JP2011237643A - Novel photosensitive resin composition and its usage - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can be finely processed due to photosensitivity and can be developed by using a dilute alkali aqueous solution and is curable at a low temperature (200°C or less) and the hardening film obtained from which is very flexible and which is excellent in terms of electric insulation reliability, solder heat resistance, organic solvent resistance and fire retardancy and has small warpage after hardening.SOLUTION: A photosensitive resin composition includes at least (A) a binder resin, (B) a photosensitive film, and (C) a photopolymerization initiator. The (A) binder resin is obtained by copolymerisation of at least (a) (meth)acrylic acid and (b) a phosphine oxide compound expressed by the following general formula (1).

Description

  Since this invention has photosensitivity, it can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or lower), and the resulting cured film is highly flexible and has an electrical insulation reliability. , Solder heat resistance, organic solvent resistance, flame resistance, and a cured photosensitive resin composition with low warpage of the substrate, a resin film obtained therefrom, an insulating film, and a printed wiring board with an insulating film is there.

  Conventionally, in the printed wiring board manufacturing industry, a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film has been used as a surface protective material for a flexible circuit board. When bonding this coverlay film on a flexible circuit board, there is a method in which an opening is provided in advance by a method such as punching in a terminal portion of a circuit or a joint portion with a component, and after aligning, a method of thermocompression bonding by a hot press or the like is used. It is common.

  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 an epoxy resin or the like is used. This photosensitive solder resist is excellent in electrical insulation reliability as an insulating material, but has mechanical properties such as flexibility. However, since the curing shrinkage is large, when it is laminated on a thin and flexible circuit board such as a flexible circuit board, the warpage of the board becomes large and it is difficult to use it for a flexible circuit board. Further, the flame retardancy is poor, and when a flame retardant is added for the purpose of imparting flame retardancy, there are problems such as deterioration in physical properties and contact failure due to bleeding out from the cured film and process contamination.

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

  For example, in Patent Literature 1, a binder polymer, a polymerizable compound containing an ethylenically unsaturated group, which is excellent in flame retardancy and plating resistance and can form a cured film having various properties required for a solder resist, A photosensitive resin composition containing a polymerization initiator and a phosphinate has been proposed. Moreover, in patent document 2, the phosphine oxide compound which has the specific structure which is excellent in the flame retardance of cured resin, the reactive compound which has two or more active energy ray reactive functional groups in a molecule | numerator, a photoinitiator There has been proposed an active energy ray-curable resin composition containing. Patent Document 3 proposes a photosensitive resin composition containing a phosphorus-containing alkali-soluble resin, a phosphorus-containing photopolymerizable compound, and a photopolymerization initiator, which has sufficient flame retardancy and high resolution. ing. Further, Patent Document 4 and Patent Document 5 propose a resin composition containing a phosphorus-containing polymer having a specific structural unit, which has sufficient flame retardancy and has reduced bleeding problems.

JP 2009-294319 A JP 2009-256622 A JP 2007-303542 A JP 2007-177203 A JP 2008-274003 A

  In the above-mentioned patent documents, various methods for solving the problems of the photosensitive solder resist are proposed. However, since the photosensitive resin composition described in Patent Document 1 contains a phosphinate that is a phosphorus-containing compound, it is excellent in flame retardancy, plating resistance, solder heat resistance, HAST resistance, etc. There is a problem that the interfacial adhesion between the acid salt and the photosensitive resin composition is insufficient, and the folding resistance is poor. Although the photosensitive resin composition described in Patent Document 2 or 3 contains a phosphorus-containing photopolymerizable compound, the problem of bleed-out is reduced. There is a problem of causing deterioration in physical properties, such as an increase in warpage. Since the photosensitive resin composition described in Patent Documents 3 to 5 has a structure including a resin having phosphorus in the skeleton, it has excellent bleed-out properties, but has a structure that facilitates hydrolysis. There is a problem in the long-term electrical insulation reliability of the cured product.

  As a result of intensive studies to solve the above problems, the inventors of the present invention include at least (A) a binder resin, (B) a photosensitive resin, and (C) a photopolymerization initiator. , At least (a) a phosphine oxide compound represented by the following general formula (1) and (b) a compound having a carboxyl group and a double bond copolymerizable with the above (a). The photosensitive resin composition characterized in that it has photosensitivity, can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or lower), and the resulting cured film has Based on these findings, we have obtained knowledge that a flexible resin composition with excellent electrical insulation reliability, solder heat resistance, organic solvent resistance, flame resistance, and low cured substrate warpage can be obtained. And reached the present invention Than is. The present invention can solve the above problems by the following novel photosensitive resin composition.

(Wherein R is H or CH ₃ )

  That is, the present invention includes at least (A) a binder resin, (B) a photosensitive resin, and (C) a photopolymerization initiator, and the (A) binder resin is at least (a) the following general formula (1). And a phosphine oxide compound represented by (b) and a compound having a carboxyl group and a double bond copolymerizable with the above (a). It is.

