JP5858740B2 - Novel photosensitive resin composition preparation kit and use thereof - Google Patents

Description

  The present invention relates to a photosensitive resin composition preparation kit. Furthermore, this invention relates to the preservation | save method of the compound which comprises the photosensitive resin composition obtained from the said photosensitive resin composition preparation kit.

  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.

  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.

  In recent years, various proposals have been made as this photosensitive solder resist.

  For example, Patent Document 1 discloses a photocurable / thermosetting resin composition having excellent dryness to touch, adhesion, and resolution, little mist generated during heat curing, high sensitivity, and excellent storage stability. Proposed.

  Patent Documents 2 and 3 propose a flame-retardant photo-curable resin composition that can form a cured film having a non-halogen composition, a low environmental load, excellent flame retardancy and storage stability, and high flexibility. Yes.

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

  In the above patent document, various methods for solving the problem of the coverlay are proposed. The photocurable / thermosetting resin composition described in Patent Document 1 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. Blended and composed in at least a two-component system, and each composition is mixed and used immediately before use, so that the carboxyl group in the carboxyl group-containing resin and the oxime ester photopolymerization initiator for a long time contact This prevents deterioration of the oxime ester-based photopolymerization initiator due to. 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, the inventors of the present application have found a new problem regarding the photocurable thermosetting resin composition described in Patent Document 1. It has insufficient reflectivity of the cured film obtained from the above photocurable / thermosetting resin composition, and when used for a printed wiring board mounting an LED chip, it efficiently utilizes the light from the LED chip. It is a problem that it is difficult to do.

  In addition, since the resin compositions described in Patent Documents 2 and 3 have a non-halogen composition, they can form a coverlay that has low environmental impact and excellent flame retardancy, but the carboxyl group-containing resin has a photosensitive group. Therefore, there is a problem that the crosslink density of the cured film is increased and sufficient flexibility cannot be obtained. In addition, when the phosphazene compound is heated and dissolved and cooled and stored in a low temperature environment for a long period of time, the dissolved phosphazene compound is recrystallized and precipitated in the composition. There is a description about the long-term storage stability of the photosensitivity and the reflectivity of the cured film is insufficient, and when used for a printed wiring board on which the LED chip is mounted, the light from the LED chip can be used efficiently. It is not described that it is difficult, and the essence is different from the invention of the present application.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present application are photosensitive resin composition preparation kits comprising at least two agents of agent A and agent B, wherein the agent A has (A1) a carboxyl group. And a compound having no photosensitive group, and the agent B contains (B) a compound having a reactive group that reacts with a carboxyl group, (C) an oxime ester photopolymerization initiator, agent A and According to the photosensitive resin composition preparation kit, which contains (D) a white colorant in the agent B / or B, (A1) a carboxyl group in a compound having a carboxyl group and not having a photosensitive group Deterioration of the oxime ester photopolymerization initiator due to long-time contact between the oxime ester photopolymerization initiator and (C) the photosensitivity after long-term storage by using the oxime ester photopolymerization initiator. Decline Furthermore, the photosensitive resin composition produced using the photosensitive resin composition production kit is sufficient to use a white colorant by using a highly sensitive (C) oxime ester photopolymerization initiator. Good fine workability is obtained even in a system colored so as to obtain reflectivity, and (A1) flexibility of cured film and electrical insulation reliability by using a compound having a carboxyl group and no photosensitive group. The knowledge which can obtain the property and the flame retardancy is obtained, and the present invention has been achieved based on these findings.

  This invention can solve the said subject with the following novel photosensitive resin compositions. 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 (A1) a compound having a carboxyl group and not having a photosensitive group. The B agent contains (B) a compound having a reactive group that reacts with a carboxyl group, (C) an oxime ester photopolymerization initiator, and (D) white coloring in the A agent and / or B agent. It is a photosensitive resin composition preparation kit characterized by containing an agent.

  In the photosensitive resin composition preparation kit according to the present invention, it is preferable that the agent A further contains (A2) a compound having a carboxyl group and a photosensitive group.

  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 an epoxy resin.

