JP5789454B2 - Novel photosensitive resin composition preparation kit and use thereof - Google Patents

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.

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

  In the above patent document, various methods for solving the problem of the coverlay are proposed. However, the flame retardant photocurable resin compositions 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 the carboxyl group-containing resin is photosensitive. Since it has a group, the crosslinking density of the cured film is increased, and 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, and the essence is different from the invention of this application.

  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 mix and use each composition immediately before use, it is a long time between the carboxyl group in the carboxyl group-containing resin and the oxime ester photopolymerization initiator. Degradation of the oxime ester photopolymerization initiator due to contact with the water is prevented. Furthermore, since it is possible to avoid long-time contact between the highly sensitive oxime ester photopolymerization initiator and the reactive diluent, it is considered that the reaction of the reactive diluent is prevented and the storage stability is excellent.

  However, since the carboxyl group-containing resin has a photosensitive group, the crosslinking density increases, and the cured film cannot obtain sufficient flexibility. Furthermore, since the structure which acquires a flame retardance is not assumed, it is scarce in a flame retardance, and when a flame retarder is used and sufficient flame retardance is obtained, it will be assumed that another characteristic fall is brought about.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors are a photosensitive resin composition preparation kit comprising at least two agents of agent A and agent B, wherein agent A is (a1) urethane A compound having a bond and no photosensitive group is contained, and the agent B contains (b1) an epoxy resin and (b2) an oxime ester photopolymerization initiator. The kit consists of (b1) oxime ester photopolymerization initiation by long-term contact between (a1) a urethane bond in a compound having a urethane bond and no photosensitive group and (b2) an oxime ester photopolymerization initiator. Deterioration of the agent is prevented, the photosensitive property does not decrease after long-term storage, and the photosensitive resin composition prepared using the photosensitive resin composition preparation kit has photosensitivity and can be finely processed. And It can be developed with dilute alkaline aqueous solution, can be cured at low temperature (200 ° C or less), has no deterioration in photosensitivity after long-term storage, has excellent storage stability, and has a cured film that is flexible and has electrical insulation reliability. The knowledge of obtaining a photosensitive resin composition having excellent solder heat resistance, organic solvent resistance, flame retardancy, and low warpage of the substrate after curing has been obtained, and based on these findings, the present invention has been achieved. is there.

  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,
The agent A contains (a1) a compound having a urethane bond and no photosensitive group,
The agent B is a photosensitive resin composition preparation kit characterized by containing (b1) an epoxy resin and (b2) an oxime ester photopolymerization initiator.

  Moreover, as for the photosensitive resin composition preparation kit concerning this invention, it is preferable that the compound which does not have (a1) urethane bond and has a photosensitive group has a carboxyl group.

  Moreover, it is preferable that the photosensitive resin composition preparation kit concerning this invention contains the compound which does not have a carboxyl group (c1) at least in B agent, and has a photosensitive group further.

  Moreover, it is preferable that the photosensitive resin composition preparation kit concerning this invention contains the compound which has (a2) carboxyl group and a photosensitive group further in A agent.

  Moreover, as for the photosensitive resin composition preparation kit concerning this invention, it is preferable that the said (b1) epoxy resin exists in solid in B agent at room temperature (25 degreeC).

  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 relates to a compound constituting a photosensitive resin composition comprising at least (a1) a compound having a urethane bond and no photosensitive group, (b1) an epoxy resin, and (b2) an oxime ester photopolymerization initiator. (A1) A agent containing a compound having a urethane bond and no photosensitive group, and (b1) an epoxy resin and (b2) an oxime ester-based photopolymerization initiator B Two or more preparations with the agent,
It also includes a storage method characterized by storing at least A agent and B agent separately.

  Moreover, as for the preservation | save method of the compound which comprises the photosensitive resin composition concerning this invention, it is preferable that the said (a1) compound which has a urethane bond and does not have a photosensitive group has a carboxyl group.

  Moreover, it is preferable that the preservation | save method of the compound which comprises the photosensitive resin composition concerning this invention contains the compound which does not have a carboxyl group (c1) at least in B agent, and has a photosensitive group.

  The photosensitive resin composition preparation kit of the present invention is excellent in storage stability with no decrease in photosensitivity after long-term storage. 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.

It is the schematic diagram which has measured the curvature amount of the film.

  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 comprising at least two agents of agent A and agent B,
The agent A contains (a1) a compound having a urethane bond and no photosensitive group,
The agent B may be a photosensitive resin composition preparation kit characterized by containing (b1) an epoxy resin and (b2) an oxime ester photopolymerization initiator.

  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.

