JP2014167509A - Kit for preparing photosensitive resin composition and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a kit for preparing a photosensitive resin composition, which suppresses reduction in photosensitivity after long-term storage and has excellent storage stability, which is excellent in microprocessing property, developability, low-temperature curability, flexibility of a cured film, reliability of electric insulation, solder heat resistance, organic solvent resistance, flame retardancy, and the like, and which induces little warpage of a substrate after cured.SOLUTION: The kit for preparing a photosensitive resin composition comprises at least two agents of at least A agent and B agent. The A agent comprises (A) a compound having a carboxyl group and (C) an oxime ester-based photopolymerization initiator; and the water content in the A agent is 5000 ppm or less. The B agent comprises (B) a compound having a reactive group that reacts with a carboxyl group.

Description

  The present invention relates to a photosensitive resin composition preparation kit, a method for producing a resin composition using the same, a method for producing a resin film, a method for producing an insulating film, a method for producing a printed wiring board with an insulating film, and a storage method. It is.

  More specifically, the present invention includes (i) a photosensitive resin composition preparation kit excellent in storage stability after long-term storage, (ii) microfabrication property, developability, low-temperature curability, flexibility of a cured film, A method for producing a photosensitive resin composition obtained from the photosensitive resin composition preparation kit, which is excellent in electrical insulation reliability, solder heat resistance, organic solvent resistance, and flame retardancy, and has low warpage of the substrate after curing, (iii) It is related with the manufacturing method of the resin film obtained from the said photosensitive resin composition, the manufacturing method of an insulating film, and the manufacturing method of a printed wiring board with an insulating film.

  Furthermore, this invention relates to the preservation | save method of the compound which comprises the photosensitive resin composition.

  Conventionally, in the printed wiring board manufacturing industry, a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film has been used as a surface protective material for a flexible circuit board. When bonding this coverlay film on a flexible circuit board, there is a method in which an opening is provided in advance by a method such as punching in a terminal portion of a circuit or a joint portion with a component, and after aligning, a method of thermocompression bonding by a hot press or the like is used. It is common. Further, the cover lay film is required to have excellent characteristics such as heat resistance, chemical resistance, flame retardancy, adhesion, and electrical insulation reliability. Regarding flame retardancy, good flame retardancy can be obtained by using a halogen-based flame retardant, but from the viewpoint of environmental impact, a flame-retarding technique that does not contain a halogen-based flame retardant is required.

  The cover lay film having the above configuration is difficult to provide a high-precision opening, and the positioning at the time of pasting is often performed manually, so that the positional accuracy is poor and the pasting workability is also poor. Therefore, a solder resist having a photosensitive function may be used, and it is excellent in fine workability. As this photosensitive solder resist, a photosensitive resin composition mainly composed of an epoxy resin or the like is used. This photosensitive solder resist is excellent in electrical insulation reliability as an insulating material, but has mechanical properties such as flexibility. However, since the curing shrinkage is large, when it is laminated on a thin and flexible circuit board such as a flexible circuit board, the warpage of the board becomes large and it is difficult to use it for a flexible circuit board. Further, the flame retardancy is poor, and when a flame retardant is added for the purpose of imparting flame retardancy, there are problems such as deterioration in physical properties and contact failure due to bleeding out from the cured film and process contamination.

  In recent years, various proposals have been made that can exhibit flame retardancy as the photosensitive solder resist.

  For example, Patent Document 1 proposes a flame-retardant photocurable resin composition containing a phosphazene compound, a carboxyl group-containing resin, and a photopolymerization initiator that are liquid at room temperature.

  Patent Document 2 proposes a flame retardant photocurable resin composition containing a carboxyl group-containing resin, a soluble phosphazene compound that is soluble in a carboxyl group-containing resin by 5 wt% or more, and a photopolymerization initiator.

  On the other hand, in Patent Document 3, a photo-curing / thermosetting resin composition having excellent dryness to touch, adhesion, and resolution, little mist generated at the time of heat curing, high sensitivity and excellent storage stability. Proposed.

  Patent Document 4 proposes a photocurable / thermosetting resin composition having high sensitivity, good curing depth, excellent storage stability and workability, and excellent developability with an aqueous alkali solution. Yes.

JP 2010-39389 A JP 2010-113245 A International Publication No. 2004/048434 JP 2008-299294 A

  In the above patent document, various methods for solving the problem of the coverlay are proposed. However, the flame retardant photocurable resin composition described in Patent Documents 1 and 2 can form a coverlay that has a non-halogen composition and has a low environmental load and excellent flame retardancy, but is cured with a large amount of photosensitive group. Since the crosslink density of the film is increased, sufficient flexibility cannot be obtained. Moreover, the viewpoint in the long-term storage stability of the photosensitivity which is the effect of this invention is not described, but the essence is different from the invention of the present application composed of two or more agents.

  Moreover, the photocurable thermosetting resin composition described in Patent Document 3 is a composition different from the composition in which the oxime ester photopolymerization initiator is blended with a carboxyl group-containing resin and a reactive diluent. In order to avoid the long-term contact between the oxime ester photopolymerization initiator and the reactive diluent, since each composition is mixed and used immediately before use. Therefore, it is considered that the reaction of the reactive diluent is prevented and the storage stability is excellent. However, since the oxime ester photopolymerization initiator is blended in a different mixture from the carboxyl group-containing resin and reactive diluent, the solvent for dissolving and dispersing the oxime ester photopolymerization initiator is scarce and stored for a long time. The oxime ester-based photopolymerization initiator may be precipitated. In addition, the insulating film obtained from the resin composition is poor in flame retardancy because it does not assume a configuration to obtain flame retardancy, and when a flame retardant is used to obtain sufficient flame retardancy, It is assumed that the characteristic is deteriorated.

  Moreover, the photocurable thermosetting resin composition described in Patent Document 4 is a mixture of a carboxyl group-containing resin and mercaptobutanoic acid or a derivative thereof, and an oxime photopolymerization initiator and an epoxy resin. It is blended in a composition different from the composition and is composed of at least a two-component system. Since each composition is mixed and used immediately before use, it is considered that the storage stability is excellent. However, since the oxime ester photopolymerization initiator is blended in a different mixture from the carboxyl group-containing resin and reactive diluent, the solvent for dissolving and dispersing the oxime ester photopolymerization initiator is scarce and stored for a long time. The oxime ester-based photopolymerization initiator may be precipitated. In addition, the insulating film obtained from the resin composition is poor in flame retardancy because it does not assume a configuration to obtain flame retardancy, and when a flame retardant is used to obtain sufficient flame retardancy, It is assumed that the characteristic is deteriorated.