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

  Furthermore, the present invention is a method for preparing a photosensitive resin composition using the photosensitive resin composition preparation kit described above, wherein the agent A and the agent B are mixed together. A method for producing a photosensitive resin composition is also included.

  Furthermore, the present invention is a method for producing a resin film using the above-described photosensitive resin composition production kit, wherein a mixture of at least two agents, A agent and B agent, is applied to a substrate surface, and then the mixture is applied. A method for producing a resin film characterized by being obtained by drying is also included.

  The present invention further includes a method for producing an insulating film obtained by curing the above-described resin film.

  Furthermore, the present invention includes a method for producing a printed wiring board with an insulating film in which the above-described insulating film is coated on the printed wiring board.

  The present invention further comprises (A1) a compound having a carboxyl group and no photosensitive group, (B) a compound having a reactive group that reacts with a carboxyl group, (C) an oxime ester photopolymerization initiator, and (D) A method for preserving a compound constituting a photosensitive resin composition comprising a white colorant, wherein (A1) A agent contains a compound having a carboxyl group and no photosensitive group; and (B) Prepare a compound having a reactive group that reacts with a carboxyl group and (C) two or more agents containing B agent containing an oxime ester photopolymerization initiator, and store at least A agent and B agent separately. A storage method characterized by the above is also included.

  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 prepared using the kit has photosensitivity and can be finely processed, can be developed with a dilute alkaline aqueous solution, and can be cured at a low temperature (200 ° C. or lower).

  In addition, 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, reflectance, and has good physical properties, Small warpage after curing. Therefore, the photosensitive resin composition of the present invention can be used for protective films of various circuit boards and exhibits 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 the photosensitive resin composition.

(I) Photosensitive resin composition preparation kit The photosensitive resin composition of the present invention is a photosensitive resin composition preparation kit comprising at least two agents of agent A and agent B, and the agent A is (A1 ) Contains a compound having a carboxyl group and no photosensitive group, the agent B contains (B) a compound having a reactive group that reacts with the carboxyl group, and (C) an oxime ester photopolymerization initiator. The photosensitive resin composition preparation kit is characterized by containing (D) a white colorant in the A agent and / or the B agent.

  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.

  In this specification, (A1) a compound having a carboxyl group and not having a photosensitive group is referred to as “(A) component”, and (B) a compound having a reactive group that reacts with a carboxyl group is referred to as “(B) component”. ”, (C) the oxime ester photopolymerization initiator may be referred to as“ (C) component ”, and (D) the white colorant may be referred to as“ (D) component ”.

  Here, since the productivity is generally excellent, the photopolymerization initiator is often used as a component of the agent A. However, when (A1) a compound having a carboxyl group and no photosensitive group used in the present invention and (C) an oxime ester photopolymerization initiator are used as the composition of the agent A, the component (A1) Since the deterioration of the component (C) is promoted by prolonged contact between the carboxyl group of the component and the component (C) and the photosensitivity is lowered, the storage stability is greatly reduced and it can be used in a general composition. There wasn't.

  However, the photosensitive resin composition preparation kit of the present invention has high storage stability because there is no decrease in photosensitivity after long-term storage despite the use of the (C) oxime ester photopolymerization initiator. The inventors of the present application have found that is excellent in various properties. The present inventors speculate that this may be due to the following reason. That is, the photosensitive resin composition preparation kit of the present invention includes (A1) a compound having a carboxyl group and no photosensitive group in agent A, and (C) an oxime ester photopolymerization initiator in agent B. By containing and separating, the deterioration of the component (C) due to long-time contact between the component (A1) and the component (C) is suppressed, and the photosensitivity does not decrease. For this reason, the storage stability of the photosensitive resin composition preparation kit is improved. In addition, the agent A contains (A1) a compound that has a carboxyl group and does not have a photosensitive group, and the agent B contains a compound having a reactive group that reacts with the carboxyl group (B). Reaction progress due to long-time contact between the component (A1) and the component (B) is suppressed, and the storage stability of the photosensitive resin composition preparation kit is improved.