  Moreover, as for the photosensitive resin composition preparation kit concerning this invention, it is preferable that the compound which does not have (a1) urethane bond and has a photosensitive group has a carboxyl group.

  Here, since the productivity is generally excellent, the photopolymerization initiator is often used as a component of the agent A. However, when the (b2) oxime ester-based photopolymerization initiator used in the present invention is used as the composition of the agent A, the storage stability is greatly reduced, so that it cannot be used in a general composition. Surprisingly, however, the kit for preparing a photosensitive resin composition of the present invention has high storage stability and excellent various properties even though (b2) an oxime ester photopolymerization initiator is used. The inventors have found. This is presumed to be due to the following reasons. That is, the photosensitive resin composition preparation kit of the present invention contains at least (a1) a compound having a urethane bond and no photosensitive group. By having a urethane bond, the cured film is excellent in flexibility and chemical resistance, and by having substantially no photosensitive group, the crosslinked density of the cured film is not excessively increased and sufficient flexibility is obtained. Can be obtained. In addition, (a1) A agent containing a compound having a urethane bond and no photosensitive group, and (b1) epoxy resin, (b2) B agent containing an oxime ester photopolymerization initiator And after long-term storage, it is excellent in the storage stability of the photosensitive resin composition preparation kit. The reason why the storage stability of the photosensitive resin composition preparation kit is excellent is presumed to be due to the elimination of the stability-decreasing factors as described below. When (a1) a compound having a urethane bond and not having a photosensitive group and (b2) an oxime ester photopolymerization initiator coexist, a urethane bond acts, and (b2) an oxime ester photopolymerization initiator Promotes decomposition of the resin and decreases stability. Furthermore, when a carboxyl group coexists, the acidic atmosphere acts as a catalyst, the oxime ester is hydrolyzed, and the stability is lowered synergistically. Also, when (a1) a compound having a urethane bond and no photosensitive group and (b1) an epoxy resin coexist, the reaction between the residue of the raw material used for the urethane reaction and the epoxy group gradually proceeds at room temperature. And the stability is reduced. Furthermore, when a carboxyl group coexists, the reaction between the carboxyl group and the epoxy group gradually proceeds, and the stability is lowered.

  Hereinafter, the present invention will be described in detail with respect to the photosensitive resin composition.

<(A1) Compound having urethane bond and no photosensitive group>
The compound (a1) having a urethane bond and not having a photosensitive group used in the present invention has at least one urethane bond, and has a radical polymerizable group that undergoes a polymerization reaction substantially by a radical polymerization initiator. The compound is not particularly limited as long as it is not contained in the molecule. Here, “substantially not containing a photosensitive group in the molecule” means that the molecule does not need to contain any photosensitive group such as a (meth) acryloyl group or a vinyl group, and the effect of the present invention is manifested. If it is the range which does not impair this, you may contain. The range that does not impair the manifestation of the effect of the present invention is that the value determined by measuring the photosensitive group in the molecule of the component (a1) as an iodine value is less than 5. The iodine value is a value obtained by converting the amount of halogen bonded to 100 g of a sample into the number of g of iodine, and can be measured by a method defined in JIS K0070.

  The compound having a urethane bond can be obtained by an arbitrary reaction. For example, the following general formula (1)

(Wherein R ₁ represents a divalent organic group)
A diol compound represented by the following general formula (2)

(Wherein X ₁ represents a divalent organic group)
By reacting the diisocyanate compound represented by the following general formula (3)

(Wherein R ₁ and X ₁ each independently represent a divalent organic group, and n represents an integer of 1 or more)
It is obtained as a structure containing a repeating unit containing a urethane bond represented by

  The diol compound is not particularly limited. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol , Alkylene diols such as 1,4-cyclohexanedimethanol, polyoxyalkylene diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymers of tetramethylene glycol and neopentyl glycol, and polyhydric alcohols Polyols obtained by ring-opening addition reaction of lactones such as polyester diol, polycarbonate diol having carbonate skeleton, γ-butyllactone, ε-caprolactone, δ-valerolactone, etc. Examples include caprolactone diol, bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, and the like. These can be used alone or in combination of two or more.

The diisocyanate compound of the present invention is not particularly 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'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, Such as tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate Aromatic diisocyanate compounds, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, Diisocyanate, trimethylhexamethylene diisocyanate, aliphatic diisocyanate compounds such lysine diisocyanate, etc. These can be used alone or in combinations of two or more.
The reaction temperature between the diol compound and the diisocyanate compound is preferably 40 to 160 ° C, and more preferably 60 to 150 ° C. When the temperature is lower than 40 ° C., the reaction time becomes too long. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.