(Wherein R is H or CH ₃ )

  Moreover, as for the photosensitive resin composition concerning this invention, it is preferable that said (b) is a compound which has (meth) acrylic acid and / or a (meth) acryloyl group, and a carboxyl group.

  Moreover, as for the photosensitive resin composition concerning this invention, it is preferable that said (b) is (meth) acrylic acid.

  Moreover, it is preferable that the photosensitive resin composition concerning this invention is what the said (A) binder resin further copolymerized (c) (meth) acrylic-acid alkylester. In the photosensitive resin composition according to the present invention, the phosphorus element content of the binder resin (A) is preferably 2.0 to 9.5% by weight. Moreover, it is preferable that the acid value of the said (A) binder resin is 40-200 mgKOH / g in the photosensitive resin composition concerning this invention.

  Moreover, as for the photosensitive resin composition concerning this invention, it is preferable that the said (C) photoinitiator is an oxime ester type compound.

  Moreover, the photosensitive resin composition concerning this invention is (A) binder resin in the said photosensitive resin composition, (B) photosensitive resin, and (C) photoinitiator is (A) binder resin 100. It is preferable that 10 to 200 parts by weight of the photosensitive resin (B) and 0.1 to 50 parts by weight of the photopolymerization initiator (C) are blended with respect to parts by weight.

  Moreover, it is preferable that the photosensitive resin composition concerning this invention contains (D) a flame retardant further.

  Moreover, it is preferable that the photosensitive resin composition concerning this invention is 1 to 7 weight% in phosphorus element content rate in the said photosensitive resin composition.

  Moreover, it is preferable that the photosensitive resin composition concerning this invention contains (E) thermosetting resin further.

  In the photosensitive resin composition according to the present invention, the (E) thermosetting resin is preferably an epoxy resin.

  In the photosensitive resin composition according to the present invention, the blending ratio of the (E) thermosetting resin includes (A) a binder resin, (B) a photosensitive resin, and (C) a photopolymerization initiator. It is preferable that the blended amount is 0.5 to 100 parts by weight with respect to 100 parts by weight in total.

  Moreover, the photosensitive resin composition solution concerning this invention is a thing obtained by melt | dissolving the said photosensitive resin composition in the organic solvent.

  Moreover, the resin film concerning this invention is obtained by drying, after apply | coating the said photosensitive resin composition or the said photosensitive resin composition solution to a 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 obtained by coating the insulating film on the printed wiring board.

  The cured film obtained from the photosensitive resin composition of the present invention is rich in flexibility, excellent in electrical insulation reliability, solder heat resistance, organic solvent resistance, flame resistance, and has good physical properties, and after curing. Small warpage. Therefore, the photosensitive resin composition of the present invention can be used for protective films of various circuit boards and exhibits excellent effects.

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

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

(I) Photosensitive resin composition The photosensitive resin composition of the present invention comprises at least (A) a binder resin, (B) a photosensitive resin, and (C) a photopolymerization initiator. A resin obtained by copolymerizing at least (a) a phosphine oxide compound represented by the following general formula (1) and (b) a compound having a carboxyl group and a double bond copolymerizable with the above (a). It is.

(Wherein R is H or CH ₃ )

Here, although the present inventors discovered that the 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,
(A) The binder resin comprises at least (a) a phosphine oxide compound represented by the following general formula (1) and (b) a compound having a carboxyl group and a double bond copolymerizable with the above (a). Since it is polymerized and has a carboxyl group in the molecule, it becomes soluble in a developer typified by a dilute alkaline aqueous solution, and can be finely processed by exposure and development. Moreover, since it has a phosphaphenanthrene structure in the skeleton by copolymerizing the phosphine oxide compound represented by the following general formula (1) in the molecule, the bending resistance of the cured film is lowered and the substrate is warped after curing. Sufficient flame retardancy can be obtained without causing deterioration of physical properties such as an increase in the size, and further, long-term durability is also excellent.

(Wherein R is H or CH ₃ )

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

<(A) Binder resin>
The (A) binder resin used in the present invention is composed of (a) a phosphine oxide compound represented by the following general formula (1), (b) a carboxyl group and a compound having a double bond copolymerizable with the above (a). And are copolymerized.

(Wherein R is H or CH ₃ )

  (B) The compound having a carboxyl group and a double bond copolymerizable with the above (a) is not particularly limited. For example, (meth) acrylic acid, propiolic acid, crotonic acid, isocrotonic acid, myristoleic acid, palmitoleic acid , Oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, ω-carboxy-polycaprolactone (meth) acrylate, phthalate monohydroxyethyl (meth) acrylate, (meth) acrylic acid dimer 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, atropic acid, cinnamic acid, linoleic acid, eicosadiene Acid, docosadienoic acid, linolenic acid, pinolenic acid, Leostearic acid, mead acid, dihomo-Y-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, boseopentaenoic acid, eicosapentaenoic acid, ozbondic acid, iwashi acid, tetracosapenta Examples include enoic acid, docosahexaenoic acid, nisic acid, 2,2,2-trisacryloyloxymethyl succinic acid, and 2-trisacryloyloxymethylethylphthalic acid.