  That is, the reason why the storage stability of the photosensitive resin composition preparation kit is improved is that (A1) a compound having a carboxyl group and not having a photosensitive group and (B) a reactive group that reacts with the carboxyl group. When the compound coexists, the reaction of the carboxyl group and the reactive group with respect to the carboxyl group gradually proceeds, and (A1) the compound having a carboxyl group and no photosensitive group, and (C) the oxime ester system In the case where a photopolymerization initiator coexists, the present inventor said that this was due to the elimination of two stability-decreasing factors, that is, an acidic atmosphere in which a carboxyl group is present acts as a catalyst and hydrolysis of the oxime ester occurs. Have estimated. Thus, if the storage stability of the photosensitive resin composition preparation kit improves, the storage stability of the photosensitive resin composition prepared using the photosensitive resin composition preparation kit will improve.

  In addition, as mentioned above, (A1) A agent containing the compound which has a carboxyl group and does not have a photosensitive group, (B) The compound which has a reactive group which reacts with a carboxyl group, (C) Oxime ester light To improve the storage stability as a photosensitive resin composition preparation kit by preparing two or more agents with a B agent containing a polymerization initiator, and storing at least the A agent and the B agent separately. Can do. That is, (A1) a compound having a carboxyl group and not having a photosensitive group, (B) a compound having a reactive group that reacts with a carboxyl group, and (C) an oxime ester-based light constituting the photosensitive resin composition It can be said that the present invention can provide a stable method for storing a compound comprising a polymerization initiator.

  Moreover, in order to improve the reflectance of the cured film obtained from the photosensitive resin composition which is a new subject of the present invention, it is necessary to add (D) a white colorant to an extent that sufficient reflectance can be obtained. However, in this case, the photosensitivity of the photosensitive resin composition is lowered, so that the fine workability is deteriorated and a good fine opening pattern cannot be obtained. May cause problems such as worsening. Therefore, in order to solve the decrease in photosensitivity, it was necessary to use a highly sensitive (C) oxime ester photopolymerization initiator. Among them, (A1) a compound having a carboxyl group and not having a photosensitive group When (C) and the oxime ester photopolymerization initiator are combined, the fine colorability, the flexibility of the cured film, and the electrical insulation reliability are excellent even in a system colored so that sufficient reflectance is obtained using a white colorant. And found to be excellent in flame retardancy.

  The following (A1) a compound having a carboxyl group and no photosensitive group, (A2) a compound having a carboxyl group and a photosensitive group, (B) a compound having a reactive group that reacts with the carboxyl group, (C) oxime The ester photopolymerization initiator, (D) white colorant, other components, and the mixing method of the A agent and B agent will be described. Here, (meth) acrylic acid in the present invention means acrylic acid and / or methacrylic acid, and (meth) acrylate has the same meaning.

<(A1) Compound having a carboxyl group and no photosensitive group>
The compound (A1) having a carboxyl group and not having a photosensitive group used in the present invention is not particularly limited as long as it is a compound having at least one carboxyl group in the molecule and not having a photosensitive group. Further, the component (A1) may be contained alone, or both the component (A1) and the compound (A2) having a carboxyl group and a photosensitive group may be contained. The carboxyl group may be a carboxylic acid anhydride in which two carboxyl groups are dehydrated.

  In order to improve the reflectance of the cured film obtained from the photosensitive resin composition, which is a new problem in the present invention, it is necessary to add (C) a white colorant to an extent that sufficient reflectance can be obtained. In this case, there is a problem that the photosensitivity is lowered due to the decrease in the transmittance of the photosensitive resin composition. In order to solve this problem, it is necessary to use the (C) oxime ester photopolymerization initiator which is a highly sensitive photopolymerization initiator. In this case, the (C) oxime ester photopolymerization initiator is highly sensitive. For this reason, the crosslink density of the cured film obtained from the photosensitive resin composition is excessively increased and the flexibility may be lowered. Therefore, by combining (A1) a compound having a carboxyl group and not having a photosensitive group, which is a feature of the present invention, it becomes possible to independently adjust the carboxyl group concentration and the photosensitive group concentration. The cross-linking density of the cured film obtained from the resin composition does not increase too much, and both good micro workability and the flexibility of the cured film are compatible even in a system colored so that sufficient reflectance can be obtained using a white colorant. Can do.