  The above reaction can be carried out in the absence of a solvent. However, in order to control the reaction, it is desirable to carry out the reaction in an organic solvent system. For example, examples of the organic solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N , N-dimethylformamide, formamide solvents such as N, N-diethylformamide, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2 Examples include pyrrolidone solvents such as -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, a solvent may be used ethers such as ethyl ether also ethylene glycol. Of these, symmetrical glycol diethers are preferably used because side reactions are unlikely to occur. The amount of solvent used in the reaction is desirably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. The solute weight concentration in the reaction solution is more preferably 10 wt% or more and 80 wt% or less. When the solution concentration is 5% or less, the polymerization reaction is difficult to occur, the reaction rate is lowered, and a desired structural substance may not be obtained.

  Moreover, it is preferable that the compound (a1) which has a urethane bond and does not have a photosensitive group has a carboxyl group. (A1) Introduction of a carboxyl group into a compound having a urethane bond and not having a photosensitive group can be obtained by any reaction. For example, in addition to the diol compound and the diisocyanate compound, the following general formula (4)

(Wherein R ₄ represents a trivalent organic group)
It can be obtained by reacting a compound containing two hydroxyl groups and one carboxyl group.

  The compound containing two hydroxyl groups and one carboxyl group of the present invention is not particularly limited as long as it has the above structure. For example, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2- Hydroxyethyl) propionic acid, 2,2-bis (3-hydroxymepropyl) propionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-bis (hydroxymethyl) butanoic acid, 2,2-bis (2-hydroxyethyl) butanoic acid, 2,2-bis (3-hydroxypropyl) butanoic acid, 2,3-dihydroxybutanoic acid, 2,4-dihydroxy-3,3-dimethylbutanoic acid, 2,3-dihydroxy Hexadecanoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxy Benzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, etc. These can be used alone or in combinations of two or more.

  In addition, the carboxyl group may be a carboxylic acid anhydride obtained by dehydration of two carboxyl groups. For example, the following general formula (5) is added to the isocyanate terminal of the reaction product of the diol compound and the diisocyanate compound.

(Wherein Y represents a tetravalent organic group)
It is obtained by reacting a tetracarboxylic dianhydride represented by

  The tetracarboxylic dianhydride of the present invention is not particularly limited as long as it has the above structure. 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) Propane dibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′- Biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic Tetracarboxylic acid dianhydride anhydrides, etc. These can be used alone or in combinations of two or more.

  A terminal carboxylic acid compound can be obtained by reacting a 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.

  The compound (a1) having a urethane bond and not having a photosensitive group is a base resin in the photosensitive resin composition of the present invention, and the weight average molecular weight is 1,000 or more in terms of polyethylene glycol. The range is preferably 2,000,000 or less, and more preferably 2,000 or more and 200,000 or less. 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.

<(B1) Epoxy resin>
The (b1) epoxy resin used in the present invention is blended in the B agent different from the A agent containing the compound (a1) having a urethane bond and not having a photosensitive group. By setting it as the said structure, there is no photosensitive fall after long-term storage, and the storage stability of the photosensitive resin composition preparation kit improves. The (b1) epoxy resin used in the present invention is a compound containing at least one epoxy group in the molecule. For example, as the bisphenol A type epoxy resin, trade names jER828 and jER1001 manufactured by Japan Epoxy Resin Co., Ltd. , JER1002, Adeka Resin EP-4100E, Adeka Resin EP-4300E manufactured by ADEKA Co., Ltd., RE-310S, RE-410S manufactured by Nippon Kayaku Co., Ltd., and Epicron 840S, Epicron 850S manufactured by DIC Corporation, Epicron 1050, Epicron 7050, product names Epototo YD-115, Epototo YD-127, Epototo YD-128, manufactured by Toto Kasei Co., Ltd. 806, 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. Trade name Epicron EXA-1514 and hydrogenated bisphenol A type epoxy resin include trade names jERYX8000, jERYX8034, jERYL7170, and ADEKA trade names ADEKA manufactured by Japan Epoxy Resin Co., Ltd. Jin 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, Japan Epoxy Resin Corporation product Names jERYX4000, jERYL6121H, jERYL6640, jERYL6677, trade names NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd. Epoxy resins include DIC Corporation's trade names Epicron HP-4032, Epicron HP-4700, Epicron HP-4200, and Nippon Kayaku Co., Ltd. trade names NC-700. As a 0L, 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., and trade name Epicron N-740 manufactured by DIC Corporation, Epicron N-770, trade name Epototo YDPN-638 manufactured by Toto Kasei Co., Ltd., cresol novolac type epoxy resin, trade names EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. DIC Corporation's product names Epicron N-660, Epicron N-670, Epicron N-680, Epicron N-695, Trisphenolmethane type epoxy resin, trade names EPPN-501H manufactured by Nippon Kayaku Co., Ltd., EPPN-501HY, E As PN-502H, dicyclopentadiene type epoxy resin, trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd., trade name Epicron HP-7200 manufactured by DIC Corporation, and as epoxy type resin, Japan Epoxy Resin Co., Ltd. Product names jER604, jER630 manufactured by Toto Kasei Co., Ltd., Epototo YH-434, Epototo YH-434L, Mitsubishi Gas Chemical Co., Ltd. trade names TETRAD-X, TERRAD-C, and flexible epoxy resins Trade names jER871, jER872, jERYL7175, jERYL7217, DIC Corporation's trade name Epicron EXA-4850 manufactured by Japan Epoxy Resin Co., Ltd., and urethane-modified epoxy resins are trade names Adeka Resin EPU-6 manufactured by ADEKA Corporation. Adeka Resin EPU-73, Adeka Resin EPU-78-11, and rubber-modified epoxy resins are trade names of Adeka Resin EPR-4023, Adeka Resin EPR-4026, Adeka Resin EPR-1309, and Chelate-modified Epoxy Resins Examples of trade names Adeka Resin EP-49-10, Adeka Resin EP-49-20, and heterocyclic-containing epoxy resins manufactured by ADEKA include trade names TEPIC manufactured by Nissan Chemical Co., Ltd. Among them, when the (b1) epoxy resin is present in the B agent in a solid state at room temperature (25 ° C.), the deterioration of the (b2) oxime ester photopolymerization initiator mixed in the B agent is small. The photosensitive resin composition is preferred in that it has no reduction in photosensitivity and is excellent in storage stability. For example, trade names jERYX4000, jERYX4000K, jERYX4000H, jERYX4000HK, jERYX8800, manufactured by Nissan Chemical Industries, Ltd. TEPIC-G, TEPIC-P, TEPIC-S, TEPIC-SP, Nippon Kayaku Co., Ltd. GTR-1800, etc. are mentioned.

