JP2012237864A - Novel black photosensitive resin composition and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black photosensitive resin composition which has excellent tack-free properties after drying of a coated film, enables microfabrication because of its photosensitivity, can obtain a cured film excellent in flexibility, fire retardancy and electrical insulation reliability, and has little warpage of a substrate after curing; a resin film; an insulator film; and a printed wiring board with an insulator film.SOLUTION: A black photosensitive resin composition contains at least (A) binder polymer, (B) crosslinked polymer particles, (C) thermosetting resin, (D) photopolymerization initiator, (E) phosphorus-based flame retardant, and (F) black colorant.

Description

  This invention is excellent in tack-free property after drying of the coating film and has photosensitivity so that it can be finely processed. The resulting cured film is excellent in flexibility, flame retardancy and electrical insulation reliability, and is a substrate after curing. The present invention relates to a black photosensitive resin composition, a resin film, an insulating film, and a printed wiring board with an insulating film.

  Polyimide resins are widely used in electrical and electronic applications because of their excellent heat resistance, electrical insulation reliability, chemical resistance, and mechanical properties. For example, it is used to form insulating films and protective coatings on semiconductor devices, base materials such as flexible circuit boards and integrated circuits, surface protective materials, and further, interlayer insulating films and protective films for fine circuits. .

  In particular, when used as a surface protection material for a flexible circuit board, a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film has been used. 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.

  However, it is difficult to provide a high-accuracy opening in a thin coverlay film, and since the alignment at the time of lamination is often performed manually, the positional accuracy is poor and the workability of the lamination is also poor. The cost was high.

  On the other hand, a solder resist or the like may be used as a surface protection material for a circuit board. In particular, a solder resist having a photosensitive function is preferably used when fine processing is required. As this photosensitive solder resist, a photosensitive resin composition mainly composed of acid-modified epoxy acrylate, epoxy resin, or the like is used. This photosensitive solder resist is excellent in electrical insulation reliability as an insulating material, but is bent. Therefore, when it is laminated on a thin and flexible circuit board such as a flexible circuit board, the warpage of the board becomes large and it is difficult to use it for a flexible circuit board. Further, the flame retardancy is poor, and when a flame retardant is added for the purpose of imparting flame retardancy, there are problems such as deterioration in physical properties and contact failure due to bleeding out from the cured film and process contamination.

  In recent years, a coverlay film or photosensitive solder resist, which is an insulating protective film on a circuit board, is colored black to conceal the circuit pattern, thereby attempting to protect confidential information contained in the circuit pattern. Has been made.

  Particularly in the case of a photosensitive solder resist, it is important to make the photosensitivity, flexibility, heat resistance, plating resistance, blackness and hiding properties compatible, and various proposals that can manifest these characteristics have been made.

  For example, a black photo solder resist that has sufficient blackness and excellent resolution is proposed (see, for example, Patent Document 1).

  In addition, a photosensitive resin composition excellent in high sensitivity, plating properties, bendability (flexibility), heat resistance, and low tack and a photosensitive film using the same have been proposed (for example, Patent Document 2). reference.).

  On the other hand, one of the important characteristics when carrying out the photosensitive solder resist processing is that the coating film surface is less sticky (tack-free) after the coating film is applied and the solvent is dried. This prevents the photomask from sticking to the coating film when it is irradiated with UV light by placing a photomask necessary for fine pattern formation on the surface of the coating film. This is an important characteristic for preventing the circuit boards from sticking to each other when the boards are stacked.

  As a method of improving the tack-free property after drying the coating film of this photosensitive solder resist, a technique of adding an inorganic filler to provide unevenness on the coating film surface is used, but the cured film is brittle because the inorganic filler is hard. Thus, there were problems such as generation of cracks and peeling from the substrate.

  Therefore, a high-performance photocurable liquid solder resist ink composition has been proposed that is highly sensitive and excellent in tack-free and developability of the coating film, and does not cause adhesion degradation or peeling due to cracking or volume shrinkage. (For example, refer to Patent Document 3).

JP 2008-257045 A JP 2010-282002 A Japanese Patent Laid-Open No. 9-137109

  In the above-mentioned patent documents, various methods for solving the problems of the photosensitive solder resist are proposed. However, since the black photosensitive resin composition described in Patent Document 1 contains a plurality of black colorants, it has excellent sensitivity, resolution, blackness, heat resistance, gold plating resistance, There was a problem that the warpage after curing was large due to poor flame retardancy. Although the photosensitive resin composition described in Patent Document 2 contains a polyurethane compound having excellent flexibility and a binder polymer having a carboxyl group, it has excellent sensitivity, resolution, folding resistance, and resistance to gold plating. There were problems of poor insulation reliability, tack-free properties after drying the coating film, and flame retardancy. The ink composition for solder resist described in Patent Document 3 is excellent in tack-free property of the coating film due to dispersion of polymer fine particles having a glass transition temperature of 20 ° C. or less, and adhesion due to generation of cracks and volume shrinkage. However, when used as an insulating protective film of a flexible printed wiring board, there is a problem that bending resistance and flame retardancy are poor and warpage is large.

  As a result of diligent research to solve the above problems, the present inventors have at least (A) a binder polymer, (B) a crosslinked polymer particle, (C) a thermosetting resin, (D) a photopolymerization initiator, (E) phosphorus. A black photosensitive resin composition characterized by containing a flame retardant, (F) a black colorant, has excellent tack-free properties after drying of the coating film, and has photosensitivity so that it can be finely processed. To obtain black photosensitive resin compositions, resin films, insulating films, and printed wiring boards with insulating films that have excellent flexibility, flame retardancy, electrical insulation reliability, and low warpage of the cured substrate. Based on these findings, the present invention has been achieved. This invention can solve the said subject with the black photosensitive resin composition of the following novel structures.

  That is, the present invention includes at least (A) a binder polymer, (B) a crosslinked polymer particle, (C) a thermosetting resin, (D) a photopolymerization initiator, (E) a phosphorus flame retardant, and (F) a black colorant. It is a black photosensitive resin composition characterized by containing.

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the said (A) binder polymer is resin which contains a urethane bond in a molecule | numerator.

  In the black photosensitive resin composition according to the present invention, the resin containing a urethane bond in the molecule further comprises (a1) a (meth) acryloyl group, (a2) a carboxyl group, and (a3) an imide group. It is preferable to contain at least one organic group selected from

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the said (B) crosslinked polymer particle is a crosslinked polymer particle which contains a urethane bond in a molecule | numerator.

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the said (C) thermosetting resin is a polyfunctional epoxy resin.

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the said (D) photoinitiator is an oxime ester type photoinitiator.

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the said (E) phosphorus flame retardant is a phosphinic acid salt.

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the said (F) black coloring agent is carbon black.

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the compounding quantity of the said (B) crosslinked polymer particle is 30-100 weight part with respect to 100 weight part of (A) binder polymer.

  Moreover, in the black photosensitive resin composition concerning this invention, it is preferable that the compounding quantity of the said (E) phosphorus flame retardant is 5-100 weight part with respect to 100 weight part of (A) binder polymer.

  Moreover, the resin film concerning this invention is obtained by drying, after apply | coating the said black photosensitive resin composition to the base-material surface.