  In particular, when (b) uses a compound having (meth) acrylic acid and / or a (meth) acryloyl group and a carboxyl group, the resin film obtained by drying the photosensitive resin composition has excellent developability. ,preferable. Among these, when (meth) acrylic acid is used, the reactivity is excellent during copolymerization, and a resin film obtained by drying the photosensitive resin composition is preferable because of excellent developability.

  In addition to the two components (a) a phosphine oxide compound represented by the following general formula (1) and (b) a carboxyl group and a compound having a double bond copolymerizable with the above (a), further copolymerization is possible. You may copolymerize in 3 or more components which added 1 or more component of a vinyl monomer. The copolymerizable vinyl monomer is not particularly limited as long as it is copolymerizable, and examples thereof include (meth) acrylic acid alkyl esters. The (meth) acrylic acid alkyl ester is a compound having an alkyl group having 1 to 20 carbon atoms in the ester chain of the (meth) acrylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate. , (Meth) butyl acrylate, (Meth) acrylate isobutyl, (Meth) acrylate tertiary butyl, (Meth) acrylate hexyl, (Meth) acrylate 2-ethylhexyl, (Meth) octyl acrylate, (Meth) Nonyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.

(Wherein R is H or CH ₃ )

  In addition, acrylamide such as diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) Diethylaminoethyl acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meth) (Meth) acrylic monomers such as acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, and β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, Monomethyl maleate, monoethyl maleate, and Maleic acid monomers such as maleic acid monoisopropyl, fumaric acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, styrene, and a vinyl toluene.

  These may be used alone or in combination of two or more. In particular, it is preferable to use an alkyl (meth) acrylate because the cured film of the photosensitive resin composition is excellent in flexibility and chemical resistance. Among them, it is preferable to use methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate because of excellent flexibility and chemical resistance of the cured film of the photosensitive resin composition.

  Moreover, it is preferable that the phosphorus element content rate of the said (A) binder resin is 2.0 to 9.5 weight%. When the content of the phosphorus element is 2.0% by weight or more, the flame retardancy of the (A) binder resin can be more effectively obtained. Further, when the phosphorus element content is 9.5% by weight or less, a sufficient carboxyl group in the molecular structure can be secured and becomes soluble in a developer typified by a dilute alkaline aqueous solution. Fine processing is possible. Moreover, the cured film which is rich in flexibility and excellent in other property balance can be obtained.

Here, the phosphorus element content of (A) binder resin can be calculated by the following formula 1 from the total raw material weight used for copolymerization of the binder resin and the phosphorus element content contained in the raw material. Further, for example, it is possible to perform measurement by ICP emission spectroscopic analysis after performing pressure acid decomposition with a microwave decomposition apparatus.
(P ₁ × 31 / M ₁ × m ₁ +... P _n × 31 / M _n × m _n ) / w × 100 (Formula 1)
Unit:% by weight
p: Number of phosphorus elements in one molecule of each phosphorus-containing compound M: Molecular weight of each phosphorus-containing compound m: Weight of each phosphorus-containing compound (solid content)
n: an integer greater than or equal to 1 and equal to the number of types of phosphorus-containing compound w: total weight of raw material used for copolymerization of binder resin (solid content)

  Moreover, it is preferable that the acid value of the said (A) binder resin is 40-200 mgKOH / g. When the acid value is less than 40 mgKOH / g, the alkali developability of the photosensitive resin composition may be reduced. When the acid value is more than 200 mgKOH / g, the hygroscopicity of the cured film may be increased and the electrical insulation reliability may be reduced. is there.

  Here, oxidation can be measured by the method prescribed | regulated by JISK5601-2-1, for example.

Moreover, it is preferable that the weight average molecular weight of said (A) binder resin is a polymer of 3,000 or more and 300,000 or less in conversion of polyethylene glycol. Here, the molecular weight of the carboxyl group-containing resin can be measured, for example, by the following method.
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 alkali developability of the photosensitive resin composition, the flexibility of the resulting cured film, and the chemical resistance are excellent. When the weight average molecular weight is 3,000 or less, flexibility and chemical resistance may be lowered. When the weight average molecular weight is 300,000 or more, alkali developability is lowered, and the viscosity of the photosensitive resin composition. May be higher.

  The reaction of at least (a) (meth) acrylic acid and (b) the phosphine oxide compound represented by the following general formula (1) is allowed to proceed, for example, by generating radicals with a radical polymerization initiator. Can do. Examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, t-butylhydro Organic peroxides such as peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, peracid number Hydrogen etc. are mentioned, These can be used individually or in combination of 2 or more types.