  Here, (b1) that the epoxy resin exists as a solid in the B agent at room temperature (25 ° C.) means that the epoxy resin that is solid at room temperature (25 ° C.) is completely dissolved in the B agent. It means that the whole or part of the epoxy resin is present as a solid. The presence of the solid in the agent B can be confirmed by measuring the particle diameter by a method using a gauge specified in JIS K 5600-2-5.

  The (b1) epoxy resin is blended so as to be 0.5 to 100 parts by weight with respect to 100 parts by weight of the compound (a1) having a carboxyl group and not having a photosensitive group. This is preferable because the heat resistance, chemical resistance, and electrical insulation reliability of the cured film of the conductive resin composition can be improved.

  When the amount of the epoxy resin is less than the above range, it is difficult to obtain the effect by adding, and when the amount is too large, it is obtained by applying the photosensitive resin composition on the substrate and drying the solvent. Since the stickiness of the coating film to be obtained increases, the productivity is lowered, and when the crosslinking density becomes too high, the cured film may become brittle and easily cracked.

<(B2) Oxime ester photopolymerization initiator>
The (b2) oxime ester photopolymerization initiator in the present invention is a compound having an oxime ester structure, activated by energy such as UV, and initiating / promoting a reaction of a radical polymerizable group. In addition, the (b2) oxime ester photopolymerization initiator needs to be separated from the (a1) agent A containing a compound having a urethane bond and no photosensitive group. Although it will not specifically limit if it is divided with A agent, Since it is excellent in productivity and operativity, it is preferable to mix | blend with B agent similarly to the said (b1) epoxy resin. By setting it as the said structure, there is no photosensitive fall after long-term storage, and the storage stability of the photosensitive resin composition preparation kit improves. Examples of the (b2) oxime ester photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxyome) and the like.

  The (b2) oxime ester photopolymerization initiator is blended so as to be 0.01 to 50 parts by weight with respect to 100 parts by weight of the compound (a1) having a urethane bond and not having a photosensitive group. It is preferable. The blending ratio is preferable because the photosensitivity of the photosensitive resin composition is improved. When the amount of component (b2) is less than the above range, the reaction of the radical polymerizable group at the time of light irradiation hardly occurs and the curing is often insufficient. Moreover, when there are more (b2) components than the said range, adjustment of light irradiation amount becomes difficult and it may be in an overexposed state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.