  The insulating film according to the present invention is obtained by curing the resin film.

  The printed wiring board with an insulating film according to the present invention is formed by coating the insulating film on the printed wiring board.

  As described above, the black photosensitive resin composition of the present invention comprises at least (A) a binder polymer, (B) crosslinked polymer particles, (C) a thermosetting resin, (D) a photopolymerization initiator, and (E) phosphorus. Since the composition containing a flame retardant, (F) a black colorant, the black photosensitive resin composition of the present invention is excellent in concealing property, excellent in tack-free properties after drying the coating film, and photosensitive. Therefore, the cured film obtained is excellent in flexibility, flame retardancy, and electrical insulation reliability, and the warpage of the substrate after curing is small. Therefore, the black 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 black photosensitive resin composition and (II) a method of using a black photosensitive resin composition.

(I) Black photosensitive resin composition The black photosensitive resin composition of the present invention is at least (A) a binder polymer, (B) crosslinked polymer particles, (C) a thermosetting resin, and (D) a photopolymerization initiator. (E) A phosphorus flame retardant and (F) a black colorant may be contained.

  Here, although the present inventors discovered that the black photosensitive resin composition of this invention was excellent in various characteristics, it estimates that this may be based on the following reasons. In other words, the crosslinked polymer particles as the component (B) have the function of providing irregularities on the coating film surface, so that they are excellent in tack-free properties after drying the coating film, can make the coating film matt, and the polymer particles are soft. Therefore, the flexibility of the cured film is not reduced. Furthermore, since the polymer particles have a crosslinked structure, they are excellent in heat resistance and chemical resistance. Furthermore, surprisingly, in general, when the filler component is highly filled, the flexibility to withstand repeated bending is lowered. However, the combination of the component (A) and the component (B) makes the coating film very soft and resistant to bending. It will be excellent. This is presumed that the (A) component constituting the cured film matrix penetrates into the (B) component so that strong adhesiveness can be obtained at the interface between the (A) component and the (B) component. doing. Further, even when a black colorant such as component (F) is used, when combined with component (B), component (B) exhibits a stress relaxation effect in the cured film, and the cured film withstands repeated bending. It is possible to develop a good folding resistance.

  (A) binder polymer, (B) crosslinked polymer particles, (C) thermosetting resin, (D) photopolymerization initiator, (E) phosphorus flame retardant, (F) black colorant, other components, and The method for mixing the black photosensitive resin composition will be described.

<(A) Binder polymer>
The (A) binder polymer of the present invention is a polymer that is soluble in an organic solvent and has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.

  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, can be measured as parts by weight of the base polymer dissolved in 100 parts by weight of the organic solvent, and is soluble in 100 parts by weight of the organic solvent. If the weight part of the base polymer is 5 parts by weight or more, it can be made soluble in an organic solvent. The organic solvent solubility measurement method is not particularly limited. For example, 5 parts by weight of the base polymer is added to 100 parts by weight of the organic solvent, stirred at 40 ° C. for 1 hour, cooled to room temperature, and left for 24 hours or longer. It can be measured by a method for confirming that the solution is uniform without generation of insoluble matter or precipitates.

  The weight average molecular weight of the component (A) of the present invention 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, the flexibility and chemical resistance may be lowered. When the weight average molecular weight is 1,000,000 or more, the viscosity of the black photosensitive resin composition is increased. There is.

  The component (A) of the present invention is not particularly limited. For example, polyurethane resin, poly (meth) acrylic resin, polyvinyl resin, polystyrene resin, polyethylene resin, polypropylene resin, polyimide resin, polyamide resin, for example. Resin, polyacetal resin, polycarbonate resin, polyester resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether sulfone resin, polyether ether ketone resin, and the like. These may be used alone or in combination of two or more. Can be used in combination. In particular, when a polyurethane-based resin or a poly (meth) acrylic resin, which is a resin containing a urethane bond in the molecule, is used, the (A) component easily penetrates into the oil-absorbing (B) component. Strong adhesiveness is obtained at the interface between the component (A) and the component (B), and the flexibility of the cured film obtained by curing the black photosensitive resin composition containing the component (A) and the component (B). This is preferable because the folding resistance is improved and the warp of the cured film is reduced.

  The resin containing a urethane bond in the molecule of the present invention is soluble in an organic solvent, contains a repeating unit containing at least one urethane bond in the molecule, and has a weight average molecular weight of polyethylene glycol It is a polymer of 1,000 to 1,000,000 in terms of conversion.

  Although the resin containing a urethane bond in the molecule of the present invention can be obtained by any reaction, for example, the following general formula (1)

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

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

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

  The diol compound of the present invention is not particularly limited as long as it has the above structure. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neo Pentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decane Polyoxya such as diol, alkylene diol such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a random copolymer of tetramethylene glycol and neopentyl glycol Ring-opening addition reaction of lactones such as xylene diol, polyester diol obtained by reacting polyhydric alcohol and polybasic acid, polycarbonate diol having carbonate skeleton, γ-butyllactone, ε-caprolactone, δ-valerolactone Polycaprolactone diol, bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide addition of hydrogenated bisphenol A The thing etc. are mentioned, These can be used individually or in combination of 2 or more types.

  In particular, when a long-chain diol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyalkylene diol, polyester diol, polycarbonate diol, or polycaprolactone diol is used, it is obtained by curing the black photosensitive resin composition. It is preferable in that the elastic modulus of the cured film is lowered and the flexibility and low warpage are excellent.

  The diisocyanate compound of the present invention is not particularly limited as long as it has the above structure. 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, diph Nylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-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 Aromatic diisocyanates such as diisocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate Compounds, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, aliphatic diisocyanate compounds such lysine diisocyanate, etc. These can be used alone or in combinations of two or more.

  In particular, when an alicyclic diisocyanate and an aliphatic diisocyanate compound are used, it is preferable in terms of excellent photosensitivity of the black photosensitive resin composition.

  In the method of synthesizing a resin containing a urethane bond in the molecule of the present invention, the blending amount of the diol compound and the diisocyanate compound is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group / hydroxyl group = 0.5 or more and 2.0. It mix | blends so that it may become the following, and it is obtained by making it react in a solvent-free or organic solvent.

  Moreover, when using 2 or more types of diol compounds, reaction with a diisocyanate compound may be performed after mixing 2 or more types of diol compounds, or each diol compound and diisocyanate compound may be made to react separately. Good. Moreover, after making a diol compound and a diisocyanate compound react, you may make the obtained terminal isocyanate compound react with another diol compound, and also make this react with a diisocyanate compound. The same applies when two or more types of diisocyanate compounds are used. In this way, a resin containing a urethane bond in a desired molecule can be produced.

  The reaction temperature between the diol compound and the diisocyanate compound is preferably 40 to 160 ° C, and more preferably 60 to 150 ° C. If it is less than 40 ° C., the reaction time becomes too long. If it exceeds 160 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.

  The above reaction can be carried out without solvent, but it is desirable to carry out the reaction in an organic solvent system in order to control the reaction. Although the organic solvent used here is not specifically limited, For example, what was illustrated above can be used.