(Wherein R is H or CH ₃ )

  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 above reaction can be carried out in the absence of a solvent. However, in order to control the reaction, it is desirable to carry out the reaction in an organic solvent system. For example, examples of the organic solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N , N-dimethylformamide, formamide solvents such as N, N-diethylformamide, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2 Examples include pyrrolidone solvents such as -pyrrolidone, hexamethylphosphoramide, and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  Furthermore, for example, methyl monoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (Bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2 Symmetric glycol diethers such as -butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Cetate (aka carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether Acetates such as acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n Propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a solvent may be used ethers such as ethyl ether also ethylene glycol. Of these, symmetrical glycol diethers are preferably used because side reactions are unlikely to occur.

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

  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) Photosensitive resin>
The photosensitive resin (B) used in the present invention is a compound containing in its molecule a radical polymerizable group that undergoes a polymerization reaction with a radical polymerization initiator. Among these, a resin having at least one unsaturated double bond in the molecule is preferable. Furthermore, the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.

  Examples of the photosensitive resin (B) include bisphenol F EO modified (n = 2 to 50) diacrylate, bisphenol A EO modified (n = 2 to 50) diacrylate, and bisphenol S EO modified (n = 2 to 50). Diacrylate, bisphenol F EO modified (n = 2-50) dimethacrylate, bisphenol A EO modified (n = 2-50) dimethacrylate, bisphenol S EO modified (n = 2-50) dimethacrylate, 1,6-hexane Diol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethyl Propane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipenta Erythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2- Hide Xylpropyl 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- (Methacryloxyethoxy ) 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-methacryl Roxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene group Cole acrylate, nonylphenoxy polyethylene glycol acrylate, nonyl phenoxy polypropylene 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, propoxylation Pentathritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl ali Ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, arborbital, 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 Redene diphenol diacrylate and the like are preferable, but are not limited thereto. In particular, the repeating unit of EO (ethylene oxide) contained in one molecule of diacrylate or dimethacrylate is preferably in the range of 2-50, more preferably 2-40. By using an EO repeating unit in the range of 2 to 50, the solubility of the photosensitive resin composition in an aqueous developer typified by an alkaline aqueous solution is improved, and the development time is shortened. Furthermore, it is difficult for stress to remain in the cured film obtained by curing the photosensitive resin composition. For example, among the printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, curling of the printed wiring board is prevented. Features such as being able to be suppressed.

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

(Where a + b = 6 and n = 12.)
A compound represented by the following general formula (3)

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

A compound represented by the following general formula (5)

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

(Where a + b + c = 3.6)
A compound represented by the following formula (7):

A compound represented by the following general formula (8)

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

  In addition, hydroxyl groups in the molecular structure skeleton such as 2-hydroxy-3-phenoxypropyl acrylate, monohydroxyethyl acrylate phthalate, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, pentaerythritol tri and tetraacrylate, A compound having a carbonyl group is also preferably used.

  Other molecules such as acid-modified vinyl ester resins, epoxy-modified (meth) acrylic resins, urethane-modified (meth) acrylic resins, polyester-modified (meth) acrylic resins, (meth) acrylic acid-modified epoxy resin acid adducts, etc. A radically polymerizable compound containing a radically polymerizable group may be used.

  In addition, as a radically polymerizable compound containing a radically polymerizable group in the molecule, it is possible to use one kind, but using two or more kinds in combination improves the heat resistance of the cured film. preferable.

  (B) The photosensitive resin in the photosensitive resin composition of the present invention is blended so as to be 10 to 200 parts by weight with respect to 100 parts by weight of component (A). It is preferable at the point which photosensitivity improves.

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

<(C) Photopolymerization initiator>
The (C) photopolymerization initiator in the present invention is a compound that is activated by energy such as UV and initiates / promotes a reaction of a radical polymerizable group. Examples of the (C) photopolymerization initiator include Mihilaz ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, and 2,2 ′. -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, acetophenone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1- Hydroxycyclohexyl phenyl ketone, diacetylbenzyl, benzyldimethyl Ketal, benzyldiethylketal, 2 (2′-furylethylidene) -4,6-bis (trichloromethyl) -S-triazine, 2 [2 ′ (5 ″ -methylfuryl) 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-propan-1-one, 1- [4- (2-hydroxyethoxy)- Enyl] -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-cyclopentadiene -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2- Kutandione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], iodium, (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) etc. are mentioned. The photopolymerization initiator is preferably selected as appropriate, and one or more types are preferably mixed and used. In particular, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole When an oxime ester-based compound such as -3-yl]-, 1- (O-acetyloxyome) is used, the photosensitive resin composition can be cured with a small amount of addition, so that flexibility and chemical resistance are improved. Since it becomes an excellent cured film, it is preferable.