  Furthermore, when it contains both (A1) a compound having a carboxyl group and not having a photosensitive group, and (A2) a compound having a carboxyl group and a photosensitive group, the cured film obtained from the photosensitive resin composition The flexibility and the photosensitivity of the photosensitive resin composition can be well balanced, which is preferable.

  Furthermore, when the carboxyl group in the compound (A1) having a carboxyl group and not having a photosensitive group has a structure in which it is directly bonded to an aromatic ring, the balance between alkali developability and alkali resistance is good. Conditions such as time are possible in a wide range. For this reason, it is preferable that the carboxyl group in the compound (A1) having a carboxyl group and not having a photosensitive group has a structure in which it is directly bonded to an aromatic ring.

  The compound (A1) having a carboxyl group and not having a photosensitive group used in the present invention is soluble in an organic solvent, and the weight average molecular weight is 1,000 or more, 1,000,000 in terms of polyethylene glycol. In the case of a polymer of 000 or less, since an appropriate viscosity is imparted to the photosensitive resin composition, the film-forming property and thickness uniformity when the photosensitive resin composition is applied onto the substrate are improved, and It is preferable because the flexibility and chemical resistance of the cured film obtained are improved.

  Examples of the organic solvent include, but are not limited to, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, formamide solvents such as N, N-diethylformamide, N, N-dimethylacetamide, Examples thereof include acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-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, ethers such solvents such as ethyl ether also ethylene glycol.

  The solubility of the organic solvent, which is an index that becomes soluble in the organic solvent, is measured as parts by weight of the compound that has a carboxyl group and does not have a photosensitive group that is soluble in 100 parts by weight of the organic solvent (A1). Soluble in 100 parts by weight of the organic solvent (A1) If the weight part of the compound having a carboxyl group and not having a photosensitive group is 5 parts by weight or more, it is soluble in the organic solvent. be able to. The organic solvent solubility measurement method is not particularly limited. For example, 5 parts by weight of the compound (A1) having a carboxyl group and not having a photosensitive group is added to 100 parts by weight of the organic solvent, and 1 at 40 ° C. After stirring for a period of time, it can be measured by a method of cooling to room temperature and allowing it to stand for 24 hours or more, and confirming that the solution is uniform without generation of insoluble matter or precipitates.

  The weight average molecular weight can be measured, for example, by the following method.

(Weight average molecular weight measurement)
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)

  Controlling the weight average molecular weight within the above range is preferable because the resulting cured film has excellent flexibility and chemical resistance. When the weight average molecular weight is 1,000 or less, flexibility and chemical resistance may decrease, and when the weight average molecular weight is 1,000,000 or more, the viscosity of the photosensitive resin composition may increase. is there.

  The component (A1) is not particularly limited. For example, a carboxyl group-containing (meth) acrylic copolymer, a carboxyl group-containing vinyl copolymer, an acid-modified polyurethane, an acid-modified polyester, an acid-modified polycarbonate, an 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, boseopentaenoic 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, aliphatic diisocyanate compounds such 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.

  The reaction for obtaining the compound (A1) having a carboxyl group and not having a photosensitive group can be reacted in the absence of a solvent, but in order to control the reaction, the reaction can be performed in an organic solvent system. For example, as the organic solvent, those exemplified above can be used.

  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.

<(A2) Compound having carboxyl group and photosensitive group>
The compound (A2) having a carboxyl group and a photosensitive group in the present invention is a compound having at least one carboxyl group and a photosensitive group in the molecule. When the component (A2) is used together with the component (A1), it is preferable because the flexibility of the cured film obtained from the photosensitive resin composition and the photosensitivity of the photosensitive resin composition can be balanced. .

  The component (A2) is not particularly limited. For example, 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. There is. 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 compound having the carboxyl group and the photosensitive group (A2) is blended so as to be 10 to 200 parts by weight with respect to 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 is lowered, and it may be difficult to obtain contrast when exposed and developed. Moreover, when there are more (A2) components than the said range, since the stickiness of the coating film obtained by apply | coating the photosensitive resin composition on a base material and drying a solvent becomes large, productivity will fall. 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.