  The amount of the organic solvent used in the reaction is desirably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. The solute weight concentration in the reaction solution is more preferably 10 wt% or more and 80 wt% or less. When the solution concentration is 5% or less, the polymerization reaction is difficult to occur, the reaction rate is lowered, and a desired structural substance may not be obtained.

  The resin containing a urethane bond in the molecule of the present invention further contains at least one organic group selected from the group consisting of (a1) (meth) acryloyl group, (a2) carboxyl group, and (a3) imide group. It is preferable. (A1) The (meth) acryloyl group is an acryloyl group and / or a methacryloyl group. When the (a1) (meth) acryloyl group is contained, the photosensitivity of the black photosensitive resin composition is improved. It can be cured by ultraviolet irradiation over time. In addition, when (a2) a carboxyl group is contained, the solubility of the black photosensitive resin composition in a developing solution of a dilute alkaline aqueous solution is improved, so that a fine pattern can be formed by developing in a short time. In addition, when it contains (a3) an imide group, the heat resistance of the black photosensitive resin composition and the electrical insulation reliability under high temperature and high humidity conditions are improved. A printed wiring board having excellent properties can be obtained.

  Here, (a1) a resin containing a urethane bond in the molecule containing a (meth) acryloyl group can be obtained by any reaction. For example, in addition to the diol compound and the diisocyanate compound, The following general formula (4)

(In the formula, R ₂ represents an m + 1 valent organic group, R ₃ represents hydrogen or an alkyl group, and m represents an integer of 1 to 3)
And / or a compound containing at least one (meth) acryloyl group and / or the following general formula (5)

(Wherein X ₂ represents an l + 1 valent organic group, X ₃ represents hydrogen or an alkyl group, and l represents an integer of 1 to 3)
It is obtained by reacting a compound containing an isocyanate group represented by the formula (1) and at least one (meth) acryloyl group.

  The compound containing a hydroxyl group and at least one (meth) acryloyl group of the present invention is not particularly limited as long as it has the above structure. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, o-phenylphenol glycidyl ether (meth) acrylate, polyethylene glycol mono (Meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hy Roxyphenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) acrylate, N-methylol acrylamide, 3,5-dimethyl-4-hydroxybenzyl acrylamide, etc. may be mentioned, and these may be used alone or in combination of two or more. Can be used in combination.

  The compound containing an isocyanate group and at least one (meth) acryloyl group of the present invention is not particularly limited as long as it has the above structure. For example, 2- (meth) acryloyloxyethyl isocyanate, 1,1- (bisacryloyl) And oxymethyl) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, and the like. These can be used alone or in combination of two or more.

  Further, (a2) a resin containing a urethane bond in a molecule containing a carboxyl group can be obtained by any reaction. For example, in addition to the diol compound and the diisocyanate compound, the following general formula ( 6)

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

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

  In particular, when a compound containing two aliphatic hydroxyl groups and one carboxyl group is used, it is preferable in terms of excellent photosensitivity of the black photosensitive resin composition.

  In addition, (a3) a resin containing a urethane bond in the molecule containing an imide group can be obtained by any reaction. For example, in addition to the diol compound and the diisocyanate compound, the following general formula ( 7)

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

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

  The poly (meth) acrylic resin of the present invention is soluble in an organic solvent and contains repeating units obtained by copolymerizing (meth) acrylic acid and / or (meth) acrylic acid ester derivatives. The polymer has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol. Here, (meth) acryl is methacryl and / or acrylic.

  The poly (meth) acrylic resin of the present invention can be obtained by any reaction. For example, a (meth) acrylic acid and / or a (meth) acrylic ester derivative is present in a solvent in the presence of a radical polymerization initiator. Obtained by reacting under

  The (meth) acrylic acid ester derivative of the present invention is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Tertiary butyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , Stearyl (meth) acrylate, benzyl (meth) acrylate, and the like, and these can be used alone or in combination of two or more. Among these (meth) acrylic acid ester derivatives, in particular, the use of methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate is the flexibility of the cured film of the black photosensitive resin composition. It is preferable from the viewpoint of chemical resistance.

  Examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, t- Organic peroxides such as butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, Acid value hydrogen etc. are mentioned, These can be used individually or in combination of 2 or more types.

  The amount of the radical polymerization initiator used is preferably 0.001 to 5 parts by weight and more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer used. When the amount is less than 0.001 part by weight, the reaction hardly proceeds, and when the amount is more than 5 parts by weight, the molecular weight may be lowered.

  The amount of solvent used in the above reaction is preferably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5 wt% or more and 90 wt% or less, and is 20 wt% or more and 70 wt% or less. More preferably. 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.

  The reaction temperature is preferably 20 to 120 ° C, and more preferably 50 to 100 ° C. When the temperature is lower than 20 ° C., the reaction time becomes too long, and when it exceeds 120 ° C., gelation due to rapid progress of reaction or three-dimensional crosslinking accompanying side reaction may be caused. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.

<(B) Crosslinked polymer particles>
The (B) crosslinked polymer particle of the present invention is a spherical polymer having a crosslinked structure in the molecule and an average particle diameter of 1 to 100 μm. When the average particle diameter is 1 μm or less, the viscosity and thixotropy of the black photosensitive resin composition are increased, and appearance defects may occur due to foaming of the coating film during coating or insufficient leveling. In the case of 100 μm or more, there are cases where particles are exposed to the opening when forming a fine pattern, resulting in poor resolution. Here, the spherical shape may be a true spherical shape or an elliptical shape.

  The average particle size of the component (B) of the present invention is preferably 1 to 50 μm, more preferably 1 to 10 μm, so that the resolution of the fine pattern, the flexibility of the resulting cured film, and the chemical resistance are excellent. Therefore, it is preferable.

  The average particle diameter of the component (B) of the present invention can be measured, for example, as a volume-based median diameter (particle diameter with respect to an integrated distribution value of 50%) by the following method.

(Average particle size measurement)
Equipment used: LA-950V2 or equivalent manufactured by Horiba, Ltd. Measurement method: Laser diffraction / scattering method

  The content of the component (B) of the present invention is preferably 30 to 100 parts by weight, more preferably 40 to 80 parts by weight with respect to 100 parts by weight of the component (A), and the effect on the surface of the obtained cured film. It is possible to form irregularities on the surface and is excellent in tack-free properties. Since the filling and curing by the component (B) is obtained, the warpage of the cured film is reduced, and the flexibility that can withstand repeated bending by improving the stress relaxation effect and fracture toughness. Improves. When component (B) is less than 30 parts by weight, it may be inferior in tack-free properties and flexibility to withstand repeated bending, and when it is more than 100 parts by weight, it is applied with flame retardant or black photosensitive resin composition solution. The coating properties at the time of application may deteriorate, and appearance defects may occur due to foaming of the coating film during coating or insufficient leveling.