  As a result of intensive studies to solve the above problems, the inventors of the present invention are photosensitive resin composition preparation kits comprising at least two agents of agent A and agent B, wherein agent A is (A) carboxyl A compound having a group, and (C) an oxime ester-based photopolymerization initiator, the water content in the agent A is 5000 ppm or less, and the agent B has a reactive group that reacts with the carboxyl group (B) The photosensitive resin composition preparation kit characterized in that the present invention has a moisture content of 5000 ppm or less, so that the present inventors (A) occur in an acidic atmosphere in which a compound having a carboxyl group is present. (C) It is considered that hydrolysis of the oxime ester photopolymerization initiator is suppressed. Therefore, the photosensitivity deterioration after storage for a long period of time hardly occurs. Since the photosensitive resin composition produced using the toner has photosensitivity, it can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or less), and is stored for a long time. The cured film obtained has excellent flexibility, electrical insulation reliability, solder heat resistance, organic solvent resistance, flame resistance, and low warpage of the substrate after curing. The knowledge which a photosensitive resin composition is obtained was obtained, and based on these knowledge, it reached the present invention.

  The present invention can solve the above problems by the following novel photosensitive resin composition.

  That is, the present invention is a photosensitive resin composition preparation kit comprising at least two agents of agent A and agent B, wherein agent A is (A) a compound having a carboxyl group, and (C) oxime. An ester photopolymerization initiator is contained, the water content in the agent A is 5000 ppm or less, and the agent B contains (B) a compound having a reactive group that reacts with a carboxyl group. It is a photosensitive resin composition preparation kit.

  In the photosensitive resin composition preparation kit according to the present invention, the compound (B) having a reactive group that reacts with a carboxyl group is preferably (b1) an epoxy resin.

  Furthermore, it is preferable that the agent A and / or the agent B contain (D) a compound having a photosensitive group without having a carboxyl group.

  Further, the present invention is a method for producing a photosensitive resin composition produced using the photosensitive resin composition production kit, wherein at least two agents of the A agent and the B agent are mixed. A method for producing a photosensitive resin composition is also included.

  Further, the present invention is a method for producing a resin film produced using the photosensitive resin composition production kit described above, after applying a mixture of at least two agents of the agent A and agent B to the substrate surface, Also encompassed is a method for producing a resin film, which is obtained by drying the mixture.

  The present invention also encompasses an insulating film manufacturing method characterized by being obtained by curing a resin film obtained by the above resin film manufacturing method.

  The present invention also encompasses a method for producing a resin film, which is obtained by coating a printed wiring board with an insulating film obtained by the method for producing an insulating film.

  Furthermore, the present invention constitutes a photosensitive resin composition comprising at least (A) a compound having a carboxyl group, (C) an oxime ester photopolymerization initiator, and (B) a compound having a reactive group that reacts with the carboxyl group. A method for preserving a compound, comprising (A) a compound having a carboxyl group, (C) an oxime ester-based photopolymerization initiator, and an A agent having a water content of 5000 ppm or less, and (B) a carboxyl A storage method comprising preparing two or more agents with a B agent containing a compound having a reactive group that reacts with a group and storing at least the A agent and the B agent separately is also included.

  Moreover, as for the preservation | save method of the compound which comprises the photosensitive resin composition concerning this invention, it is preferable that the compound which has the reactive group which reacts with the said (B) carboxyl group is (b1) epoxy resin.

  The photosensitive resin composition preparation kit of the present invention tends to be less susceptible to lowering of photosensitivity after long-term storage, and is excellent in storage stability. The photosensitive resin composition produced using the kit has photosensitivity and can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or lower), and The cured film obtained from the photosensitive resin composition is rich in flexibility, excellent in electrical insulation reliability, solder heat resistance, organic solvent resistance, flame resistance, and has good physical properties and warpage after curing. Is small. Therefore, the photosensitive resin composition produced using the photosensitive resin composition production kit of the present invention can be used for protective films of various circuit boards and has excellent effects.

  Hereinafter, the present invention will be described in detail in the order of (I) a photosensitive resin composition preparation kit and (II) a method of using a photosensitive resin composition preparation kit.

(I) Photosensitive resin composition preparation kit The photosensitive resin composition preparation kit of the present invention is a photosensitive resin composition preparation kit including at least two agents of agent A and agent B, and the agent A Contains (A) a compound having a carboxyl group, and (C) an oxime ester-based photopolymerization initiator, the water content in agent A is 5000 ppm or less, and the agent B reacts with (B) the carboxyl group. Any photosensitive resin composition preparation kit characterized by containing a compound having a functional group may be used.

  The “photosensitive resin composition preparation kit” is a kit for preparing a photosensitive resin composition, and a photosensitive resin composition is prepared by mixing two or more agents contained in the kit. Means what you can do.

  Here, in general, since the productivity is excellent, the photopolymerization initiator is often used as a component of the agent A, but the (C) oxime ester photopolymerization initiator used in the present invention is used as a component of the agent A. When used as a composition, the storage stability is greatly reduced, so it cannot be used with a general composition. However, although the photosensitive resin composition preparation kit of the present invention uses (C) an oxime ester photopolymerization initiator, the present inventors show that it has high storage stability and is excellent in various properties. Found. When (A) a compound having a carboxyl group and (C) an oxime ester photopolymerization initiator coexist, an acidic atmosphere in which a carboxyl group exists acts as a catalyst, hydrolysis of the oxime ester occurs, and storage stability However, it is speculated that hydrolysis could be suppressed by controlling the water content to 5000 ppm or less.

  When (A) a compound having a carboxyl group and (B) a compound having a reactive group that reacts with a carboxyl group coexist, the reaction between the carboxyl group and the reactive group that reacts with the carboxyl group gradually proceeds, Since the stability is lowered, (B) a compound having a reactive group that reacts with a carboxyl group is blended with a B agent different from the A agent containing the compound (A) having a carboxyl group. Stability is improved.

  In addition, as described above, (A) a compound having a carboxyl group and (C) an A agent containing an oxime ester photopolymerization initiator, the agent A having a water content of 5000 ppm or less, and (B) a carboxyl group Preparation of two or more agents with a B agent containing a compound having a reactive group that reacts with the agent, and storage of the A agent and the B agent separately allows storage stability as a photosensitive resin composition preparation kit Can be improved. That is, the photosensitive resin composition comprising (A) a compound having a carboxyl group, (B) a compound having a reactive group that reacts with a carboxyl group, and (C) a compound comprising an oxime ester photopolymerization initiator. It can be said that the present invention can provide a stable storage method.

  Hereinafter, the present invention will be described in detail with respect to the photosensitive resin composition. Here, (meth) acrylic acid in the present invention means acrylic acid and / or methacrylic acid, and (meth) acrylate has the same meaning.

  Further, in this specification, (A) a compound having a carboxyl group is referred to as “(A) component”, (B) a compound having a reactive group that reacts with a carboxyl group is referred to as “(B) component”, and (C) oxime. The ester photopolymerization initiator may be referred to as “(C) component”, and (D) a compound having no carboxyl group and having a photosensitive group may be referred to as “(D) component”.