  The photopolymerization initiator (C) in the photosensitive resin composition of the present invention is blended so as to be 0.1 to 50 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). It is preferable. The blending ratio is preferable because the photosensitivity of the photosensitive resin composition is improved. When the component (C) is less than the above range, the reaction of the radical polymerizable group at the time of light irradiation hardly occurs and the curing is often insufficient. Moreover, when there are more (C) components than the said range, adjustment of light irradiation amount becomes difficult and may be in an overexposed state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.

<(D) Flame retardant>
The flame retardant (D) in the present invention can be added to impart flame retardancy. A flame retardant means a substance that acts to make a flammable substance difficult to burn by adding or reacting with a flammable substance such as plastic, wood, or fiber. Although it does not specifically limit as said flame retardant, Phosphorus ester, condensed phosphate ester, phosphine oxide, phosphine, phosphorus-type flame retardants, such as a phosphazene compound having a phosphorus-nitrogen double bond, the content of aromatic rings Examples thereof include high silicone compounds. Among these flame retardants, one kind or a combination of two or more kinds may be used. In the present invention, the phosphorus-based flame retardant refers to a compound containing phosphorus such as a phosphate ester, a condensed phosphate ester, a phosphine oxide, a phosphine, and a phosphazene compound.

  From the viewpoint of compatibility with the photosensitive resin composition and flame retardancy, it is preferable to use a condensed phosphate ester and a phosphazene compound phosphorus flame retardant.

  Examples of the condensed phosphate ester include CR-733S (resorcinol diphosphate) (manufactured by Daihachi Chemical), CR-741 (manufactured by Daihachi Chemical), CR-747 (manufactured by Daihachi Chemical), and PX-200 ( Daihachi Chemical Co., Ltd.), and the phosphazene compounds include SPE-100 (Otsuka Chemical Co., Ltd.), SPH-100 (Otsuka Chemical Co., Ltd.), and the like.

  As for the usage-amount of the said flame retardant, it is preferable that the phosphorus element content rate in the photosensitive resin composition is 1 to 7 weight%. When the phosphorus element content is less than 1% by weight, a sufficient flame retardant effect may not be obtained. On the other hand, if it exceeds 7% by weight, the photosensitive resin composition after drying may be found to be sticky, and the physical properties of the cured product may be adversely affected.

<(E) Thermosetting resin>
In addition to the above components, (E) a thermosetting resin can be added to the photosensitive resin composition of the present invention.

  Examples of the (E) thermosetting resin used in the photosensitive resin composition of the present invention include epoxy resins, oxetane resins, phenol resins, isocyanate resins, block isocyanate resins, bismaleimide resins, bisallyl nadiimide resins, polyester resins ( 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 resin , Aniline resin, polyurea resin, thiourethane resin, polyazomethine resin, episulfide resin, ene-thiol resin, benzoxazine resin, polyimide resin, copolymer resins thereof, modified resins obtained by modifying these resins Or mixtures of these resins with each other or other resins and the like.

  As the thermosetting resin, it is preferable to use an epoxy resin or a blocked isocyanate resin. By containing these components, heat resistance can be imparted to a cured film obtained by curing the photosensitive resin composition.

  The epoxy resin is a compound containing at least one epoxy group in the molecule. For example, as a bisphenol A type epoxy resin, product names jER828, jER1001, jER1002, and ADEKA manufactured by Japan Epoxy Resin Co., Ltd. Trade names of Adeka Resin EP-4100E, Adeka Resin EP-4300E, trade names RE-310S and RE-410S manufactured by Nippon Kayaku Co., Ltd., trade names Epicron 840S, Epicron 850S, Epicron 1050, Epicron 1505, Toto, manufactured by DIC Corporation Trade names of EPOTOTO YD-115, EPOTOTO YD-127, EPOTOTO YD-128, and bisphenol F type epoxy resin manufactured by Kasei Co., Ltd. are trade names of jER806 and jER807 manufactured by Japan Epoxy Resin Co., Ltd. Trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, Nippon Kayaku Co., Ltd. trade names RE-303S, RE-304S, RE-403S, RE-404S, DIC Corporation Product names Epicron 830, Epicron 835, product names Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001, and bisphenol S-type epoxy resins manufactured by Toto Kasei Co., Ltd. are trade names Epicron EXA manufactured by DIC Corporation. -1514, as hydrogenated bisphenol A type epoxy resin, trade names jERYX8000, jERYX8034, jERYL7170 manufactured by Japan Epoxy Resin Co., Ltd., trade names Adeka Resin EP-4080E manufactured by ADEKA Corporation, Product name Epicron EXA-7015 manufactured by IC Co., Ltd. Product names Epototo YD-3000, Epototo YD-4000D manufactured by Toto Kasei Co., Ltd., and biphenyl type epoxy resins include product names jERYX4000, jERYL6121H manufactured by Japan Epoxy Resin jERYL6640, jERYL6677, Nippon Kayaku Co., Ltd. trade names NC-3000, NC-3000H, phenoxy type epoxy resins, Japan Epoxy Resin Co., Ltd. trade names jER1256, jER4250, jER4275, naphthalene type epoxy resins, DIC Corporation trade name Epicron HP-4032, Epicron HP-4700, Epicron HP-4200, Nippon Kayaku Co., Ltd. trade name NC-7000L, Phenol Novola Examples of the epoxy resin include 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 and Epicron N- manufactured by DIC Corporation. 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-502H As the pentadiene type epoxy resin, trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd., trade name Epicron HP-7200 manufactured by DIC Corporation, and as the amine type epoxy resin, trade name jER604 manufactured by Japan Epoxy Resin Co., Ltd. jER630, Toto Kasei Co., Ltd. trade name Epototo YH-434, Epototo YH-434L, Mitsubishi Gas Chemical Co., Ltd. trade names TETRAD-X, TERRAD-C, and flexible epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd. The product names jER871, jER872, jERYL7175, jERYL7217, product names Epicron EXA-4850 manufactured by DIC Corporation, and urethane-modified epoxy resins include product names Adeka Resin EPU-6 and Adeka Resin EPU-7 manufactured by ADEKA Corporation. Adeka Resin EPU-78-11, rubber-modified epoxy resins, trade names of Adeka Resin EPR-4023, Adeka Resin EPR-4026, Adeka Resin EPR-1309, and Chelate-modified epoxy resins, products of ADEKA Corporation Examples of the name Adeka Resin EP-49-10, Adeka Resin EP-49-20, and the heterocyclic ring-containing epoxy resin include trade name TEPIC manufactured by Nissan Chemical Co., Ltd.