  The component (B) of the present invention is not particularly limited. For example, as polymethyl methacrylate-based crosslinked polymer particles, product names Gantz Pearl GM-0600, GM-0600W, and crosslinked polymethacrylic acid manufactured by Gantz Kasei Co., Ltd. As methyl-based crosslinked polymer particles, product names Gantz Pearl GM-0105, GM-0205S, GM-0401S, GM-0407S, GM-0449S, GM-0630H, GM-0801S, GM-0807S, manufactured by Gantz Kasei Co., Ltd. GM-0849SGM-1001, GM-1001-S, GM-1007S, GM-1407S, GM-1505S-S, GM-2001, GM-2003S-S, GM-2007S, GM-2801, GM-4003, GM- 5003, GM-9005, GMX-0610, GM -0810, GMP-0800, GMDM-050M, GMDM-080M, GMDM-100M, GMDM-150M, product names manufactured by Sekisui Plastics Co., Ltd. Techpolymer MBX-5, MBX-8, MBX-12, crosslinked polymethacryl Examples of acid butyl-based crosslinked polymer particles include Gantz Pearl GB-05S, GB-08S, GB-10S, GB-15S, and Sakusui Chemicals Co., Ltd. , BM30X-8, the cross-linked acrylic cross-linked polymer particles are manufactured by Gantz Kasei Co., Ltd. product name Gantz Pearl GMP-0820, and the acrylic copolymer cross-linked polymer particles are manufactured by Gantz Kasei Co., Ltd. As crosslinked styrene-based crosslinked polymer particles, As product names GANTZPARL GS-0605, GS-1105 manufactured by Tsusei Corporation, product names Techpolymer SBX-6, SBX-8, and crosslinked polyacrylate ester-based crosslinked polymer particles manufactured by Sekisui Chemicals Co., Ltd. Product names manufactured by Sekisui Plastics Co., Ltd. Techpolymer ABX-8, AF10X-8, AFX-15, ARX-15, and nylon-based crosslinked polymer particles include product names Gantz Pearl GPA-550, manufactured by Gantz Kasei Co., Ltd. As the silicone-based crosslinked polymer particles, the product names Gantz Pearl SI-020, SI-030, SI-045 manufactured by Gantz Kasei Co., Ltd. As the crosslinked silicone-based crosslinked polymer particles, the product name Gantz Pearl SIG manufactured by Gantz Chemical Co., Ltd. -070, a crosslinked urethane-based crosslinked polymer particle is a product of Dainichi Seika Kogyo Co., Ltd. Product Name Dymic Beads UCN-8070CM Clear, UCN-8150CM Clear, UCN-5070D Clear, UCN-5150D Clear, Trade Names Art Pearl C-100 Transparent, C-200 Transparent, C-300 Transparent, C -300WA, C-400 transparent, C-400WA, C-600 transparent, C-800 transparent, C-800WA, P-400T, P-800T, U-600T, CF-600T, JB-400T, JB-800T, CE-400T, CE-800T etc. are mentioned, These can be used individually or in combination of 2 or more types.

  The component (B) of the present invention uses a crosslinked polymer particle that contains a urethane bond in the molecule among the crosslinked polymer particles, in order to improve the flexibility of the cured film to reduce warpage and to withstand repeated bending. Is preferred.

<(C) Thermosetting resin>
The (C) thermosetting resin of the present invention is a compound containing at least one thermosetting organic group in the molecule.

  (C) component of this invention will not be specifically limited if it is the said structure, For example, an epoxy resin, an oxetane resin, a phenol resin, an isocyanate resin, a block isocyanate resin, a bismaleimide resin, a bisallyl nadiimide resin, a polyester resin (For example, unsaturated polyester resin), diallyl phthalate resin, silicon resin, vinyl ester resin, melamine resin, polybismaleimide triazine resin (BT resin), cyanate resin (for example, cyanate ester resin), urea resin, guanamine resin, sulfoamide Resins, aniline resins, polyurea resins, thiourethane resins, polyazomethine resins, episulfide resins, ene-thiol resins, benzoxazine resins, copolymer resins thereof, modified resins obtained by modifying these resins, or these Mixtures of resins with each other or other resins and the like.

  As the component (C) of the present invention, among the above thermosetting resins, the use of a polyfunctional epoxy resin can impart heat resistance to a cured film obtained by curing a black photosensitive resin composition. It is preferable because adhesion to a conductor such as a metal foil or a circuit board can be imparted.

  The polyfunctional epoxy resin is a compound containing at least two epoxy groups in the molecule. For example, as the bisphenol A type epoxy resin, trade names jER828, jER1001, jER1002, and Japan Corporation made by Japan Epoxy Resin Co., Ltd. ADEKA brand name Adeka Resin EP-4100E, Adeka Resin EP-4300E, Nippon Kayaku Co., Ltd. trade names RE-310S, RE-410S, DIC Corporation trade names Epicron 840S, Epicron 850S, Epicron 1050, Epicron 7050 Toto Kasei Co., Ltd. trade names Epototo YD-115, Epototo YD-127, Epototo YD-128, Bisphenol F type epoxy resin, trade names jER806, jE made by Japan Epoxy Resin Co., Ltd. 807, trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, manufactured by Adeka Co., Ltd., trade names RE-303S, RE-304S, RE-403S, RE-404S, DIC manufactured by Nippon Kayaku Co., Ltd. Product names Epicron 830 and Epicron 835 manufactured by Co., Ltd. Product names Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001, and Bisphenol S type epoxy resin manufactured by Toto Kasei Co., Ltd. As Epiklon EXA-1514 and hydrogenated bisphenol A type epoxy resin, trade names jERYX8000, jERYX8034, jERYL7170, manufactured by Japan Epoxy Resin Co., Ltd., and Adeka Resin EP-4 manufactured by ADEKA Co., Ltd. 80E, DIC Corporation trade name Epicron EXA-7015, Toto Kasei Co., Ltd. trade name Epototo YD-3000, Epototo YD-4000D, biphenyl type epoxy resin, Japan Epoxy Resin Corporation trade name jERYX4000, jERYL6121H, jERYL6640, jERYL6667, Nippon Kayaku Co., Ltd. trade name NC-3000, NC-3000H, phenoxy type epoxy resin, Japan Epoxy Resin Co., Ltd. trade name jER1256, jER4250, jER4275, naphthalene type epoxy resin Are DIC Corporation's trade names Epicron HP-4032, Epicron HP-4700, Epicron HP-4200, Nippon Kayaku Co., Ltd. trade names NC-7000L, Phenoh As the lenovolac 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, product names Epototo YDPN-638 manufactured by Tohto Kasei Co., Ltd., and cresol novolak type epoxy resins include product names EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, DIC shares manufactured by Nippon Kayaku Co., Ltd. Brand names EPIKRON N-660, Epicron N-670, Epicron N-680, Epicron N-695, and trisphenol methane type epoxy resins manufactured by the company include trade names EPPN-501H and EPPN-501HY manufactured by Nippon Kayaku Co., Ltd. EPPN-502 As a dicyclopentadiene type epoxy resin, trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd., as trade name Epicron HP-7200 manufactured by DIC Corporation, and as an amine type epoxy resin, a product manufactured by Japan Epoxy Resin Co., Ltd. Names jER604, jER630, Toto Kasei Co., Ltd. trade names Epototo YH-434, Epototo YH-434L, Mitsubishi Gas Chemical Co., Ltd. trade names TETRAD-X, TERRAD-C, and flexible epoxy resins include Japan Epoxy Resin Trade names jER871, jER872, jERYL7175, jERYL7217, DIC Corporation's trade name Epicron EXA-4850, and urethane-modified epoxy resins include ADEKA Corporation's trade names Adeka Resin EPU-6, Adeka Resin Examples of PU-73, Adeka Resin EPU-78-11, and rubber-modified epoxy resins include Adeka Resin EPR-4023, Adeka Resin EPR-4026, Adeka Resin EPR-1309, and Adeka Resin EPR-1309. Examples of the product names Adeka Resin EP-49-10, Adeka Resin EP-49-20, and heterocyclic-containing epoxy resins include the product names TEPIC manufactured by Nissan Chemical Co., Ltd.