<(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, (B) the compound having a reactive group that reacts with a carboxyl group is blended with B agent different from A agent containing (A1) a compound having a carboxyl group and no photosensitive group. Yes. 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 having a reactive group that reacts with the carboxyl group (B) used in the present invention is an epoxy resin, the cured film obtained from the photosensitive resin composition is preferably excellent in heat resistance and electrical insulation reliability. 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. In particular, when the epoxy resin is present in the B agent in a solid state at room temperature (25 ° C.), the deterioration of the (C) oxime ester photopolymerization initiator mixed in the B agent is small, and after long-term storage, The resin composition is preferable in that it has no decrease in photosensitivity and is excellent in storage stability. For example, product names jERYX4000, jERYX4000K, jERYX4000H, jERYX4000HK, jERYX8800, and product names TEPIC manufactured by Nissan Chemical Industries, Ltd. -G, TEPIC-P, TEPIC-S, TEPIC-SP, Nippon Kayaku Co., Ltd. GTR-1800, etc. are mentioned.

  Here, the epoxy resin exists in the B agent in a solid state at room temperature (25 ° C.) means that the epoxy resin that is a solid at room temperature (25 ° C.) does not completely dissolve in the B agent. It means that the whole or part of the resin exists 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 compound (B) having a reactive group that reacts with a carboxyl group is 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. It is preferable to be blended in the above because the heat resistance, chemical resistance and electrical insulation reliability of the cured film obtained from 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 and accelerates the reaction of a photosensitive group. The (C) oxime ester-based photopolymerization initiator is divided as the B agent separately from the (A1) agent A containing a compound having a carboxyl group and no photosensitive group. With the above configuration, the deterioration of the component (C) due to the long-time contact between the component (A1) and the component (C) is suppressed and the photosensitivity does not decrease. Therefore, the storage stability of the photosensitive resin composition preparation kit Improves.

  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.

  The (C) 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 carboxyl group 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 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) White colorant>
The (D) white colorant of the present invention is a substance having an effect of coloring other substances white, and a white pigment is preferable from the viewpoint of colorability and heat resistance. The white pigment is not particularly limited. For example, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow Resin particles can be mentioned, and these can be used alone or in combination of two or more. Among these, when titanium oxide is used, it is preferable because high colorability and reflectance can be obtained. Further, when rutile type titanium oxide is used, it is preferable because of excellent colorability, concealability and stability.

The rutile-type titanium oxide in the present invention is an oxide of titanium having a tetragonal crystal structure and an inorganic compound represented by the composition formula TiO ₂ , and the production method is not particularly limited. It can be produced by a so-called sulfuric acid method in which a titanium solution is hydrolyzed and the resulting hydrous titanium oxide is fired, or a so-called chlorine method in which titanium halide is vapor-phase oxidized. In addition, in the titanium oxide of the sulfuric acid method, for example, a metal such as zinc, potassium, aluminum, lithium, niobium, magnesium, or a compound such as phosphorus can be added as a baking treatment agent in the production process. In the case of the method titanium oxide, a compound such as aluminum or potassium may be added as a treating agent during the oxidation process of titanium tetrachloride in the production process. In particular, in the case of titanium oxide produced by the chlorine method, the reflectance and concealment of the cured film obtained from the photosensitive resin composition are good, and discoloration at low temperatures or low reflectance is unlikely to occur. This is preferable.

  Specific examples of the rutile-type titanium oxide include trade names T-PEKE R-550, R-580, R-630, R-670, R-680, R-780, and R-780- manufactured by Ishihara Sangyo Co., Ltd. 2, R-820, R-830, R-850, R-855, R-930, R-980, CR-50, CR-50-2, CR-57, CR-58, CR-58-2, CR-60, CR-60-2, CR-63, CR-67, CR-Super70, CR-80, CR-85, CR-90, CR-90-2, CR-93, CR-95, CR- 953, CR-97, PF-736, PF-737, PF-742, PF-690, PF-691, PF-711, PF-739, PF-740, PC-3, S-305, CR-EL, PT-301, PT-401M, PT- 01A, PT-501R, trade names R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44 manufactured by Sakai Chemical Industry Co., Ltd. , R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, trade names of JR, JRNC, JR- 301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR-800, JR-805, JR-806, JR-1000, MT-01, MT-05, MT-10EX, MT-100S, MT-100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-150EX, MT-15 W, MT-300HD, MT-500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700HD, trade names KR-310, KR-380, manufactured by Titanium Industry Co., Ltd. Examples include, but are not limited to, KR-380N, trade names TR-600, TR-700, TR-750, TR-840, TR-900 manufactured by Fuji Titanium Industry Co., Ltd.