<(A) Compound having a carboxyl group>
The compound (A) having a carboxyl group in the present invention is a compound having at least one carboxyl group in the molecule. The carboxyl group may be a carboxylic acid anhydride in which two carboxyl groups are dehydrated.

  The component (A) is not particularly limited. For example, a carboxyl group-containing (meth) acrylic copolymer, a carboxyl group-containing vinyl copolymer, acid-modified polyurethane, acid-modified polyester, acid-modified polycarbonate, acid-modified polyamide, Examples thereof include acid-modified polyimide, and these can be used alone or in combination of two or more. In terms of developability of the photosensitive resin composition, flexibility of the resulting cured film, chemical resistance, and the like, a carboxyl group-containing (meth) acrylic copolymer, acid-modified polyurethane, acid-modified polyamide, and acid-modified polyimide are preferable. .

  Specific examples of the carboxyl group-containing (meth) acrylic copolymer include (meth) acrylic acid, propiolic acid, crotonic acid, isocrotonic acid, myristoleic acid having a carboxyl group and a copolymerizable double bond. , Palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, (meth) Acrylic acid dimer, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, atropic acid, cinnamic acid, linol Acid, eicosadienoic acid, docosadienoic acid, linolene , Pinolenic acid, eleostearic acid, mead acid, dihomo-Y-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, boseopentenoic acid, eicosapentaenoic acid, ozbond acid, sardine Homopolymerization or copolymer of acid, tetracosapentaenoic acid, docosahexaenoic acid, nisinic acid, 2,2,2-trisacryloyloxymethyl succinic acid, 2-trisacryloyloxymethylethylphthalic acid, etc. Further, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, octyl (meth) acrylate, (meth) acrylic Acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid alkyl esters such as stearyl (meth) acrylate, acrylamide such as diacetone acrylamide, acrylonitrile and vinyl-n-butyl ether Esters of vinyl alcohol, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-tri There are copolymers obtained by adding a compound having a double bond capable of copolymerization, such as fluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, styrene, vinyltoluene and the like. The above-mentioned homopolymerization or copolymerization can proceed by generating radicals with a radical polymerization initiator, for example. Examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, t-butylhydro Organic peroxides such as peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, peracid number Hydrogen etc. are mentioned, These can be used individually or in combination of 2 or more types.

  Moreover, the said acid-modified polyimide is obtained by reaction of a diisocyanate compound and tetracarboxylic dianhydride, for example. By adding tetracarboxylic dianhydride in excess of the equivalent of the diisocyanate compound, a compound of terminal carboxylic acid anhydride having an imide bond can be obtained. Furthermore, the terminal carboxylic acid compound can be obtained by reacting the terminal carboxylic acid anhydride compound with water and / or a primary alcohol. In addition, although it does not specifically limit as primary alcohol, For example, methanol, ethanol, propanol, a butanol etc. can be used suitably.

  Although the said diisocyanate compound is not specifically limited, For example, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- Or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3 ' -Or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2 '-Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate , Diphenylmethane-3,3'- Isocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2 , 6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate Compound, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc., hexamethylene diisocyanate Isocyanate, trimethyl hexamethylene diisocyanate, alicyclic diisocyanate compounds such as lysine diisocyanate. Further, it may be a reaction product of a compound having two or more functional groups capable of reacting with an isocyanate group of a diisocyanate compound, for example, a terminal isocyanate group compound that reacts with a diol compound and has a urethane bond. . These can be used alone or in combination of two or more.

  The tetracarboxylic dianhydride is not particularly limited, but is preferably aromatic, and more preferably an anhydrous carboxyl group is directly bonded to the aromatic, for example, 3, 3 ′, 4, 4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) ) Phenyl] propane dianhydride, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 5- (2,5 -Geoki Tetrahydro-3-furanyl) methyl-3-cyclohexene-1,2-tetracarboxylic dianhydride, such as dicarboxylic acid anhydride can be used. These can be used alone or in combination of two or more.

  The acid-modified polyamide is obtained, for example, by a reaction between a diamino compound and tetracarboxylic dianhydride and becomes a compound having an amic acid structure.

  The diamino compound is not particularly limited, but m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, (3-amino Phenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide Bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3 , 3'-Diaminobenzophenone, 3 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- (3-aminophenoxy) Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfide Bis [4- (aminophenoxy) phenyl] sulfide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfide, 3,3′-diaminobenzanilide, 3,4′-diaminobenzanilide, 4, 4′-diaminobenzanilide, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, [4- (4-aminophenoxyphenyl)] [4- ( 3-aminophenoxyphenyl)] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1- [ 4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- (3-amino Phenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] Ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4-aminophenoxy) Phenyl)] [4- (3-aminophenoxyphenyl)] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2 , 2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2- [4- (4-aminophenoxyphenyl)] [4- (3-amino Enoxyphenyl)]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, Bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino Phenoxy) phenyl] ether, polytetramethylene oxide-di-P-aminobenzoate, poly (tetramethylene / 3-methyltetramethyle) Ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis ( 4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4 ′ -Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, [bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino- 3-carboxy) phenyl] methane, [bis (3-amino-4-carboxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] methane, 2 2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane 2,2-bis [4-amino-3-carboxyphenyl] hexafluoropropane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxy Diphenyl ether, 4,4′-diamino-2,2′-dicarboxydiphenyl ether, 3,3′-diamino-4,4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′-dicarboxydiphenyl Sulfone, 4,4′-diamino-2,2′-dicarboxydiphenylsulfone, 2,3-diaminophenol, 2,4 Diaminophenols such as diaminophenol, 2,5-diaminophenol, 3,5-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxy Hydroxybiphenyl compounds such as biphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino Dihydroxydiphenylmethanes such as -4,4'-dihydroxydiphenylmethane, 4,4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [ 3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hi Bis [hydroxyphenyl] propanes such as loxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoro Bis [hyhydroxyphenyl] hexafluoropropanes such as propane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino Hydroxydiphenyl ethers such as -2,2'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 4,4 ' -Diamino-2,2'-dihydroxydiphenylsulfo Dihydroxydiphenyl sulfones such as 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2,2 Dihydroxydiphenyl sulfides such as' -dihydroxydiphenyl sulfide, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfoxide, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfoxide, 4,4'-diamino Dihydroxydiphenyl sulfoxides such as -2,2'-dihydroxydiphenyl sulfoxide, and bis [(hydroxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane 4,4′-bis (4-a Bis ((hydroxyphenoxy)) such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, bis (hydroxyphenoxy) biphenyl compounds such as (no-3-hydroxyphenoxy) biphenyl Phenyl] sulfone compound, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxy Bis (hydroxyphenoxy) biphenyl compounds such as phenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl can be used. These can be used alone or in combination of two or more.

  Moreover, the said tetracarboxylic dianhydride can use the compound similar to the case of acid-modified polyimide, These can be used individually or in combination of 2 or more types.