  Although it does not specifically limit as a hardening | curing agent of the said thermosetting compound in the photosensitive resin composition of this invention, For example, phenol resins, such as a phenol novolak resin, a cresol novolak resin, a naphthalene type phenol resin, an amino resin, and a urea resin , Melamine, dicyandiamide and the like, 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.

  The blocked isocyanate resin is a compound that is inactive at room temperature and is heated to dissociate blocking agents such as oximes, diketones, phenols, caprolactams, etc., and regenerate isocyanate groups. Product names Duranate 17B-60PX, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-K60X, Duranate E402-B80T manufactured by Asahi Kasei Chemicals Co., Ltd. Trade names Takenate B-830, Takenate B- 815N, Takenate B-846N, Takenate B-882N, trade names Coronate AP-M, Coronate 2503, Coronate 2507, Coronate 2513, Coronate 2515, Millionone manufactured by Nippon Polyurethane Industry Co., Ltd. Preparative MS-50 and the like. Particularly, the blocked isocyanate resin suitably used in the present invention is a block isocyanate compound such as hexamethylene diisocyanate type isocyanurate type, biuret type, adduct type, etc. whose dissociation temperature of the blocking agent is 160 ° C. or less, hydrogenated diphenylmethane diisocyanate type, This is an additive xylylene diisocyanate block isocyanate resin.

  It is preferable to use the above-mentioned blocked isocyanate resin because the cured film obtained when the photosensitive resin composition is cured can be imparted with high adhesion to the substrate.

  These blocked isocyanate resins can be used alone or in combination of two or more.

  Among them, an epoxy resin is used because heat resistance can be imparted to a cured film obtained by curing the photosensitive resin composition, and adhesion to a conductor such as a metal foil or a circuit board can be imparted. More preferred.

  The (E) thermosetting resin in the photosensitive resin composition of the present invention is 0.5 to 100 parts by weight with respect to a total of 100 parts by weight of the component (A), the component (B), and the component (C). It is preferable to be blended so that the heat resistance, chemical resistance and electrical insulation reliability of the cured film of the photosensitive resin composition can be improved.

  When the thermosetting resin is less than the above range, it is difficult to obtain the effect by adding, and when it is too much, the photosensitive resin composition is applied on the substrate and the solvent is dried. As a result, the stickiness of the coating film obtained is increased, resulting in a decrease in productivity. Further, when the crosslinking density becomes too high, the cured film may be brittle and easily cracked.

<Other ingredients>
Various additives such as a filler, an adhesion assistant, an antifoaming agent, a leveling agent, a colorant, and a polymerization inhibitor can be further added to the photosensitive resin composition of the present invention as necessary. As the filler, fine inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, and calcium carbonate, and fine organic polymer fillers may be contained. Moreover, as said antifoamer, a silicon type compound, an acryl-type compound, etc. can be contained, for example. Moreover, as said leveling agent, a silicon type compound, an acryl-type compound, etc. can be contained, for example. Moreover, as said coloring agent, a phthalocyanine type compound, an azo type compound, carbon black, a titanium oxide etc. can be contained, for example. Moreover, as said adhesion assistant (it is also called adhesiveness imparting agent), a silane coupling agent, a triazole type compound, a tetrazole type compound, a triazine type compound, etc. can be contained. Moreover, as said polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, etc. can be contained, for example. Moreover, since the photosensitive resin composition of this invention contains an imide flame retardant, it is excellent in flame retardance, but in order to obtain a higher flame retardant effect, you may add another flame retardant. Examples of flame retardants that can be added include phosphate ester compounds, halogen-containing compounds, metal hydroxides, and organic phosphorus compounds. The above various additives can be used alone or in combination of two or more. Moreover, it is desirable to select each content suitably.