  The black photosensitive resin composition of the present invention is not particularly limited as a curing agent for the thermosetting resin. For example, phenol novolak resin, cresol novolak resin, phenol resin such as naphthalene type phenol resin, amino resin, urea Resins, melamine, dicyandiamide and the like can be mentioned, and these can be used alone or in combination of two or more.

  Further, the curing accelerator is not particularly limited, but for example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine and tetraethanolamine; 1,8- Borate compounds such as diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-un Imidazoles such as decylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline, 2- Ethyl imidazoline, 2 Imidazolines such as isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ Examples include azine-based imidazoles such as -ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, and these can be used alone or in combination of two or more.

<(D) Photopolymerization initiator>
The (D) photopolymerization initiator of the present invention is a compound that is activated by energy such as UV and initiates / promotes a reaction of a radical polymerizable group.

  The component (D) of the present invention is not particularly limited as long as it has the above structure. For example, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) ) Triphenylmethane, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, acetophenone, benzoin, 2-methylbenzoin, benzoinmethyl ester -Tell, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethyl Thioxanthone, 2-isopropylthioxanthone, 1-hydroxycyclohexyl phenyl keto , Diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, 2 (2′-furylethylidene) -4,6-bis (trichloromethyl) -S-triazine, 2 [2 ′ (5 ″ -methyl) Furyl) ethylidene] -4,6-bis (trichloromethyl) -S-triazine, 2 (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,6-di (p-azidobenzal) ) -4-methylcyclohexanone, 4,4'-diazidochalcone, di (tetraalkylammonium) -4,4'-diazidostilbene-2,2'-disulfonate, 2,2-dimethoxy-1,2 -Diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl- Propane-1-ketone, bis (n5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pi 1-yl) -phenyl) titanium, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], iododium, (4-methylphenyl) [ 4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-), ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxyome) and the like, and these can be used alone or in combination of two or more.

  The component (D) of the present invention includes 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl), which is an oxime ester photopolymerization initiator, among the photopolymerization initiators. Oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxyome) is used as a black photosensitive resin It is preferable for improving the photosensitivity, sensitivity and resolution of the composition.

<(E) Phosphorus flame retardant>
The (E) phosphorus flame retardant of the present invention is a compound that contains at least one phosphorus element in the molecule and has an effect of suppressing the combustion of organic matter.

  The component (E) of the present invention is not particularly limited as long as it has the above structure. For example, red phosphorus, condensed phosphate ester compounds, cyclic organic phosphorus compounds, phosphazene compounds, phosphorus-containing (meth) acrylate compounds , Phosphorus-containing epoxy compounds, phosphorus-containing polyol compounds, phosphorus-containing amine compounds, ammonium polyphosphate, melamine phosphate, phosphinate, and the like, and these can be used alone or in combination of two or more. .

  Among the phosphorus-based flame retardants, component (E) of the present invention uses phosphinates in particular, and imparts excellent flame retardancy to a cured film obtained by curing a black photosensitive resin composition. In addition, since the bleed-out of the flame retardant from the cured film is small, contact failure and process contamination can be suppressed, which is preferable.

  The phosphinic acid salt of the present invention is a compound represented by the following general formula (8).

(In the formula, R ₅ and R ₆ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and M represents Mg, Ca, Al, Sb, Sn, Ge, Ti. , Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, and K represent metals selected from the group consisting of at least one of t.

  The phosphinic acid salt of the present invention is not particularly limited as long as it has the above structure. For example, aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, bismethylethylphosphine Examples thereof include zinc oxide, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanyl bismethylethylphosphinate, titanyl bisdiphenylphosphinate, and the like. These can be used alone or in combination of two or more. Of these, aluminum trisdiethylphosphinate and aluminum trismethylethylphosphinate are particularly preferable because high flame retardancy can be obtained.

  The content of the component (E) of the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the component (A). Excellent in electrical insulation reliability. When the amount of the component (E) is less than 5 parts by weight, the flame retardancy may be inferior. When the amount is more than 100 parts by weight, the crease resistance may be inferior, or when the black photosensitive resin composition solution is applied. Workability deteriorates and appearance defects may occur due to foaming of the coating film during coating or insufficient leveling.

<(F) Black colorant>
The (F) black colorant of the present invention is a substance having an effect of coloring other substances such as black dyes and black pigments black, and a black pigment is preferable from the viewpoint of colorability and heat resistance. The black pigment is not particularly limited. For example, carbon black, lamp black, titanium black, graphite, iron oxide, copper oxide, cobalt oxide, nickel oxide, iron-manganese composite oxide, iron-cobalt-chromium composite oxide Products, iron-chromium-manganese composite oxides, copper-chromium composite oxides, copper-chromium-manganese composite oxides, aniline compounds, anthraquinone compounds, perylene compounds, etc. Alternatively, two or more types can be used in combination. Among these, carbon black is particularly preferable because high colorability and concealability can be obtained.

  The content of the component (F) of the present invention is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, with respect to 100 parts by weight of the component (A). Excellent blackness and concealment. When the component (E) is less than 0.1 parts by weight, the blackness and the hiding property may be inferior. When the component is more than 20 parts by weight, the transmittance of the black photosensitive resin composition solution is lowered, and thus the photosensitivity is low. May decrease.

<Other ingredients>
The black photosensitive resin composition of the present invention further includes various additives such as a radical polymerizable compound, a filler, an adhesion aid, an antifoaming agent, a leveling agent, other colorants, and a polymerization inhibitor as necessary. Can be added.

  The said radically polymerizable compound is a compound which contains the radically polymerizable group which a polymerization reaction advances with a radical polymerization initiator in a molecule | numerator. Among these, a resin having at least one unsaturated double bond in the molecule is preferable. Furthermore, the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.

  The radical polymerizable compound is preferably used when the component (A) does not contain a (meth) acryloyl group. Further, the component (A) may be used even if it contains a (meth) acryloyl group.

  Examples of the radical polymerizable compound 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-hexanediol dimethacrylate Acrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethyl Roll propane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol Hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hy Roxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (Methacryloxytoki Si) phenyl] propane, 2,2-bis [4- (methacryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate , Polypropylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3- Methacryloxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene Recall acrylate, nonylphenoxypolyethylene glycol acrylate, nonylphenoxypolypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol di Methacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate , Tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4- Diethyl-1,5-pentanediol diacrylate, ethoxylated tomethylolpropane triacrylate, propoxylated tomethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxy Pentathritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl Ryl ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, arobarbital, diallylamine, diallyldimethylsilane, diallyl Disulfide, diallyl ether, zalyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4′-isopropylidene diphenol dimethacrylate, 4,4′-isopropyl Examples thereof include redene diphenol diacrylate, and these can be used alone or in combination of two or more. In particular, when one containing 2 to 50 mol of EO (ethylene oxide) repeating units contained in one molecule of diacrylate or dimethacrylate is used, an aqueous system represented by an alkaline aqueous solution of a black photosensitive resin composition This is preferable because the solubility in the developer is improved and the development time is shortened.