  The content of the component (D) of the present invention is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the component (A1), and the reflectance of the cured film obtained. Excellent in concealment. When the component (D) is less than 5 parts by weight, the reflectivity and concealment may be inferior. When the component is more than 200 parts by weight, the transmittance of the photosensitive resin composition is lowered, so that the photosensitivity may be lowered. is there.

<Other ingredients>
Various additives such as a compound having a photosensitive group, a flame retardant, a filler, an adhesion aid, an antifoaming agent, a leveling agent, and a polymerization inhibitor are further added to the photosensitive resin composition of the present invention as necessary. be able to.

  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 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.

  The compound having a photosensitive group in the present invention is a compound containing in the molecule a radical polymerizable group that undergoes a polymerization reaction by a radical polymerization initiator, and having at least one unsaturated double bond in the molecule. It is preferable that Furthermore, the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group. Examples of such a compound 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 to 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-hexane Diol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tet Methylolpropane 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, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene Recall 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, neo Pentyl 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 polyethoxy) phenyl] propane, poly Reethylene 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, nonylphenoxy polyethylene glycol acrylate, Nonylphenoxy polypropylene glycol acrylate, isostearyl acrylate, polio Siethylene 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- Nthanediol diacrylate, ethoxylated totimethylolpropane 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'-isopropylidenediphenol dimethacrylate 4,4′-isopropylidenediphenol diacrylate and the like are preferable, but are not limited thereto. There. 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 hardly remains in the cured film obtained by curing the composition, and curling of the printed wiring board can be suppressed when laminated on a flexible printed wiring board based on a polyimide resin, for example, among printed wiring boards. The compound having a photosensitive group is preferably blended in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of the component (A1) in terms of improving the photosensitivity of the photosensitive resin composition. . When the amount is less than the above range, the alkali resistance of the cured film after photo-curing the photosensitive resin composition is lowered, and it may be difficult to obtain contrast when exposed and developed. On the other hand, if the amount 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 and a crosslink density. When it 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.

<Method of mixing agent A and agent B>
The agent A in the present invention can be obtained, for example, by pulverizing and dispersing the compound (A1) having a carboxyl group and not having a photosensitive group, other components, and an organic solvent. 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 mixture of (B) a compound having a reactive group that reacts with a carboxyl group, (C) an oxime ester photopolymerization initiator, other components, and an organic solvent. Can be obtained. 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 obtained 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. This invention can also provide the photosensitive resin composition, the resin film, the insulating film, and the printed wiring board with an insulating film which were obtained in this way.