  Further, (A) the compound having a carboxyl group may have a photosensitive group. Although there is no particular limitation, for example, there is an epoxy acrylate obtained by adding a saturated or unsaturated polycarboxylic acid anhydride to an ester obtained by reacting an epoxy compound with an unsaturated monocarboxylic acid. Examples of the saturated or unsaturated polybasic acid anhydride include anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, and trimellitic acid. Moreover, for example, there is urethane acrylate which is a polymer of a diol compound having an ethylenically unsaturated group and / or a carboxyl group and a diisocyanate compound. Also, a copolymer is obtained with (meth) acrylic acid and (meth) acrylic ester having a carboxyl group and a copolymerizable double bond, and a part of the side chain carboxyl group is (meth) such as glycidyl methacrylate. There is an acrylated acrylate obtained by reacting with an epoxy group of a compound having an acrylic group and an epoxy group. Examples of the epoxy acrylate include ZFR series, ZAR series, ZCR series, CCR series, and PCR series manufactured by Nippon Kayaku Co., Ltd., and urethane acrylates include, for example, UXE series manufactured by Nippon Kayaku Co., Ltd. Can be mentioned. Examples of the acrylated acrylate include Cyclomer ACA series manufactured by Daicel Cytec Co., Ltd.

  The reaction for obtaining the compound having a carboxyl group (A) can be carried out without a solvent, but in order to control the reaction, it is desirable to carry out the reaction in an organic solvent system. For example, as an organic solvent, Sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, N Examples include pyrrolidone solvents such as -methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, hexamethylphosphoramide, and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  Furthermore, for example, methyl monoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (Bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2 Symmetric glycol diethers such as -butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Cetate (aka carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether Acetates such as acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n Propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the solvent of ethers such as ethylene glycol monoethyl ether.

  The amount of solvent used in the reaction is preferably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% to 90% by weight, and is 20% to 70% by weight. It is more preferable. When the solution concentration is less than 5%, the polymerization reaction is difficult to occur and the reaction rate is lowered, and a desired structural substance may not be obtained. When the solution concentration is more than 90% by weight, the reaction solution has a high viscosity. And the reaction may be non-uniform.

  In addition, the component (A) has a weight average molecular weight in the range of 1,000 to 1,000,000 in terms of polyethylene glycol, and more preferably in the range of 2,000 to 200,000. preferable. When the weight average molecular weight is 1,000 or less, flexibility and chemical resistance may be lowered, but when it is 2,000 or more, sufficient flexibility and chemical resistance are easily obtained. In addition, when the weight average molecular weight is 1,000,000 or more, the alkali developability may be lowered, or the viscosity of the photosensitive resin composition may become too high, and the coating film formation may be difficult. When it is 000 or less, sufficient alkali developability is easily obtained, and the viscosity of the photosensitive resin composition does not become too high, and the coating film is easily formed.

<(B) Compound having a reactive group that reacts with a carboxyl group>
The (B) compound having a reactive group that reacts with a carboxyl group used in the present invention is not particularly limited as long as it has a reactive group that reacts with at least one carboxyl group in the molecule. Here, examples of the reactive group that reacts with the carboxyl group include an epoxy group, an oxetanyl group, an isocyanate group, an amino group, and a hydroxyl group, and any of a monomer, an oligomer, and a polymer can be used. In addition, the compound (B) having a reactive group that reacts with a carboxyl group is blended in the agent B different from the agent A containing the compound (A) having a carboxyl group. By setting it as the said structure, reaction progress by the long-time contact with (A) component and (B) component is suppressed, and the storage stability of the photosensitive resin composition preparation kit improves.

  When the compound (B) having a reactive group that reacts with a carboxyl group used in the present invention is (b1) an epoxy resin, the heat resistance and electrical insulation reliability of a cured film obtained by curing the photosensitive resin composition It is preferable because of its excellent properties. The epoxy resin is a resin having at least one epoxy group in the molecule and is not particularly limited. For example, as a bisphenol A type epoxy resin, trade names jER828, jER1001, jER1002, manufactured by Japan Epoxy Resin Co., Ltd. Product names Adeka Resin EP-4100E, Adeka Resin EP-4300E manufactured by Adeka Co., Ltd., product names RE-310S and RE-410S manufactured by Nippon Kayaku Co., Ltd., and product names Epicron 840S, Epicron 850S and Epicron 1050 manufactured by DIC Corporation, Epicron 7050, product names Epototo YD-115, Epototo YD-127, Epototo YD-128, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin, product names jER8 manufactured by Japan Epoxy Resin Co., Ltd. 6, jER807, trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950 manufactured by ADEKA Corporation, trade names RE-303S, RE-304S, RE-403S, RE-404S manufactured by Nippon Kayaku Co., Ltd. DIC Corporation's trade name Epicron 830, Epicron 835, Toto Kasei Co., Ltd. trade names Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001, and bisphenol S type epoxy resin are manufactured by DIC Corporation. Product names Epicron EXA-1514 and hydrogenated bisphenol A type epoxy resins include product names jERYX8000, jERYX8034, jERYL7170, and ADEKA Corporation's product names ADEKA RESIDENCE. EP-4080E, DIC Corporation trade name Epicron EXA-7015, Toto Kasei Co., Ltd. trade name Epototo YD-3000, Epototo YD-4000D, biphenyl type epoxy resin, trade name of Japan Epoxy Resin Co., Ltd. jERYX4000, jERYL6121H, jERYL6640, jERYL6677, trade names NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd. As the resin, trade names “Epicron HP-4032”, “Epicron HP-4700”, “Epicron HP-4200” manufactured by DIC Corporation, and “NC-7000L” trade names manufactured by Nippon Kayaku Co., Ltd. As the phenol novolac type epoxy resin, trade names jER152 and jER154 manufactured by Japan Epoxy Resin Co., Ltd., trade names EPPN-201-L manufactured by Nippon Kayaku Co., Ltd., trade names Epicron N-740 manufactured by DIC Corporation, and Epicron N-770, trade name Epototo YDPN-638 manufactured by Toto Kasei Co., Ltd., and cresol novolac type epoxy resin include trade names EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. Product names Epicron N-660, Epicron N-670, Epicron N-680, Epicron N-695, and trisphenolmethane type epoxy resin manufactured by DIC Corporation include trade names EPPN-501H and EPPN manufactured by Nippon Kayaku Co., Ltd. -501HY, EPP As the -502H, dicyclopentadiene type epoxy resin, trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd., the trade name Epicron HP-7200 manufactured by DIC Corporation, and as the amine type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. Trade names of jER604 and jER630, trade names of Toto Kasei Co., Ltd. Epototo YH-434, Epototo YH-434L, trade names of TEGAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd. Product names jER871, jER872, jERYL7175, jERYL7217, product names Epicron EXA-4850 manufactured by DIC Corporation, and urethane-modified epoxy resins include product names Adeka Resin EPU-6 manufactured by ADEKA Corporation, A As the Kalejin EPU-73, Adeka Resin EPU-78-11, rubber-modified epoxy resin, trade names Adeka Resin EPR-4023, Adeka Resin EPR-4026, Adeka Resin EPR-1309, and Chelate-modified epoxy resin manufactured by ADEKA Co., Ltd. ADEKA brand names Adeka Resin EP-49-10, Adeka Resin EP-49-20, and heterocyclic ring-containing epoxy resins include the brand name TEPIC made by Nissan Chemical Co., Ltd. These may be used alone or in combination of two or more. Can be used in combination.