(II) Method of using photosensitive resin composition Using the photosensitive resin composition of the present invention directly or after preparing a photosensitive resin composition solution, a cured film or a relief pattern is formed as follows. can do. First, the photosensitive resin composition or the 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 photosensitive resin composition of the present invention is preferably 0.01 to 20% by weight, particularly preferably 0.02 to 10% by weight. Further, the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. Is preferably used.

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

  Next, heat treatment 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 photosensitive resin composition of the present invention is excellent in flame retardancy, heat resistance, chemical resistance, electrical and mechanical properties, and excellent in flexibility.

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

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

  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 reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g of methacrylic acid, 58.0 g of butyl acrylate, 30.0 g of a phosphine oxide compound represented by the following formula (9), and azobisisobutyroyl as a radical polymerization initiator were previously mixed at room temperature. 0.3 g of nitrile was dropped from the 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The resulting carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 35,000, an acid value of 78 mgKOH / g, and a phosphorus element content of 3.1% by weight. The solid content concentration, weight average molecular weight, and acid value were measured by the following methods.

<Concentration of solid content>
The measurement was performed according to JIS K 5601-1-2. The drying conditions were 150 ° C. × 1 hour.

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

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

(Synthesis Example 2)
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g of methacrylic acid, 48.0 g of butyl acrylate, 40.0 g of a phosphine oxide compound represented by the following formula (9), and azobisisobutyroyl as a radical polymerization initiator were previously mixed at room temperature. 0.3 g of nitrile was dropped from the 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The obtained carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 45,000, an acid value of 78 mgKOH / g, and a phosphorus element content of 4.1% by weight. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 3)
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g of methacrylic acid, 48.0 g of butyl acrylate, 40.0 g of a phosphine oxide compound represented by the following formula (10), and azobisisobutyroyl as a radical polymerization initiator were previously mixed at room temperature. 0.3 g of nitrile was dropped from the 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The resulting carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 45,000, an acid value of 78 mgKOH / g, and a phosphorus element content of 3.9% by weight. 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 reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g of acrylic acid, 48.0 g of butyl methacrylate, 40.0 g of a phosphine oxide compound represented by the following formula (9), and azobisisobutyroyl as a radical polymerization initiator were previously mixed at room temperature. 0.3 g of nitrile was dropped from the 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The resulting carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 52,000, an acid value of 78 mgKOH / g, and a phosphorus element content of 3.6% by weight. 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 reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 25.0 g of methacrylic acid, 35.0 g of butyl acrylate, 40.0 g of a phosphine oxide compound represented by the following formula (9), and azobisisobutyroyl as a radical polymerization initiator were mixed in advance at room temperature. 0.3 g of nitrile was dropped from the 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The resulting carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 46,000, an acid value of 162 mgKOH / g, and a phosphorus element content of 4.1% by weight. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 6)
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 7.0 g of methacrylic acid, 53.0 g of butyl acrylate, 40.0 g of a phosphine oxide compound represented by the following formula (9), and azobisisobutyroyl as a radical polymerization initiator were mixed in advance at room temperature. 0.3 g of nitrile was dropped from the 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The obtained carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 46,000, an acid value of 45 mgKOH / g, and a phosphorus element content of 4.1% by weight. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 7)
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 10.0 g of methacrylic acid, 20.0 g of butyl acrylate, 70.0 g of a phosphine oxide compound represented by the following formula (9), and azobisisobutyroyl as a radical polymerization initiator were previously mixed at room temperature. 0.3 g of nitrile was dropped from the 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The obtained carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 43,000, an acid value of 65 mgKOH / g, and a phosphorus element content of 7.0% by weight. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 8)
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g of methacrylic acid, 48.0 g of butyl acrylate, diphenyl- (2-methacryloyloxyethyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: MR-) previously mixed at room temperature 260) 40.0 g, and 0.6 g of azobisisobutyronitrile as a radical polymerization initiator were added dropwise from a dropping funnel over a period of 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The obtained carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 61,000, an acid value of 78 mgKOH / g, and a phosphorus element content of 3.4% by weight. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 9)
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g of methacrylic acid, 40.0 g of butyl acrylate, diphenyl- (2-methacryloyloxyethyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: MR-) previously mixed at room temperature 260) 48.0 g, and 0.6 g of azobisisobutyronitrile as a radical polymerization initiator were added dropwise from the dropping funnel over a period of 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 further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The obtained carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 60,000, an acid value of 78 mgKOH / g, and a phosphorus element content of 4.1% by weight. The solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 10)
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and nitrogen introduction tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a solvent for polymerization, under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. To this, 12.0 g of methacrylic acid, 28.0 g of methyl methacrylate, 60.0 g of butyl acrylate, and 0.5 g of azobisisobutyronitrile as a radical polymerization initiator previously mixed at room temperature were heated to 80 ° C. It was dripped from the dropping funnel over 3 hours while keeping the temperature. After completion of the dropwise addition, the reaction solution was heated to 90 ° C. while stirring, and further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. to obtain a carboxyl group-containing resin solution of the present invention. The resulting carboxyl group-containing resin solution had a solid content concentration of 47%, a weight average molecular weight of 45,000, and an acid value of 78 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 1-7)
(A) binder resin, (B) photosensitive resin, (C) photopolymerization initiator, (D) flame retardant, (E) thermosetting resin, other components, and organic obtained in Synthesis Examples 1-7 A photosensitive resin composition was prepared by adding 1,2-bis (2-methoxyethoxy) ethane as a solvent. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. The amount of 1,2-bis (2-methoxyethoxy) ethane added was adjusted so that the solid content of the photosensitive resin composition was 60% by weight. The composition was subjected to the following evaluation by completely defoaming bubbles in the solution with a defoaming apparatus.