  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 1 of Compound Having Carboxyl Group and No Photosensitive 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 dropping, the reaction solution is heated to 90 ° C. while stirring, and further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. The compound solution having a carboxyl group and having no photosensitive group of the present invention Got. The resulting compound solution having a carboxyl group and no photosensitive group 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 150 ° 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)
<Synthesis 2 of (A1) Compound Having Carboxyl Group 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 polymerization solvent, and norbornene diisocyanate was added to 10. 3 g (0.050 mol) was charged and dissolved by heating to 80 ° C. A solution obtained by dissolving 50.0 g (0.025 mol) of polycarbonate diol (trade name: PCDL T5652; average molecular weight: 2000) in methyltriglyme (50.0 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, 31.02 g (0.100 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride (hereinafter referred to as “ODPA”) and methyltriglyme (20.0 g) were added to the above reaction solution. Added to. After the addition, the mixture was heated to 200 ° C. and reacted for 3 hours. By performing the above reaction, a compound solution having a carboxyl group and no photosensitive group was obtained. The resulting compound solution having a carboxyl group and no photosensitive group had a solid content concentration of 50%, a weight average molecular weight of 9,000, and an acid value of the solid content of 75 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 a carboxyl group and not having a photosensitive group obtained in Synthesis Examples 1 and 2, (D) White colorant, other components, and 1,2-bis (2- Methoxyethoxy) ethane is added to prepare agent A, (B) a compound having a reactive group that reacts with a carboxyl group, (C) an oxime ester photopolymerization initiator, (D) a white colorant, and other components And B, an organic solvent, 1,2-bis (2-methoxyethoxy) ethane, 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. Incidentally, 1,2-bis (2-methoxyethoxy) ethane, which is an organic solvent in the table, is the total amount of the solvent including the solvent contained in the synthesized resin solution. At this time, the agent A and the agent B were mixed and dispersed by two passes each with three rolls. The obtained agent A and agent B were confirmed in particle size using a grindometer manufactured by Yasuda Seiki Seisakusho with a groove depth of 0 to 50 μm according to the method described in JIS K 5600-2-5. Only the component (B) was confirmed to be 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 Table 1. For example, in Example 1, 190 g of the A agent and 44 g of the B agent were mixed.

In Table 1, descriptions of <1> to <6> are as follows.
<1> Compound having a carboxyl group and a photosensitive group (product name of Nippon Kayaku Co., Ltd. carboxyl group and photosensitive group-containing resin, solid content concentration: 65%, solid content acid value: 98 mgKOH / g)
<2> Oxime ester photopolymerization initiator (product name of 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] manufactured by BASF Japan Ltd.)
<3> Product name of white colorant (rutile titanium oxide) manufactured by Ishihara Sangyo Co., Ltd. <4> Product name of phosphazene compound (phosphorus flame retardant) manufactured by Otsuka Chemical Co., Ltd. <5> Liquid epoxy manufactured by Japan Epoxy Resin Co., Ltd. Product name of resin <6> Product name of powder epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. <7> Oxime ester photopolymerization initiator (manufactured by BASF Japan, Etanone, 1- [9-ethyl-6- (2- Product name of methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxyome))
<8> Trade name of Hitachi Chemical Co., Ltd. EO-modified (n = 10) bisphenol A dimethacrylate

<Preparation of coating film on polyimide film>
Using the photosensitive resin composition obtained by mixing the above agent A and agent B, a final dry thickness of 20 μm is applied to a 25 μm polyimide film (manufactured by Kaneka Corporation: trade name 25 NPI) using a baker type applicator. Then, it 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 required, 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 90 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 of photosensitive resin composition>
A coating film was prepared by the above method, 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, A agent and B agent before mixing were stored at 40 degreeC, and the same evaluation was performed after each elapsed days. Thereafter, a determination was made based on the following criteria.
A: After 300 days, the number of step tablet steps is within a range of ± 1 with respect to the reference value.
○: After 50 days, the step tablet plate number is in the range of ± 1 with respect to the reference value.
Δ: After 10 days, the number of step tablet steps is within a range of ± 1 with respect to the reference value.
X: After 10 days, the step tablet plate number is not in the range of ± 1 with respect to the reference value.

(Ii) Reflectance Curing 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 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A film laminated film was produced. Using the obtained cured film laminated film, the reflectance of the photosensitive resin composition cured film layer was measured by the following method, and the measured value at 450 nm was defined as the reflectance.
Equipment used: UV-visible spectrophotometer V-650 manufactured by JASCO Corporation
Measurement wavelength region: 300 to 800 nm
Standard white board: Spectralon TM manufactured by Labsphere.

(Iii) 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 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of a coating film on a 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.

(Iv) 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 in 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.

(V) Flame retardancy In accordance with the UL94VTM method for the flammability test of plastic materials, the flammability test 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.
X: Some samples do not extinguish within 10 seconds, or the flame rises above the rating line and burns.