  The compound (B) having a reactive group that reacts with a carboxyl group is blended so as to be 0.5 to 200 parts by weight with respect to 100 parts by weight of the compound (A) having a carboxyl group, It is preferable because the heat resistance, chemical resistance, and electrical insulation reliability of the cured film obtained by curing the photosensitive resin composition can be improved.

  (B) When the compound having a reactive group that reacts with a carboxyl group is less than the above range, it is difficult to obtain the effect by adding, and when it is too much, the photosensitive resin composition is used as a base material. Since the stickiness of the coating film obtained by applying and drying the coating film increases, the productivity decreases, and when the crosslinking density becomes too high, the cured film may become brittle and easily cracked.

<(C) Oxime ester photopolymerization initiator>
The (C) oxime ester photopolymerization initiator in the present invention is at least one of the following general formula (1) in the molecule.

Wherein R ₁ and R ₂ are each independently hydrogen, an alkyl group (which may be substituted with a hydroxyl group, and may have one or more oxygen atoms in the middle of the alkyl chain), cycloalkyl A group, an alkanoyl group, a benzoyl group (which may be substituted with an alkyl group or a phenyl group), or a phenyl group (which may be substituted with an alkyl group, a phenyl group or a halogen atom).
It is a compound that has an oxime ester structure represented by the following formula, is activated by energy such as UV, and initiates / promotes a reaction of a radical polymerizable group. Moreover, the said (C) oxime ester photoinitiator is mix | blended with the A agent containing the said (A) compound which has a carboxyl group. By adopting the above configuration, it is easy to dissolve and disperse the component (C) using the organic solvent used in the reaction when the component (A) is obtained, and thus the storage stability is excellent.

  The (C) oxime ester photopolymerization initiator is not particularly limited. For example, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxyome), (acetyloxyiminomethyl) thioxanthen-9-one, etc. It is done. By using the (C) oxime ester photopolymerization initiator, a highly sensitive photosensitive resin composition can be obtained in a small amount.

  The (C) oxime ester photopolymerization initiator is preferably blended in an amount of 0.01 to 50 parts by weight with respect to 100 parts by weight of the compound (A) having a carboxyl group. The blending ratio is preferable because the photosensitivity of the photosensitive resin composition is improved. When the component (C) is less than the above range, the reaction of the radical polymerizable group at the time of light irradiation hardly occurs, and the curing may be insufficient. Moreover, when there are more (C) components than the said range, adjustment of light irradiation amount becomes difficult and may be in an overexposed state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.

<(D) Compound not having a carboxyl group but having a photosensitive group>
In the present invention, (D) a compound having no carboxyl group and having a photosensitive group substantially has no carboxyl group and contains in the molecule a radical polymerizable group that undergoes a polymerization reaction with a radical polymerization initiator. It is a compound. Moreover, it is preferable to contain the said (D) compound which does not have a carboxyl group but has a photosensitive group in A agent and / or B agent.

  The compound (D) having no carboxyl group and having a photosensitive group is preferably a resin having at least one unsaturated double bond in the molecule. Furthermore, the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.

  Examples of the compound (D) having no carboxyl group and having a photosensitive group include bisphenol F EO-modified (n = 2 to 50) diacrylate, bisphenol A EO-modified (n = 2 to 50) diacrylate, and bisphenol S. EO modified (n = 2-50) diacrylate, bisphenol F EO modified (n = 2-50) dimethacrylate, bisphenol A EO modified (n = 2-50) dimethacrylate, bisphenol S EO modified (n = 2-50) ) Dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol Hexahexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate Methacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate Phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol Dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [ 4- (methacryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy-polyeth) Xyl) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2-bis [4- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy. Polyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, Nonylphenoxypolyethylene glycol acrylate, nonylphenoxypolypropylene glycol acrylate, isos Allyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol Dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane 2,4-diethyl-1,5-pentanediol diacrylate, ethoxylated tomethylolpropane triacrylate, propoxylated tomethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol Tetraacrylate, propoxylated pentathritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloylhexahydro-s-triazine, 4 , 4′-isopropylidene diphenol dimethacrylate, 4,4′-isopropylidene diphenol diacrylate, etc. Better Iga, but are not limited to these.

  In particular, the repeating unit of EO (ethylene oxide) contained in one molecule of diacrylate or dimethacrylate is preferably in the range of 2-50, more preferably 2-40. By using a resin having an EO repeating unit in the range of 2 to 50, the solubility of the photosensitive resin composition in an aqueous developer typified by an alkaline aqueous solution is improved and the development time is shortened. Stress is unlikely to remain in the cured film obtained by curing the composition. For example, among printed wiring boards, curling of the printed wiring board can be suppressed when laminated on a flexible printed wiring board based on a polyimide resin. It has the characteristics of.

  The photosensitive resin composition is such that the compound (D) having no carboxyl group and having a photosensitive group is blended in an amount of 10 to 200 parts by weight per 100 parts by weight of the component (A). This is preferable in terms of improving the photosensitivity.

  When the component (D) is less than the above range, the alkali resistance of the cured coating after photo-curing the photosensitive resin composition is lowered, and the contrast when exposed and developed may be difficult to attach. In addition, when the component (D) is more than the above range, the coating film obtained by applying the photosensitive resin composition on the substrate and drying the solvent becomes more sticky, resulting in decreased productivity. Moreover, when the crosslinking density becomes too high, the cured film may be brittle and easily cracked. For this reason, it is possible to set the resolution at the time of exposure / development to an optimal range by setting the value within the above range.

<Moisture content>
The photosensitive resin composition preparation kit comprising at least two agents of agent A and agent B in the present invention comprises (A) a compound having a carboxyl group in agent A, and (C) an oxime ester photopolymerization initiator. And the water content in the agent A is 5000 ppm or less. More preferably, it is 3000 ppm or less, and particularly preferably 1000 ppm or less. By controlling the water content to 5000 ppm or less, hydrolysis of the (C) oxime ester photopolymerization initiator that occurs in an acidic atmosphere in which (A) a compound having a carboxyl group is present is suppressed, and excellent long-term storage stability.

  The method for measuring the amount of water is not particularly limited, and examples thereof include a Karl Fischer titration method, a drying method under normal pressure or reduced pressure, and a measuring method using infrared rays.