<(C1) Compound having no carboxyl group and having a photosensitive group>
Since the oxime ester photopolymerization initiator has low solubility in solvents and other compositions, the oxime ester dissolved when the resin composition described in Patent Document 3 is stored in a low temperature environment for a long period of time. The photopolymerization initiator may recrystallize and precipitate in the composition, but the compound (c1) having no carboxyl group and having a photosensitive group in the present invention is (c1) photosensitive without having a carboxyl group. The compound having a functional group serves as a solvent for dissolving the (b2) oxime ester photopolymerization initiator, and the solubility of the (b2) oxime ester photopolymerization initiator in the agent B is improved. Even when stored for a long period of time, the dissolved (b2) oxime ester-based photopolymerization initiator is prevented from recrystallizing and precipitating in the B agent. Masui.

  The compound (c1) having no carboxyl group and having a photosensitive group in the present invention contains a radically polymerizable group that has substantially no carboxyl group and undergoes a polymerization reaction by a radical polymerization initiator in the molecule. It is a compound. Among these, a resin having at least one unsaturated double bond in the molecule is preferable. Furthermore, the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.

  Examples of the compound (c1) 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 Hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol Trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen Succinate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, 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-dimethacrylate Roxypropane, 2, 2 -Bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) 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 Chryrate, methoxytriethylene glycol acrylate, nonylphenoxypolyethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol di Methacrylate, 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, di Propylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4- (acryloxypolyethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolypropoxy) 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, glycerin Sidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, alloverbital, diallylamine, Diallyldimethylsilane, diallyl disulfide, diallyl ether, zalyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4'-isopropylidene diphenol dimethacrylate, 4 , 4′-isopropylidene diphenol diacrylate, etc. are preferred, but not limited thereto. 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 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. Furthermore, it is difficult for stress to remain in the cured film obtained by curing the photosensitive resin composition. For example, among the printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, curling of the printed wiring board is prevented. Features such as being able to be suppressed.

  In particular, it is particularly preferable to increase the photosensitivity by using the EO-modified diacrylate or dimethacrylate together with a compound having three or more acryloyl groups or methacryloyl groups. Isocyanuric acid EO-modified trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate Ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrime Rollpropane tetraacrylate, ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 2,2,2-trisacryloyloxymethyl ethyl succinic acid, 2,2,2 -Trisacryloyloxymethylethylphthalic acid, propoxylated ditrimethylolpropane tetraacrylate, propoxylated dipentaerythritol hexaacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, caprolactone Modified ditrimethylolpropane tetraacrylate, the following general formula (6)

(Where a + b = 6 and n = 12.)
A compound represented by the following general formula (7)

(Where a + b = 4 and n = 4)
A compound represented by the following formula (8)

A compound represented by the following general formula (9)

(Where m = 1, a = 2, b = 4, or m = 1, a = 3, b = 3, or m = 1, a = 6, b = 0, or m = 2, a = 6 B = 0.)
A compound represented by the following general formula (10)

(Where a + b + c = 3.6)
A compound represented by the following formula (11)

A compound represented by the following general formula (12)

(Where m · a = 3, a + b = 3, where “m · a” is the product of m and a)
A compound represented by the formula is preferably used.

  The photosensitive resin composition is such that the compound (c1) 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 (a1). This is preferable in terms of improving the photosensitivity.

  When the amount of the component (c1) is less than the above range, the alkali resistance of the cured film after photocuring the photosensitive resin composition may be lowered, and contrast may not be easily obtained when exposed and developed. In addition, when the component (c1) is larger 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 a decrease in 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.

<(A2) Compound having carboxyl group and photosensitive group>
The compound (a2) having a carboxyl group and a photosensitive group in the present invention means a compound having at least one carboxyl group and a photosensitive group. Since the compound (a2) having a carboxyl group and a photosensitive group has a carboxyl group, it is separated from the B agent containing the (b1) epoxy resin and the (b2) oxime ester photopolymerization initiator. Need to be. Although it is not particularly limited as long as it is separated from the B agent, it is excellent in productivity and operability, so that it is a composition of the A agent in the same manner as the compound (a1) having a carboxyl group and no photosensitive group. Is preferred. The compound (a2) having a carboxyl group and a photosensitive group is not particularly limited as long as it is a compound having a carboxyl group and a photosensitive group. For example, it can be obtained by reacting an epoxy compound with an unsaturated monocarboxylic acid. There are epoxy acrylates obtained by adding saturated or unsaturated polycarboxylic anhydrides to esters. 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. In addition, (a2) the compound having a carboxyl group and a photosensitive group may be commercially available, and the epoxy acrylate is, for example, Nippon Kayaku Co., Ltd. ZFR series, ZAR series, ZCR series, CCR series, PCR series. Examples of the urethane acrylate include UXE series manufactured by Nippon Kayaku Co., Ltd. Examples of the acrylated acrylate include Cyclomer ACA series manufactured by Daicel Cytec.