(Vi) Tackiness The photosensitive resin composition is applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>, and dried. A coating film having a thickness of 20 μm after drying was obtained. The surface of the obtained coating film was bent and lightly overlapped, and a determination was made based on the following criteria.
A: The surfaces do not stick together, and no sticking marks remain.
○: The surfaces do not stick to each other, but some marks remain.
(Triangle | delta): Although surfaces adhere, it peels easily.
X: The surfaces stick to each other and cannot be easily peeled off.

(Vii) Solder heat resistance of a 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.

(Viii) 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.

(Ix) Electrical insulation reliability Line width / space width on a flexible copper-clad laminate (electrolytic copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Corporation, and copper foil is bonded with polyimide adhesive) = 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 in the same manner as in the above <Preparation of coating film on polyimide film> method, and a test piece was prepared. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and a relative humidity of 85%, 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 Example 1)
As in the examples, a photosensitive resin composition composed of agent A and agent B was prepared. In addition, (C) component was added to A agent. 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 the obtained photosensitive resin composition was used for evaluation in the same manner as in the examples. The evaluation results are shown in Table 2.

(Comparative Example 2)
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 the compound solution having a carboxyl group and a photosensitive group, (D) component as dipentaerythritol hexaacrylate 10.0 g, 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 (B), and bisphenol A type epoxy resin (product name jER828 manufactured by Japan Epoxy Resin Co., Ltd.) 10 0.0 g, (acetyloxyiminomethyl) thioxanthen-9-one (manufactured by BASF Japan Ltd., product name CGI-325 of oxime ester-based photopolymerization initiator) as component (C), 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.). 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.

1 Polyimide film laminated with a photosensitive resin composition 2 Warpage (warp height)
3 Smooth base

Claims (12)

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 carboxyl group and no photosensitive group,
The agent B contains (B) a compound having a reactive group that reacts with a carboxyl group, (C) an oxime ester photopolymerization initiator, and (D) a white colorant in agent A and / or agent B. ,
Wherein (A1) is not of Gobutsu to have a photosensitive group having a carboxyl group, Ri at least one compound der selected acid-modified polyurethane, acid-modified polyamide, and acid-modified polyimide,
Wherein A agent further (A2) the photosensitive resin composition prepared kit characterized that you containing a compound having a carboxyl group and a photosensitive group. 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 an epoxy resin. The photosensitive resin composition preparation kit according to claim 2 , wherein the epoxy resin is present in the B agent in a solid state at room temperature (25 ° C.). The said (A1) compound which has a carboxyl group and does not have a photosensitive group is an acid-modified polyimide, The photosensitive resin composition preparation kit of any one of Claims 1-3 characterized by the above-mentioned. A method for producing a photosensitive resin composition using the photosensitive resin composition production kit according to any one of claims 1 to 4 ,
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 using the photosensitive resin composition production kit according to any one of claims 1 to 4 ,
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 6 . A method for producing a printed wiring board with an insulating film, comprising coating the printed wiring board with an insulating film obtained by the method for producing an insulating film according to claim 7 . At least (A1) a compound having a carboxyl group and no photosensitive group, (B) a compound having a reactive group which reacts with a carboxyl group, (C) an oxime ester photopolymerization initiator, and (D) white coloring A method for preserving a compound constituting a photosensitive resin composition containing an agent,
(A1) A agent containing a compound having a carboxyl group and no photosensitive group;
(B) Two or more agents containing a compound having a reactive group that reacts with a carboxyl group and (C) a B agent containing an oxime ester photopolymerization initiator are prepared,
Store at least A and B separately,
A agent and / or B agent contains (D) a white colorant,
Wherein (A1) is not of Gobutsu to have a photosensitive group having a carboxyl group, Ri at least one compound der selected acid-modified polyurethane, acid-modified polyamide, and acid-modified polyimide,
Wherein A agent further (A2) stored wherein that you containing a compound having a carboxyl group and a photosensitive group. The storage method according to claim 9 , wherein the compound (A1) having a carboxyl group and not having a photosensitive group is an acid-modified polyimide. The storage method according to claim 9 or 10 , wherein the compound (B) having a reactive group that reacts with a carboxyl group is an epoxy resin. The storage method according to claim 11 , wherein the epoxy resin is present as a solid in the agent B at room temperature (25 ° C.).

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