<Other ingredients>
In the photosensitive resin composition of the present invention, a flame retardant can be further used as necessary. Examples of the flame retardant include a phosphorus flame retardant, a halogen-containing compound, a metal hydroxide, and a melamine compound. Among them, phosphorus flame retardants are preferable from the viewpoint of environmental impact and flame retardant effect. For example, red phosphorus, condensed phosphate ester compounds, cyclic organic phosphorus compounds, phosphazene compounds, phosphorus-containing (meth) acrylate compounds , Phosphorus-containing epoxy compounds, phosphorus-containing polyol compounds, phosphorus-containing amine compounds, ammonium polyphosphate, melamine phosphate, phosphinate, and the like. In particular, the use of phosphinate is preferable because it can impart excellent flame retardancy to the insulating film, and the bleedout of the flame retardant from the insulating film is small, so that contact failure and process contamination can be suppressed. . The said flame retardant can be used individually or in combination of 2 or more types.

  Various additives such as a filler, an adhesion assistant, an antifoaming agent, a leveling agent, a colorant, and a polymerization inhibitor can be further added to the photosensitive resin composition of the present invention as necessary. The above various additives can be used alone or in combination of two or more. Moreover, it is desirable to select each content suitably. As the filler, a fine inorganic filler such as silica, mica, talc, barium sulfate, wollastonite, calcium carbonate, or a fine organic polymer filler may be contained. Moreover, as said antifoamer, a silicon type compound, an acryl-type compound, etc. can be contained, for example. Moreover, as said leveling agent, a silicon type compound, an acryl-type compound, etc. can be contained, for example. Moreover, as said coloring agent, a phthalocyanine type compound, an azo type compound, carbon black, a titanium oxide etc. can be contained, for example. Moreover, as said adhesion assistant (it is also called adhesiveness imparting agent), a silane coupling agent, a triazole type compound, a tetrazole type compound, a triazine type compound, etc. can be contained. Moreover, as said polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, etc. can be contained, for example.

<Method of mixing agent A and agent B>
The agent A in the present invention is, for example, the compound (A) having a carboxyl group, (C) an oxime ester-based photopolymerization initiator, (D) a compound having a photosensitive group without having a carboxyl group, if necessary, and the like. The components and organic solvent can be obtained by grinding and dispersing and mixing. The method of pulverizing and dispersing is not particularly limited, and examples thereof include a method performed using a general kneading apparatus such as a bead mill, a ball mill, or a three roll.

  The particle diameter of the particles contained in the agent A can be measured by a method using a gauge defined in JIS K 5600-2-5. Moreover, if a particle size distribution measuring apparatus is used, an average particle diameter, a particle diameter, and a particle size distribution can be measured.

  On the other hand, the B agent in the present invention is a compound having a reactive group which reacts with the carboxyl group (B), a compound having a photosensitive group without (D) a carboxyl group as required, other components, and an organic solvent. Can be obtained by pulverizing and dispersing and mixing. The method of pulverizing and dispersing is not particularly limited, and examples thereof include a method performed using a general kneading apparatus such as a bead mill, a ball mill, or a three roll. The particle diameter of the particles contained in the agent B can be measured by a method using a gauge defined in JIS K 5600-2-5. Moreover, if a particle size distribution measuring apparatus is used, an average particle diameter, a particle diameter, and a particle size distribution can be measured.

(II) Method of using photosensitive resin composition preparation kit The photosensitive resin composition preparation kit of the present invention is composed of at least agent A and agent B, which is a composition different from agent A. The photosensitive resin composition obtained by mixing the agent and the B agent can be directly used to form a cured film or a relief pattern as follows. Moreover, after preparing the photosensitive resin composition solution which diluted the said photosensitive resin composition with the organic solvent, a cured film or a relief pattern can also be formed as follows.

  First, the said photosensitive resin composition obtained by mixing A agent and B agent, or the said photosensitive resin composition solution is apply | coated to a board | substrate, this is dried and an organic solvent is removed. Application to the substrate can be performed by screen printing, curtain roll, reverse roll, spray coating, spin coating using a spinner, or the like. The coating film (preferably thickness: 5 to 100 μm, particularly preferably 10 to 100 μm) is dried at 120 ° C. or less, preferably 40 to 100 ° C.

  Next, after drying, a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, and electron beams. Next, the relief pattern can be obtained by washing out the unexposed portion with a developer using various methods such as shower, paddle, immersion, or ultrasonic wave. Since the time until the pattern is exposed varies depending on the spraying pressure and flow rate of the developing device and the temperature of the etching solution, it is desirable to find the optimum device conditions as appropriate.

  As the developer, an aqueous alkaline solution is preferably used, and the developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, or N-methyl-2-pyrrolidone. Good. Examples of the alkaline compound that gives the alkaline aqueous solution include hydroxides, carbonates, hydrogen carbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions, and specifically sodium hydroxide. , Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium Hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triiso Etc. can be mentioned Ropiruamin, aqueous solution with compounds of other long as it exhibits basicity can also be naturally used. The concentration of the alkaline compound that can be suitably used in the development step of the photosensitive resin composition in the present invention is 0.01 to 20% by weight, particularly preferably 0.02 to 10% by weight. Further, the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. Is preferably used.

  The relief pattern formed by the development process is rinsed to remove unnecessary residues. Examples of the rinsing liquid include water and acidic aqueous solutions.

  Next, heat treatment of the relief pattern obtained above is performed. By carrying out heat treatment to react the reactive groups remaining in the molecular structure, a cured film having high heat resistance can be obtained. The thickness of the cured film is determined in consideration of the wiring thickness and the like, but is preferably about 2 to 50 μm. The final curing temperature at this time is desired to be able to be cured by heating at a low temperature for the purpose of preventing oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate.

  The curing temperature at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 180 ° C. or lower. If the final heating temperature is high, the wiring is oxidatively deteriorated, which is not desirable.

  The cured film formed from the photosensitive resin composition of the present invention is excellent in flame retardancy, heat resistance, chemical resistance, electrical and mechanical properties, and excellent in flexibility.

  In addition, for example, the insulating film obtained from the photosensitive resin composition preferably has a thickness of about 2 to 50 μm and a resolution of at least 10 μm after photocuring, particularly a resolution of about 10 to 1000 μm. For this reason, the insulating film obtained from the photosensitive resin composition is particularly suitable as an insulating material for a high-density flexible substrate. Furthermore, it is used for various photo-curing wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings, and the like.

  In addition, this invention can provide the same insulating material even if it uses the resin film obtained by apply | coating the said photosensitive resin composition or the photosensitive resin composition solution to the base-material surface, and drying.