  Examples of the filler include fine inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, and calcium carbonate.

  Examples of the antifoaming agent include acrylic compounds, vinyl compounds, butadiene compounds, and the like.

  Examples of the leveling agent include acrylic compounds and vinyl compounds.

  Examples of the other colorant include phthalocyanine compounds and azo compounds.

  Examples of the adhesion assistant (also referred to as adhesion-imparting agent) include silane coupling agents, triazole compounds, tetrazole compounds, and triazine compounds.

  Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether.

  The black photosensitive resin composition of the present invention is excellent in flame retardancy because it contains the component (E), but another flame retardant may be added to obtain a higher flame retardant effect. As the flame retardant, for example, a halogen-containing compound, a metal hydroxide, a melamine compound, or the like can be added. The above various additives can be used alone or in combination of two or more.

<Mixing method of black photosensitive resin composition>
The black photosensitive resin composition of the present invention can be obtained by pulverizing and dispersing the above components (A) to (F) and other components and mixing them. The pulverizing / dispersing method is not particularly limited, and for example, it is 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 black photosensitive resin composition 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 for Using Black Photosensitive Resin Composition Using the black photosensitive resin composition of the present invention directly or after preparing a black photosensitive resin composition solution, a cured film or a relief is as follows. A pattern can be formed. First, the black photosensitive resin composition or the black photosensitive resin composition solution is applied to a substrate and dried to remove the organic solvent. The substrate can be applied by screen printing, curtain roll, river roll, spray coating, spin coating using a spinner, or the like. Drying of the coating film (preferably thickness: 5 to 100 μm, particularly 10 to 100 μm) is performed 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 alkaline aqueous solution is preferably used. This developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, or N-methyl-2-pyrrolidone. 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 black photosensitive resin composition of 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 black 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. It is preferably used in the following.

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

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

  The cured film formed from the black photosensitive resin composition of the present invention is excellent in concealment, excellent in flexibility, flame retardancy, and electrical insulation reliability, and has little warpage of the substrate after curing.

  Further, for example, the insulating film obtained from the black 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 a black photosensitive resin composition is especially suitable as an insulating material of a 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 black photosensitive resin composition or the black photosensitive resin composition solution to the base-material surface, and drying. it can.

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

(Synthesis Example 1)
<(A) Binder polymer 1>
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a nitrogen inlet tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, and under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g (0.14 mol) of methacrylic acid, 28.0 g (0.16 mol) of benzyl methacrylate, 60.0 g (0.42 mol) of butyl methacrylate, previously mixed at room temperature, As a radical polymerization initiator, 0.5 g of azobisisobutyronitrile was added dropwise from a dropping funnel over 3 hours while keeping the temperature at 80 ° C. After completion of the dropwise addition, the reaction solution was heated to 90 ° C. while stirring, and the reaction solution was further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. for reaction. By carrying out the above reaction, an acrylic resin solution containing a carboxyl group in the molecule was obtained. The resulting resin solution had a solid content concentration of 50%, a weight average molecular weight of 48,000, and a solid content acid value of 78 mgKOH / g. The solid content concentration, weight average molecular weight, and acid value were measured by the following methods.

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

<Weight average molecular weight>
Measurement was performed 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)
<(A) Binder polymer 2>
Into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 30.00 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) was charged as a polymerization solvent, and this was mixed with norbornene diisocyanate 10 .31 g (0.050 mol) was charged and dissolved by heating to 80 ° C. with stirring under a nitrogen stream. To this solution, 50.00 g (0.025 mol) of polycarbonate diol (manufactured by Asahi Kasei Corporation, product name PCDL T5652, weight average molecular weight 2000) and 6.51 g (0.050 mol) of 2-hydroxyethyl methacrylate were added to methyltriglyme. A solution dissolved in 30.00 g was added over 1 hour. This solution was reacted by heating and stirring at 80 ° C. for 5 hours. By performing the above reaction, a resin solution containing a urethane bond and a methacryloyl group in the molecule was obtained. The resulting resin solution had a solid content concentration of 53% and a weight average molecular weight of 5,200. The solid content concentration and the weight average molecular weight were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 3)
<(A) Binder polymer 3>
Into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 30.00 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) was charged as a polymerization solvent, and this was mixed with norbornene diisocyanate 10 .31 g (0.050 mol) was charged and dissolved by heating to 80 ° C. with stirring under a nitrogen stream. To this solution, polycarbonate diol 50.00 g (0.025 mol) (manufactured by Asahi Kasei Corporation, product name PCDL T5652, weight average molecular weight 2000) and 2,2-bis (hydroxymethyl) butanoic acid 3.70 g (0.025 Mol) in 30.00 g of methyltriglyme was added over 1 hour. This solution was reacted by heating and stirring at 80 ° C. for 5 hours. By performing the above reaction, a resin solution containing a urethane bond and a carboxyl group in the molecule was obtained. The obtained resin solution had a solid content concentration of 52%, a weight average molecular weight of 5,600, and a solid content acid value of 22 mgKOH / g. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 4)
<(A) Binder polymer 4>
Into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 40.00 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) was charged as a polymerization solvent, and this was mixed with norbornene diisocyanate 20 .62 g (0.100 mol) was charged and dissolved by heating to 80 ° C. with stirring under a nitrogen stream. To this solution, 50.00 g (0.025 mol) of polycarbonate diol (manufactured by Asahi Kasei Co., Ltd., product name PCDL T5652, weight average molecular weight 2000), 3.70 g (0.025) of 2,2-bis (hydroxymethyl) butanoic acid Mol) and a solution prepared by dissolving 13.02 g (0.100 mol) of 2-hydroxyethyl methacrylate in 40.00 g of methyltriglyme was added over 1 hour. This solution was reacted by heating and stirring at 80 ° C. for 5 hours. By performing the above reaction, a resin solution containing a urethane bond, a carboxyl group, and a (meth) acryloyl group in the molecule was obtained. The obtained resin solution had a solid content concentration of 52%, a weight average molecular weight of 8,600, and a solid content acid value of 18 mgKOH / g. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 5)
<(A) Binder polymer 5>
Into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 35.00 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) was charged as a polymerization solvent, and this was mixed with norbornene diisocyanate 10 .31 g (0.050 mol) was charged and dissolved by heating to 80 ° C. with stirring under a nitrogen stream. A solution obtained by dissolving 50.00 g (0.025 mol) of polycarbonate diol (product name: PCDL T5652; weight average molecular weight 2000) in 35.00 g of methyltriglyme was added to this solution over 1 hour. This solution was heated and stirred at 80 ° C. for 2 hours. After completion of the reaction, 15.51 g (0.050 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride (hereinafter referred to as ODPA) was added to the above reaction solution. After the addition, the mixture was heated to 190 ° C. and reacted for 1 hour. The solution was cooled to 80 ° C. and 3.60 g (0.200 mol) of pure water was added. After the addition, the temperature was raised to 110 ° C. and heated to reflux for 5 hours. By performing the above reaction, a resin solution containing a urethane bond, a carboxyl group and an imide group in the molecule was obtained. The obtained resin solution had a solid content concentration of 53%, a weight average molecular weight of 9,200, and a solid content acid value of 86 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 1-6)
<Preparation of black photosensitive resin composition>
(A) Binder polymer, (B) Crosslinked polymer particles, (C) Thermosetting resin, (D) Photopolymerization initiator, (E) Phosphorous flame retardant, (F) Black colorant, obtained in Synthesis Example Other components and an organic solvent were added to prepare a black photosensitive resin composition. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. In addition, 1,2-bis (2-methoxyethoxy) ethane which is a solvent in the table is the total amount of the solvent including the solvent contained in the synthesized resin solution. The black photosensitive resin composition was first mixed with a general stirrer equipped with a stirring blade, and then passed twice with a three-roll mill to obtain a uniform solution. When the particle diameter was measured with a grindometer, all were 10 μm or less. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.