  The photosensitivity of the photosensitive resin composition is that the compound (a2) having a carboxyl group and a photosensitive group is blended in an amount of 10 to 200 parts by weight per 100 parts by weight of the component (a1). Is preferable in terms of improvement.

  When the amount of the component (a2) is less than the above range, the alkali resistance of the cured film after photocuring the photosensitive resin composition may be reduced, and contrast may not be easily obtained when exposed and developed. In addition, when the component (a2) is more than the above range, productivity decreases because the stickiness of the coating film obtained by applying the photosensitive resin composition on the substrate and drying the solvent increases. 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.

<Other ingredients>
Various additives such as a flame retardant, a filler, an adhesion assistant, an antifoaming agent, a leveling agent, a colorant, and a polymerization inhibitor can be added to the photosensitive resin composition of the present invention as necessary. As said flame retardant, a phosphate ester type compound, a halogen-containing compound, a metal hydroxide, an organic phosphorus type compound, etc. can be contained, for example. The above various additives can be used alone or in combination of two or more. Moreover, it is desirable to select each content suitably. Further, 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.

(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 mixture or the mixture solution is applied to a substrate and dried to remove the organic solvent. 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 alkali solution is preferably used. The developer is water-soluble such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone and the like. An organic solvent may be contained. 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 of the present invention is preferably 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)
<(A1) Synthesis of compound having urethane bond and no photosensitive group>
In a separable flask pressurized with nitrogen, methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) (30.0 g) was charged as a solvent for polymerization, and 30 g of norbornene diisocyanate was added thereto. 9 g (0.15 mol) was charged and dissolved by heating to 80 ° C. To this solution, 100.0 g (0.05 mol) of polycarbonate diol (manufactured by Asahi Kasei Co., Ltd .: trade name PCDL T5652, average molecular weight is 2000) and 22.2 g (0.002) of 2,2-bis (hydroxymethyl) butanoic acid. 15 mol) in methyl triglyme (123.2 g) was added over 1 hour. This solution was heated and stirred at 80 ° C. for 5 hours. By performing the above reaction, a resin solution having a urethane bond was obtained. The resulting resin solution had a solid content concentration of 50%, a weight average molecular weight of 5,000, and an acid value of the solid content of 55 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.

(Synthesis Example 2)
<(A1) Synthesis of compound having urethane bond and no photosensitive group>
In a separable flask pressurized with nitrogen, methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) (20.0 g) was charged as a solvent for polymerization. 5 g (0.075 mol) was charged and heated to 80 ° C. to dissolve. A solution obtained by dissolving 100.0 g (0.050 mol) of polycarbonate diol (trade name: PCDL T5652; average molecular weight: 2000) in methyltriglyme (82.4 g) over 1 hour was added to this solution. Added. This solution was heated and stirred at 80 ° C. for 5 hours. After completion of the reaction, 31.0 g (0.100 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride (hereinafter referred to as ODPA) and methyltriglyme (32.8 g) were added to the above reaction solution. . After the addition, the mixture was heated to 190 ° C. and reacted for 1 hour. The solution was cooled to 80 ° C. and 10.3 g of pure water was added. After the addition, the temperature was raised to 110 ° C. and heated to reflux for 5 hours. By performing the above reaction, a resin solution having a urethane bond was obtained. The resulting resin solution had a solid content concentration of 50%, a weight average molecular weight of 9,200, and an acid value of the solid content of 115 mgKOH / g. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Examples 1-4)
(A1) compound having urethane bond and having no photosensitive group obtained in Synthesis Examples 1 and 2, (b1) epoxy resin, (b2) oxime ester photopolymerization initiator, (c1) having carboxyl group A compound having a photosensitive group, (a2) a compound having a carboxyl group and a photosensitive group, other components, and 1,2-bis (2-methoxyethoxy) ethane which is an organic solvent, A photosensitive resin composition composed of agent B was prepared. 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. According to the method described in JIS K 5600-2-5, the obtained B agent was confirmed in particle size using a grindometer manufactured by Yasuda Seiki Seisakusho with a groove depth of 0 to 50 μm, and only Example 4 (b1 ) It was confirmed that the component was present in the B agent as a solid. The mixing ratio for obtaining the mixture of the A agent and the B agent is a ratio as shown in the table. For example, in Example 1, 80 g of the A agent (resin solid equivalent) and 44 g of the B agent (resin solid equivalent 31 g) ) Was mixed.

<1> Carboxyl group and photosensitive group-containing resin (product name of Nippon Kayaku Co., Ltd. carboxyl group and photosensitive group-containing resin, solid content: 65%)
<2> Product name of liquid epoxy resin manufactured by Japan Epoxy Resin <3> Product name of oxime ester photopolymerization initiator manufactured by BASF Japan <4> Product name of phosphazene compound (phosphorus flame retardant) manufactured by Otsuka Chemical Co., Ltd. <5> Product name of powder epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. <6> Product name of bisphenol A type dimethacrylate manufactured by Hitachi Chemical Co., Ltd.