  In the photosensitive resin composition preparation kit according to the present invention, the photosensitive resin composition can be prepared by mixing at least two agents of agent A and agent B. And after apply | coating the said photosensitive resin composition to a base-material surface, a resin film can be produced by drying the said mixture. Furthermore, by irradiating the resin film with light, the resin film can be cured and an insulating film can be manufactured. A printed wiring board with an insulating film can be produced by applying, drying and photocuring the photosensitive resin composition on the printed wiring board. The present invention can also provide a photosensitive resin composition, a resin film, an insulating film, and a printed wiring board with an insulating film obtained as described above.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
<(A) Synthesis of Compound Having Carboxyl Group>
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 14.0 g of methacrylic acid, 38.0 g of ethyl acrylate, 38.0 g of methyl methacrylate, 10.0 g of styrene, 0.04 of azobisisobutyronitrile as a radical polymerization initiator were previously mixed at room temperature. 4g was dripped from the dropping funnel over 3 hours in the state kept at 80 degreeC. After completion of the dropwise addition, the reaction solution was heated to 90 ° C. while stirring, and further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a compound solution having a carboxyl group of the present invention. The resulting resin solution had a solid content concentration of 50%, a weight average molecular weight of 71,000, and a solid content acid value of 90 mgKOH / g. The solid content concentration, weight average molecular weight, and acid value were measured by the following methods.

<Concentration of solid content>
The measurement was performed according to JIS K 5601-1-2. The drying conditions were 170 ° C. × 1 hour.

<Weight average molecular weight>
The weight average molecular weight was measured under the following conditions.
Equipment used: Tosoh HLC-8220GPC equivalent column: Tosoh TSK gel Super AWM-H (6.0 mm ID x 15 cm) x 2 guard columns: Tosoh TSK guard column Super AW-H
Eluent: 30 mM LiBr + 20 mM H3PO4 in DMF
Flow rate: 0.6 mL / min
Column temperature: 40 ° C
Detection conditions: RI: Polarity (+), response (0.5 sec)
Sample concentration: about 5 mg / mL
Standard product: PEG (polyethylene glycol).

<Acid value>
Measurement was performed according to JIS K 5601-2-1.

(Examples 1-5)
(A) a compound having a carboxyl group, (B) a compound having a reactive group that reacts with the carboxyl group, (C) an oxime ester photopolymerization initiator, and (D) a compound having no photosensitive group and having a photosensitive group. Then, other components and 1,2-bis (2-methoxyethoxy) ethane, which is an organic solvent, were added to prepare a photosensitive resin composition comprising an agent A and an agent B. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. At this time, each of the A agent and the B agent was mixed and dispersed by performing two passes with three rolls. Further, Examples 1 to 3 were packaged immediately after being dispersed, whereas Example 4 was packaged after being left in an environment of 25 ° C. and 50 RH for 2 days and in Example 5 for 4 days. The mixing ratio for obtaining the mixture of agent A and agent B is a ratio as shown in the table. For example, in Example 1, agent A (converted to resin solids) 91 g and agent B (converted to resin solids) 20 g Were mixed. In addition, the water content of agent A was measured using a Karl Fischer moisture meter (CA-100, VA-100 manufactured by Mitsubishi Chemical).

<1> Resin containing carboxyl group and photosensitive group (product name of Nippon Kayaku Co., Ltd. acid-modified epoxy acrylate)
<2> Resin containing carboxyl group and photosensitive group (product name of acid-modified epoxy acrylate manufactured by Nippon Kayaku Co., Ltd.)
<3> Product name of oxime ester photopolymerization initiator manufactured by BASF Japan <4> Product name of bisphenol A type dimethacrylate manufactured by Hitachi Chemical Co., Ltd. <5> Phosphazene compound (phosphorus flame retardant) manufactured by Otsuka Chemical Co., Ltd. Product name <6> Product name of liquid epoxy resin manufactured by Mitsubishi Chemical.

<Preparation of coating film on polyimide film>
The photosensitive resin composition consisting of the above-mentioned agent A and agent B is mixed, and the final dry thickness is 20 μm on a 25 μm polyimide film (manufactured by Kaneka Corporation: trade name Apical 25 NPI) using a baker type applicator. The film was cast and applied to an area of 100 mm × 100 mm and dried at 80 ° C. for 20 minutes. After placing a negative photomask as necessary, exposure was performed by irradiating with an ultraviolet ray having an accumulated exposure amount of 300 mJ / cm ² . Subsequently, spray development was performed for 60 seconds at a discharge pressure of 1.0 kgf / mm ² using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. After development, the film was thoroughly washed with pure water, and then cured by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition on the polyimide film.

<Evaluation>
A coating film was prepared by the above method using the photosensitive resin composition, and the following items were evaluated. The evaluation results are shown in Table 2.

(I) Photosensitive Storage Stability 20 μm thick photosensitivity on the surface of a 25 μm thick polyimide film (manufactured by Kaneka Corporation: Apical 25 NPI) in the same manner as in the above item <Preparation of coating film on polyimide film>. A cured film laminated film of the resin composition was produced. During the exposure, a 21-step tablet photomask (T2115 manufactured by Stouffer) was used. The step tablet step number of the cured film was used as a reference value.
The 21-step tablet photomask is divided into regions of 1 to 21 steps that are stepwise different in the light transmittance range of 0 to 100%. The photosensitive resin composition can be evaluated by covering the photosensitive resin composition with exposure and examining the number of steps to be cured.
In this example, the number of step tablet stages obtained by evaluating the photosensitive resin composition obtained by mixing the agent A and the agent B before being stored at 40 ° C. was used as a reference value.
Furthermore, the A agent and B agent before mixing were stored at 40 ° C., and the same evaluation was performed after each elapsed day. Thereafter, a determination was made based on the following criteria.
◎ After 300 days, the number of step tablet steps is in the range of ± 1 with respect to the reference value.
○ After 50 days, the number of step tablet steps is within ± 1 of the reference value.
ΔAfter 10 days, the number of steps of the step tablet is in the range of ± 1 with respect to the reference value.
× After 10 days, the step tablet plate number is not in the range of ± 1 relative to the reference value.

(Ii) Flame retardancy In accordance with the UL94VTM method of plastic material flammability test, the flammability test was conducted as follows. A cured film of photosensitive resin composition having a thickness of 20 μm on both sides of a polyimide film having a thickness of 25 μm (manufactured by Kaneka Corporation: trade name Apical 12.5 NPI) in the same manner as the above item <Preparation of coating film on polyimide film> A laminated film was produced. Cut out the sample prepared above into dimensions: 50 mm width x 200 mm length x 75 μm thickness (including the thickness of the polyimide film), put a marked line in the 125 mm part, round it into a cylinder with a diameter of about 13 mm, and above the marked line PI tape was affixed so that there was no gap in the overlapping part (75 mm location) and the upper part, and 20 flame retardant test tubes were prepared. Of these, 10 were treated at (1) 23 ° C./50% relative humidity / 48 hours, and the remaining 10 were treated at (2) 70 ° C. for 168 hours and then cooled in a desiccator containing anhydrous calcium chloride for 4 hours or more. The upper part of these samples is clamped and fixed vertically, and a burner flame is brought close to the lower part of the sample for 3 seconds to ignite. After 3 seconds, move the burner flame away and measure how many seconds after the sample flame or burning disappears.
○: For each condition ((1), (2)), the flame and combustion stopped within 10 seconds on average (average of 10) after the flame of the burner was moved away from the sample, and self-extinguishment within 10 seconds at maximum However, it has not burned to the rating line.
X: Even one of the samples does not extinguish within 10 seconds, or the flame rises to a point above the rating line and burns.