<1> manufactured by Dainichi Seika Kogyo Co., Ltd. Product name of crosslinked polymer particles containing urethane bonds in the molecule, average particle diameter of 7 μm
<2> Product name of cross-linked polybutyl methacrylate-based cross-linked polymer particles manufactured by Ganz Kasei Co., Ltd., average particle diameter of 5 μm
<3> Product name of polyfunctional epoxy resin (triglycidyl isocyanurate) manufactured by Nissan Chemical Co., Ltd. <4> Product name of oxime ester photopolymerization initiator manufactured by BASF Japan Co., Ltd. <5> Phosphorus-based difficulty manufactured by Clariant Japan Product name of flame retardant (diethylphosphinic acid aluminum salt), average particle size 2.5μm
<6> Product name of black colorant (carbon black) manufactured by Mitsubishi Chemical Co., Ltd. <7> Product name of EO-modified bisphenol A dimethacrylate manufactured by Hitachi Chemical Co., Ltd. <8> Product of butadiene type antifoaming agent manufactured by Kyoeisha Chemical Co., Ltd. product name

<Preparation of coating film on polyimide film>
Using a Baker applicator, the black photosensitive resin composition was cast and applied to a 25 μm polyimide film (manufactured by Kaneka Co., Ltd .: trade name 25 NPI) to an area of 100 mm × 100 mm so that the final dry thickness was 20 μm. Then, after drying at 80 ° C. for 20 minutes, 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 sufficiently washed with pure water, and then cured by heating in an oven at 150 ° C. for 30 minutes to prepare a cured film of a black photosensitive resin composition on the polyimide film.

<Evaluation of cured film>
The following items were evaluated. The evaluation results are shown in Table 2.

(I) Photosensitivity The surface of the cured film obtained by the same method as the above item <Preparation of coating film on polyimide film> was observed and determined. However, the exposure was performed by placing a negative photomask of line width / space width = 100 μm / 100 μm.
◯: A photosensitive pattern having a line width / space width = 100/100 μm can be drawn on the polyimide film surface without noticeable line thickness or development residue.
X: A line width / space width = 100/100 μm photosensitive pattern is not drawn on the polyimide film surface.

(Ii) Tack-free property Using the Baker type applicator, the black photosensitive resin composition is 100 mm × 100 mm so that the final dry thickness is 20 μm on a 25 μm polyimide film (manufactured by Kaneka Corporation: trade name 25 NPI). The film was cast and applied to the area and dried at 80 ° C. for 20 minutes to prepare a coating film after drying the solvent. The method for evaluating the tack-free property of the coating film is to cut out the film with the coating film after drying the solvent into 50 mm x 30 mm strips, and the coating film surfaces overlap each other with the coating film on the inside. After applying a load of 300 g for 3 seconds, the load was removed and the state when the coating film surface was peeled off was observed.
○: There is no sticking between the coating films, and no sticking marks remain on the coating film.
(Triangle | delta): The coating films stick a little and the sticking trace remains in the coating film.
X: The coating films adhered completely and cannot be peeled off.

(Iii) Folding resistance Black 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 prepared. 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 loading, 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.
A: The cured film has no cracks after being bent five times.
Δ: The cured film has no cracks after being bent three times.
X: A crack occurs in the cured film at the first folding.

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

(V) Solder heat resistance A black photosensitive resin composition having a thickness of 20 μm on the surface of a 75 μm-thick polyimide film (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 prepared.
The obtained cured film laminated film was floated so that the surface coated with the cured film of the black 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.

(Vi) Warpage Curing of a black photosensitive resin composition having a thickness of 20 μm on the surface of a polyimide film having a thickness of 25 μm (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item <Preparation of a coating film on a polyimide film> A film laminated film was produced.
The obtained cured film laminated film was cut into 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 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 rounding cylindrically, it was set as x.

(Vii) Flame retardancy In accordance with the flammability test standard UL94VTM of plastic materials, the flammability test was performed as follows. In the same manner as in the above item <Preparation of coating film on polyimide film>, a cured film of black 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: Apical 25 NPI). A film was prepared. 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) and the upper part, and 20 cylinders for flammability test were prepared. Of these, 10 were treated at (1) 23 ° C./50% relative humidity / 48 hours, and the remaining 10 were treated at (2) 70 ° C. for 168 hours and then cooled in a desiccator containing anhydrous calcium chloride for 4 hours or more. The upper part of these samples is clamped and fixed vertically, and a burner flame is brought close to the lower part of the sample for 3 seconds to ignite. After 3 seconds, move the burner flame away and measure how many seconds after the sample flame or burning disappears.
○: For each condition ((1), (2)), the flame and combustion stopped within 10 seconds on average (average of 10) after the flame of the burner was moved away from the sample, and self-extinguishment within 10 seconds at maximum However, it has not burned to the rating line.
×: Even one sample does not extinguish within 10 seconds, or the flame rises above the rating line and burns.

(Viii) Concealing property The test piece obtained in the item (vi) warping is placed on a graph paper having a 1 mm square cell, and the cell is visually concealed by checking the cell from above the test piece. Was evaluated.
○: Invisible cells.
X: What can see a grid.