<Preparation of coating film on polyimide film>
The photosensitive resin composition consisting of the above-mentioned agent A and agent B is mixed, and using a baker type applicator, 100 mm so that the final dry thickness is 20 μm on a 25 μm polyimide film (manufactured by Kaneka Corporation: trade name 25 NPI). The film was cast and applied to an area of × 100 mm and dried at 80 ° C. for 20 minutes. After placing a negative photomask as required, exposure was performed by irradiating with an ultraviolet ray having an accumulated exposure amount of 300 mJ / cm ² . Next, 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 Photosensitive resin having a thickness of 20 μm on the surface of a polyimide film having a thickness of 25 μm (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A cured film laminated film of the composition was prepared. During the exposure, a 21-step tablet photomask (T2115 manufactured by Stouffer) was used.

  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 with respect to the reference value.

(Ii) Warpage A cured film of a photosensitive resin composition having a thickness of 20 μm on the surface of a polyimide film having a thickness of 25 μm (Apical 25 NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A laminated film was produced.
The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The polyimide film (1) on which the photosensitive resin composition is laminated is placed on the smooth base (3), and the distance from the plane of the smooth base (3) to the film end ((2) in FIG. 1 ) Was measured and used as the amount of warpage (warp height). When the warp amount (warp height) at one end and the warp amount (warp height) at the other end are different, the larger one is evaluated as the warp amount (warp height) of the film. did.

  The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The warp amount is preferably 5 mm or less. In addition, when the film was rounded into a cylindrical shape, it was described as “x” in Table 2 below.

(Iii) Folding resistance of the photosensitive resin composition having a thickness of 20 μm on the surface of a polyimide film having a thickness of 25 μm (Apical 25NPI 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 evaluation method of the bending resistance of the cured film laminated film is that the cured film laminated film is cut into 50 mm × 10 mm strips, bent at 180 ° at 25 mm with the cured film on the outside, and a load of 5 kg is applied to the bent portion for 3 seconds. After placing, the load was removed, and the apex of the bent portion was observed with a microscope. After microscopic observation, the bent portion was opened, and a 5 kg load was again applied for 3 seconds, and then the load was removed to completely open the cured film laminated film. The above operation was repeated, and the number of occurrences of cracks in the bent portion was defined as the number of bending times.

(Iv) Flame retardancy In accordance with the UL94VTM method for flammability testing of plastic materials, flammability testing was performed 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.
×: Even one sample does not extinguish within 10 seconds, or the flame rises above the rating line and burns.

(V) Tackiness In the same manner as the above item <Preparation of coating film on polyimide film>, a photosensitive resin composition was applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) and dried. A coating film having a thickness of 20 μm after drying was obtained. The obtained film surface was bent and lightly overlapped, and a determination was made based on the following criteria.
◎ Faces do not stick together and no sticking marks remain.
○ Although the surfaces do not stick, there is a slight sticking mark.
ΔThe surfaces stick together but peel off easily.
X Surfaces stick together and cannot be easily removed.

(Vi) 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 in 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.

(Vii) 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.

(Viii) Electrical insulation reliability Line width / space width on flexible copper-clad laminate (thickness of electrolytic copper foil 12 μm, polyimide film is made of Kaneka Corporation's Apical 25 NPI, polyimide adhesive with 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. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. As in the examples, the particle size was confirmed, and in the agent B, it was confirmed that the component (b1) was not present as a solid. 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)
As the agent A, 30 g of a liquid phenoxyphosphazene derivative (FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd.), 150 g of a carboxyl group-containing resin (P7M50, solid content 50% manufactured by Kyoeisha), a carboxyl group-containing resin (ZCR manufactured by Nippon Kayaku Co., Ltd.) -1601H solid content 65%) 38 g, dipentaerythritol lactone-modified hexaacrylate (DPCA60, Nippon Kayaku Co., Ltd.) 20 g, phosphorus-containing compound-modified acrylate (Showa Polymer Co., Ltd. HFA-6065E) 23 g, melamine 5 g, silica (Admatechs Co., Ltd. Admafine SO-E2) 40 g, dipropylene glycol monomethyl ether 5 g, silicone-based antifoaming agent 3 g, pigment 1.1 g, B agent, photopolymerization initiator (Ciba Japan IRUGACURE907) 10 g , Photopolymerization open Agent (CGI-325 manufactured by Ciba Japan Co., Ltd.), 0.5 g of photopolymerization initiator (IRUGACURE OXE02 manufactured by Ciba Japan Co., Ltd.), biphenol novolac type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd. 70% solid content) The photosensitive resin composition which mix | blended 60g and consists of A agent and B agent was produced. As in the examples, the particle size was confirmed, and in the agent B, it was confirmed that the component (b1) was not present as a solid. Evaluation was performed in the same manner as in the Examples using the photosensitive resin composition obtained by mixing 315.1 g of Agent A and 71 g of Agent B. The evaluation results are shown in Table 2.