(Iii) Solder heat resistance of the photosensitive resin composition having a thickness of 20 μm on the surface of a polyimide film having a thickness of 75 μm (Apical 75NPI manufactured by Kaneka Corporation) in the same manner as the above item <Preparation of coating film on polyimide film>. A cured film laminated film was produced.
The coated film was floated so that the surface coated with the cured film of the photosensitive resin composition was in contact with a solder bath completely dissolved at 260 ° C., and then pulled up 10 seconds later. The operation was performed three times, and the state of the film surface was observed.
○: There is no abnormality in the coating film.
X: Abnormality such as swelling or peeling occurs in the coating film.

(Iv) Solvent resistance The solvent resistance of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated. In the evaluation method, the film was dipped in methyl ethyl ketone at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: There is no abnormality in the coating film.
X: Abnormality such as swelling or peeling occurs in the coating film.

(V) Electrical insulation reliability Line width / space width on flexible copper-clad laminate (electrolytic copper foil thickness 12μm, polyimide film is made of Kaneka Corporation Apical 25NPI, polyimide adhesive bonded copper foil) = 100 μm / 100 μm comb-shaped pattern was prepared, immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, washed with pure water, and subjected to a copper foil surface treatment. Thereafter, a cured film of a photosensitive resin composition having a thickness of 20 μm was prepared on the comb pattern by the same method as the above <Preparation of coating film on polyimide film>, and the test piece was adjusted. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
○: A resistance value of 10 8 or more in 1000 hours after the start of the test, and no occurrence of migration or dendrite.
X: Migration, dendrite, etc. occurred in 1000 hours after the start of the test.

(Comparative Examples 1-2)
As in the examples, a photosensitive resin composition composed of agent A and agent B was prepared. Moreover, after dispersion | distribution, it was allowed to stand in an environment of 25 ° C. and 50 RH for 6 days in Comparative Example 1 and for 8 days in Comparative Example 2, and then packed. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the type of raw material. Evaluation was performed in the same manner as in the Examples using the obtained photosensitive resin composition. The evaluation results are shown in Table 2.

(Comparative Example 3)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and an air introduction tube, 217.0 g of a cresol novolac type epoxy resin (epoxy equivalent 217), 0.2 g of hydroquinone as a polymerization inhibitor, and 1.0 g of triphenylphosphine as a catalyst Then, 204.8 g of carbitol acetate was charged as a polymerization solvent, and the temperature was raised to 80 ° C. with stirring under an air stream. Next, the mixture was allowed to react for 16 hours with stirring in a state where the temperature was kept at 85 to 105 ° C. while gradually adding 72.0 g of acrylic acid. Furthermore, 91.2 g of tetrahydrophthalic anhydride was subjected to an addition reaction to obtain a compound solution (A) having a carboxyl group. The obtained (A) carboxyl group-containing compound solution had a solid content concentration of 65% and an acid value of the solid content of 65 mgKOH / g. In addition, solid content concentration and acid value were measured by the same method as the synthesis example.
The agent A is (A) 100.0 g of the compound solution having a carboxyl group obtained above, 10.0 g of dipentaerythritol hexaacrylate as the component (D), an antifoaming agent (product name FLOREN AC manufactured by Kyoeisha Chemical Co., Ltd.) -300) 1.0 g, barium sulfate 80.0 g, and phthalocyanine green 0.5 g were prepared. In addition, the B agent contains 20.0 g of a cresol novolac type epoxy resin (product name EOCN1020 manufactured by Nippon Kayaku Co., Ltd.) and a bisphenol A type epoxy resin (product name jER828 manufactured by Mitsubishi Chemical Corporation) as component (B) 10. 0 g, (acetyloxyiminomethyl) thioxanthen-9-one (manufactured by BASF Japan Ltd., product name CGI-325 of oxime ester photopolymerization initiator) as component (C), diethylthioxanthone (Nippon Kayaku) It was prepared by blending 1.0 g of product name KAYACURE DETX-S manufactured by Co., Ltd. and 2.5 g of 4-dimethylaminobenzoic acid ethyl ester (product name KAYACURE EPA manufactured by Nippon Kayaku Co., Ltd.). A agent and B agent were mixed and the photosensitive resin composition was produced. 191.5g of the said mixing | blending and 38.5g of B agents were mixed, and it evaluated by the method similar to an Example using the obtained photosensitive resin composition. The evaluation results are shown in Table 2.

Claims (9)

A photosensitive resin composition preparation kit comprising at least two agents of agent A and agent B,
The agent A contains (A) a compound having a carboxyl group, and (C) an oxime ester photopolymerization initiator, and the water content in the agent A is 5000 ppm or less,
The said B agent contains the compound which has the reactive group which reacts with the carboxyl group (B), The photosensitive resin composition preparation kit characterized by the above-mentioned.   The photosensitive resin composition preparation kit according to claim 1, wherein the compound (B) having a reactive group that reacts with a carboxyl group is (b1) an epoxy resin.   Furthermore, the agent A and / or B agent contains (D) the compound which does not have a carboxyl group but has a photosensitive group, The photosensitive resin composition preparation kit of Claim 1 or 2 characterized by the above-mentioned. It is a manufacturing method of the photosensitive resin composition manufactured using the photosensitive resin composition preparation kit of any one of Claims 1-3,
A method for producing a photosensitive resin composition, comprising mixing at least two agents of agent A and agent B. It is a manufacturing method of the resin film manufactured using the photosensitive resin composition preparation kit of any one of Claims 1-3,
A method for producing a resin film, comprising: applying a mixture of at least two agents of agent A and agent B to a substrate surface, and drying the mixture.   A method for producing an insulating film, comprising: curing a resin film obtained by the method for producing a resin film according to claim 5.   A method for producing a printed wiring board with an insulating film, wherein the insulating film obtained by the method for producing an insulating film according to claim 6 is coated on a printed wiring board. A method for storing a compound constituting a photosensitive resin composition comprising at least (A) a compound having a carboxyl group, (C) an oxime ester photopolymerization initiator, and (B) a compound having a reactive group that reacts with a carboxyl group. There,
(A) a compound having a carboxyl group, (C) an A agent having an oxime ester photopolymerization initiator and having a water content of 5000 ppm or less in the A agent;
(B) Prepare 2 or more agents with the B agent containing the compound which has a reactive group which reacts with a carboxyl group,
A storage method characterized by storing at least A agent and B agent separately.   The storage method according to claim 8, wherein the compound (B) having a reactive group that reacts with a carboxyl group is (b1) an epoxy resin.