(Comparative Example 1)
After introducing air into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air introduction pipe, 210.0 g of cresol novolac type epoxy resin (manufactured by DIC Corporation, product name Epicron N-680, epoxy equivalent 210), carbitol 96.4 g of acetate was charged and dissolved by heating. Next, 0.46 g of hydroquinone as a polymerization inhibitor and 1.38 g of triphenylphosphine as a reaction catalyst were charged, and the temperature was raised to 95 ° C. with uniform stirring under an air stream. Next, 72.0 g of acrylic acid was charged into the dropping container, and acrylic acid was dropped into the reaction container while heating to 95 to 105 ° C. After the dropping was completed, the reaction was continued for about 16 hours until the acid value reached 3.0 KOHmg / g or less. I let you. Next, the reaction solution was cooled to 80 to 90 ° C., charged with 76.0 g of tetrahydrophthalic anhydride and reacted for 8 hours to obtain a resin solution. By performing the above reaction, a resin solution containing a photocurable resin was obtained. The resulting resin solution had a solid content concentration of 65% and an acid value of 78 KOH mg / g. The solid content concentration and the acid value were measured in the same manner as in Synthesis Example 1. 154 g (100 g as a solid content) of the obtained resin solution, 18 g of dipentaerythritol hexaacrylate as a radical polymerizable compound, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- as a photopolymerization initiator 15 g Propan-1-one (manufactured by BASF Japan, product name Irgacure 907), 1 g 2,4-diethylthioxanthone, and 0.1 g 4,4′-bis (dimethylamino) benzophenone, bisphenol A as a polyfunctional epoxy resin 25 g of diglycidyl ether and 15 g of triglycidyl isocyanurate, 2.2 g of carbon black (product name: Carbon Black M-50, manufactured by Mitsubishi Chemical Corporation), 5 g of melamine as a curing catalyst, 3 g of silicone-based antifoaming agent, 3 g of organic bentonite, sulfuric acid Barium 140 g and 18 g of diethylene glycol monoethyl ether acetate were mixed and stirred and dispersed by a three roll mill to obtain a black photosensitive resin composition. The physical properties of this black photosensitive resin composition were evaluated in the same manner as in Example 1. The results are listed in Table 2. In addition, (B) component and (E) component are not contained in the said black photosensitive resin composition.

(Comparative Example 2)
A resin solution obtained by copolymerizing methacrylic acid, methyl methacrylate and butyl acrylate as a binder polymer in a weight ratio of 17:62:21 (weight average molecular weight 110,000, solid acid value 110 mg KOH / g, methyl cellosolve) 150 g (solution dissolved to a solid content concentration of 40% / toluene = 6/4 (weight ratio)) (60 g as solid content), urethane-modified epoxy acrylate resin (Nippon Kayaku Co., Ltd.) containing a urethane bond Product name KAYARAD UXE-3024, solid content concentration 65%, weight average molecular weight 10,000, solid content acid value 60 mgKOH / g) 15.4 g (10 g as solid content) and urethane / unsaturated oligomer ( 3 mol of a polycarbonate compound having a hydroxyl group at the end, and isophorone diiso Photopolymerization compound obtained by reacting 4 moles of cyanate with 2 moles of 2-hydroxyethyl acrylate) 45 g as a solid content, 1.5 g of carbon black as a black pigment, and bisphenol A skeleton ethylene oxide modification as a radical polymerizable compound 30 g of dimethacrylate, 2.5 g of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF Japan Ltd., product name Irgacure 369) as a photopolymerization initiator, heat A black photosensitive resin composition was prepared by blending and stirring 17 g of melamine derivative as a curable resin and 45 g of methyl ethyl ketone and 20 g of toluene as other components and dispersing them with a three-roll mill. The physical properties of this black photosensitive resin composition were evaluated in the same manner as in Example 1. The results are listed in Table 2. In addition, (B) component and (E) component are not contained in the said black photosensitive resin composition.

(Comparative Example 3)
80.00 g of carbitol acetate was added to 100.00 g of a cresol novolac-type epoxy resin YDCN-703 (Epto equivalent 200, manufactured by Tohto Kasei Co., Ltd.), and heated and dissolved at 120 ° C. with stirring. After cooling to 60 ° C., 43.48 g (20.00 g as a solid content) of an emulsion of (meth) acrylic acid ester polymer fine particles (glass transition temperature—8 ° C., solid content: 46.0%) was added and stirred. The temperature was raised to 130 ° C. to completely remove water. Next, 36.90 g of acrylic acid, 0.14 g of chromic chloride hexahydrate and 0.11 g of methylhydroquinone were added and reacted at 110 ° C. for 3 hours. The acid value of the reaction product was 3.0 mgKOH / g, and the introduction of an acryloyl group was confirmed. Next, 45.60 g of tetrahydrophthalic anhydride, 29.00 g of ethyl carbitol acetate and 0.14 g of anhydrous lithium chloride are added and reacted at 100 ° C. for 3 hours to obtain 6.4 (meth) acrylic acid ester polymer fine particles. % And a mixed resin solution of ethyl carbitol acetate containing 58.6% of a photocurable resin having an acid value of 90 mgKOH / g. 90 g of the obtained resin solution (5.8 g of polymer fine particles as solid content, 52.7 g of photocurable resin), 15.0 g of pentaerythritol tetraacrylate as a polyfunctional monomer, 20.0 g of ethyl carbitol acetate as a diluent, light 8.0 g of Irgacure 907 (product name manufactured by BASF Japan Ltd.) as the polymerization initiator, 20.0 g of phenol novolac type epoxy resin as the thermosetting resin, 2.0 g of dicyandiamide as the epoxy curing agent, and barium sulfate 30 as the filler 1.0 g, 1.2 g of product name Floren AC300 manufactured by Kyoeisha Chemical Co., Ltd. as an antifoaming agent, and 0.6 g of phthalocyanine green as a pigment were mixed and stirred and dispersed with a three roll to obtain a photosensitive resin composition. . The physical properties of this photosensitive resin composition were evaluated in the same manner as in Example 1. The results are listed in Table 2. In addition, (E) component and (F) component are not contained in the said photosensitive resin composition.

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

Claims (13)

At least (A) a binder polymer,
(B) crosslinked polymer particles,
(C) thermosetting resin,
(D) a photopolymerization initiator,
(E) phosphorus flame retardant,
(F) A black photosensitive resin composition containing a black colorant.   The black photosensitive resin composition according to claim 1, wherein the (A) binder polymer is a resin containing a urethane bond in the molecule. The black photosensitive material according to claim 2, wherein the resin containing a urethane bond in the molecule further contains at least one organic group selected from the group consisting of the following (a1) to (a3). Resin composition.
(A1) (meth) acryloyl group (a2) carboxyl group (a3) imide group   The black photosensitive resin composition according to any one of claims 1 to 3, wherein the (B) crosslinked polymer particles are crosslinked polymer particles containing a urethane bond in the molecule.   The black photosensitive resin composition according to claim 1, wherein the (C) thermosetting resin is a polyfunctional epoxy resin.   The black photosensitive resin composition according to claim 1, wherein the (D) photopolymerization initiator is an oxime ester photopolymerization initiator.   The black photosensitive resin composition according to claim 1, wherein the (E) phosphorus flame retardant is a phosphinate.   The black photosensitive resin composition according to any one of claims 1 to 7, wherein the (F) black colorant is carbon black.   The black photosensitive composition according to any one of claims 1 to 8, wherein the blending amount of the (B) crosslinked polymer particles is 30 to 100 parts by weight with respect to 100 parts by weight of the (A) binder polymer. Resin composition.   The amount of the (E) phosphorus flame retardant is 5 to 100 parts by weight based on 100 parts by weight of the (A) binder polymer. Photosensitive resin composition.   The resin film obtained by apply | coating at least the black photosensitive resin composition of any one of Claims 1-10 to the base-material surface, and drying.   An insulating film obtained by curing the resin film according to claim 11.   A printed wiring board with an insulating film, wherein the insulating film according to claim 12 is coated on the printed wiring board.

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