Corporation CZ-8100. Then, the resin composition of Examples 1-7 and Comparative Examples 1-3 was coated on the flexible printed wiring board which performed the said pretreatment so that it might become 20 micrometers after drying by the liquid coating method. Then, it dried at 80 degreeC and 30 minutes in the hot-air circulation type drying furnace, and the resin layer was formed. Then, it light-irradiated in the form of a negative pattern with the exposure amount of 500 mJ/cm<2> with ORC company HMW680GW (metal halide lamp, scattered light).

<Evaluation of time management width of PEB process>

The substrate having the resin layer after exposure obtained by the above resin layer forming step was heated at 90° C. for 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, respectively. Minute and heat treatment for 120 minutes were performed. Thereafter, the substrate after heat treatment is immersed in a 1 mass % sodium carbonate aqueous solution at 30° C., and development is performed for 5 minutes to evaluate developability, and heat treatment time A for which the exposed portion has develop resistance, that is, no film reduction is observed. From , the time width (BA) until the heat treatment time B at which the unexposed portion could not be completely removed due to development was calculated. The larger the numerical value, the greater the range of time management of the PEB process, and the better the handleability.

<Evaluation of developability by temperature of PEB process>

The board|substrate which has the resin layer after exposure obtained by the said resin layer formation process was heat-processed for 80 degreeC 60 minutes, 90 degreeC 30 minutes, and 100 degreeC 15 minutes. Thereafter, the substrate was immersed in a 1 mass % sodium carbonate aqueous solution at 30 DEG C, and development was performed for 5 minutes to evaluate whether or not the pattern was formed. The evaluation criteria are as follows.

OK: An exposed part shows developability, an unexposed part shows developability, and pattern formation is favorable.

NG※1: Pattern cannot be formed because the exposed part dissolves in the developer.

NG※2: Pattern cannot be formed because the unexposed part does not dissolve in the developer.

* Alkali-soluble resin containing an imide ring: What was synthesized by the synthesis example of the alkali-soluble resin which has the said imide ring. Acid value 86 mgKOH/g, Mw10000

※Alkali-soluble resin 1: carboxyl group-containing polyurethane (manufactured by Negami Kogyo Co., Ltd.), acid value 50 mgKOH/g

※Alkali-soluble resin 2: Polyurethane acrylate (manufactured by Kyoe Chemical Co., Ltd.), acid value 47 mgKOH/g

※Alkali-soluble resin 3: Bisphenol F-type acrylate resin (manufactured by Nippon Chemical Co., Ltd.), acid value 98 mgKOH/g

※Alkali-soluble resin 4: Bisphenol A type acrylate resin (manufactured by Nippon Chemical Co., Ltd.) Acid value 98 mgKOH/g

※Alkali-soluble resin 5: Biphenyl type acrylate resin (manufactured by Nippon Chemical Co., Ltd.), acid value 98 mgKOH/g

※Alkali-soluble resin 6: Phenol novolac-type acrylate resin (manufactured by Nippon Kayaku Co., Ltd.), acid value 98 mgKOH/g

※E828: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical), epoxy equivalent 190 g/eq

※Irgacure OXE-2: oxime ester-based photobase generator (manufactured by BASF Japan)

As is clear from the evaluation results shown in Table 1, the photosensitive thermosetting resin compositions of Examples 1 to 7 have a large time management range for the PEB process, and heat treatment after exposure at any temperature of 80°C, 90°C, or 100°C The developability was also good.

1: Flexible printed wiring substrate
2: copper circuit
3: resin layer
4: resin layer
5: Mask
6: Alkali-soluble resin 3+Bis-A epoxy resin
7: Alkali-soluble resin 6+Bis-A epoxy resin

Claims (7)

An alkali-soluble resin having an imide ring and a carboxyl group, an alkali-soluble resin having a carboxyl group other than the alkali-soluble resin having an imide ring and a carboxyl group, an oxime ester-based photobase generator and a thermosetting component,
By using a base generated from an oxime ester-based photobase generator as a catalyst, the carboxyl group of the alkali-soluble resin and the thermosetting component are addition-reacted by heating after exposure, whereby the unexposed portion can be developed It is a photosensitive thermosetting resin composition,
The said other alkali-soluble resin has a reaction initiation temperature at the time of unexposure in the case of setting it as the composition which mixes the said other alkali-soluble resin, the bisphenol A epoxy resin of 190 g/eq of epoxy equivalent, and an oxime ester type photobase generator, 75 The photosensitive thermosetting resin composition, characterized in that it is ℃ or higher. The photosensitive thermosetting resin composition according to claim 1, wherein the other alkali-soluble resin has in its structure any one or more of a urethane bond, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, and a biphenyl skeleton. The photosensitive thermosetting resin composition according to claim 1, wherein the content of the other alkali-soluble resin is 10 to 70 parts by mass with respect to 100 parts by mass of the alkali-soluble resin having an imide ring. The photosensitive thermosetting resin composition according to claim 1, wherein the thermosetting component is a compound having at least one of a cyclic ether group and a cyclic thioether group. It is formed by apply|coating and drying the photosensitive thermosetting resin composition of Claim 1, The dry film characterized by the above-mentioned. It is obtained by hardening|curing the photosensitive thermosetting resin composition of Claim 1 or the dry film formed by apply|coating and drying the said composition, The cured coating film characterized by the above-mentioned. It has a cured coating film obtained by hardening|curing the photosensitive thermosetting resin composition of Claim 1 or the dry film formed by apply|coating and drying the said composition, The printed wiring board characterized by the above-mentioned.

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