(Comparative Example 4)
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 (a2) having a carboxyl group and a photosensitive group. The obtained compound solution having a carboxyl group and a photosensitive group 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 was obtained by the above (a2) 100.0 g of a compound solution having a carboxyl group and a photosensitive group, (c1) 10.0 g of dipentaerythritol hexaacrylate as a component, an antifoaming agent (manufactured by Kyoeisha Chemical Co., Ltd.) Product name Floren AC-300) 1.0 g, barium sulfate 80.0 g, and phthalocyanine green 0.5 g were prepared. Moreover, B agent is 20.0 g of cresol novolak type epoxy resin (product name EOCN1020 manufactured by Nippon Kayaku Co., Ltd.) as component (b1), and bisphenol A type epoxy resin (product name jER828 manufactured by Japan Epoxy Resin Co., Ltd.) 10 0.0 g and (b2) component (acetyloxyiminomethyl) thioxanthen-9-one (manufactured by BASF Japan, product name CGI-325 of oxime ester photopolymerization initiator) 5.0 g, diethylthioxanthone (Nipponization) It was prepared by blending 1.0 g of product name KAYACURE DETX-S manufactured by Yakuhin 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. As in the examples, the particle size was confirmed, and it was confirmed that the component (b1) was not present as a solid in the agent B. 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.

DESCRIPTION OF SYMBOLS 1 Polyimide film which laminated the photosensitive resin composition 2 Warpage amount 3 Smooth stand

Claims (12)

A photosensitive resin composition preparation kit comprising separately at least two agents of agent A and agent B,
The agent A contains (a1) a compound having a urethane bond and no photosensitive group,
The compound has the general formula (3)

(Wherein R ₁ and X ₁ each independently represent a divalent organic group, n represents an integer of 1 or more), and has a structure containing a repeating unit containing a urethane bond, and It is a compound that does not contain a radical polymerizable group in the molecule,
The agent B contains (b1) an epoxy resin and (b2) an oxime ester photopolymerization initiator.   The photosensitive resin composition preparation kit according to claim 1, wherein the compound (a1) having a urethane bond and not having a photosensitive group has a carboxyl group.   Furthermore, the photosensitive resin composition preparation kit of Claim 1 or 2 which contains the compound which does not have a carboxyl group in (B1) agent but has a photosensitive group at least.   Furthermore, (A2) the compound which has a carboxyl group and a photosensitive group is contained in A agent, The photosensitive resin composition preparation kit of any one of Claims 1-3 characterized by the above-mentioned.   The photosensitive resin composition preparation kit according to any one of claims 1 to 4, wherein the (b1) epoxy resin is present as a solid in the agent B at room temperature (25 ° C). It is a manufacturing method of the photosensitive resin composition manufactured using the photosensitive resin composition preparation kit of any one of Claims 1-5,
A method for producing a photosensitive resin composition, comprising mixing at least two agents of agent A and agent B. A method for producing a resin film produced using the photosensitive resin composition production kit according to any one of claims 1 to 5,
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 7.   An insulating film obtained by the method for manufacturing an insulating film according to claim 8 is coated on a printed wiring board. A method for storing a compound constituting a photosensitive resin composition comprising at least (a1) a compound having a urethane bond and no photosensitive group, (b1) an epoxy resin, and (b2) an oxime ester photopolymerization initiator. And
The compound having a urethane bond and not having a photosensitive group has the general formula (3)

(Wherein R ₁ and X ₁ each independently represent a divalent organic group, n represents an integer of 1 or more), and has a structure containing a repeating unit containing a urethane bond, and It is a compound that does not contain a radical polymerizable group in the molecule,
(A1) A agent containing a compound having a urethane bond and no photosensitive group;
(B1) Epoxy resin, (b2) Two or more agents with B agent containing an oxime ester photopolymerization initiator are prepared,
A storage method characterized by storing at least A agent and B agent separately.   The storage method according to claim 10, wherein the compound (a1) having a urethane bond and not having a photosensitive group has a carboxyl group.   Furthermore, the preservation | save method of Claim 10 or 11 containing the compound which does not have a carboxyl group in (B1) agent but has a photosensitive group at least.

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