<1> Ciba Japan Co., Ltd. product name of photopolymerization initiator <2> Shin-Nakamura Chemical Co., Ltd. product name NK Ester A-9300 (ethoxylated isocyanuric acid triacrylate)
<3> Product name NK ester BPE-1300 (bisphenol A EO-modified diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
<4> Product name of phosphazene compound (phosphorus flame retardant) manufactured by Otsuka Chemical Co., Ltd. <5> Product name of cresol novolac type polyfunctional epoxy resin manufactured by DIC Co., Ltd. <6> Product name of silica particles manufactured by Nippon Aerosil Co., Ltd.

<Preparation of coating film on polyimide film>
The above photosensitive resin composition was cast and applied to an area of 100 mm × 100 mm on a 25 μm polyimide film (manufactured by Kaneka Co., Ltd .: trade name 25 NPI) using a Baker type applicator so that the final dry thickness was 20 μm. After drying at 80 ° C. for 20 minutes, a negative photomask with a line width / space width of 50 mm × 50 mm = 100 μm / 100 μm was placed and irradiated with ultraviolet rays with an integrated exposure amount of 300 mJ / cm ² to be exposed. Subsequently, spray development was performed for 60 seconds at a discharge pressure of 1.0 kgf / mm ² using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. After development, the film was thoroughly washed with pure water, and then cured by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition on the polyimide film.

<Evaluation of cured film>
The obtained cured film was evaluated for the following items. The evaluation results are shown in Table 2.

(I) Photosensitivity evaluation The photosensitivity evaluation of the photosensitive resin composition was determined by observing the surface of the cured film obtained in the above item <Preparation of coating film on polyimide film>.
◯: 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) Adhesiveness of cured film The adhesiveness of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated by a cross-cut method according to JIS K 5600-5-6.
○: Classification 0 (the edge of the cut is completely smooth and there is no peeling in any lattice)
Δ: Classification 1 (Small peeling of the coating film at the intersection of the cuts. The influence at the crosscut part does not clearly exceed 5%.)
X: Classification 2 (The coating film is peeled along the edge of the cut and / or at the intersection. It is clearly more than 5% but not more than 15% that is affected at the crosscut portion.)

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

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

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

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

(Vii) Warpage A cured film of a photosensitive resin composition having a thickness of 20 μm on the surface of a polyimide film having a thickness of 25 μm (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A laminated film was produced.
The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The 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.

(Viii) Flame retardancy In accordance with the UL94VTM method for flammability testing of plastic materials, flammability testing was performed as follows. 12.5 μm-thick polyimide film (manufactured by Kaneka Corporation: trade name Apical 12.5 NPI), a photosensitive resin composition having a thickness of 20 μm on one side in the same manner as the above item <Preparation of coating on polyimide film> A cured film laminated film was produced. Cut out the sample prepared above into dimensions: 50 mm width × 200 mm length × 32.5 μm thickness (including the thickness of the polyimide film), put a marked line in the 125 mm portion, and the photosensitive resin composition cured film stack is on the outside Rounded into a cylindrical shape with a diameter of about 13 mm, affixed PI tape so that there is no gap between the upper part of the marked line (75 mm) and the upper part, and prepared 20 flame retardant test tubes did. 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.

(Comparative Examples 1-3)
(A) binder resin, (B) photosensitive resin, (C) photopolymerization initiator, (D) flame retardant, (E) thermosetting resin, other components, and organic obtained in Synthesis Examples 8 to 10 A photosensitive resin composition was prepared by adding 1,2-bis (2-methoxyethoxy) ethane as a solvent. Table 3 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. The amount of 1,2-bis (2-methoxyethoxy) ethane added was adjusted so that the solid content of the photosensitive resin composition was 60% by weight. The composition was defoamed completely with a defoaming apparatus, and the physical properties were evaluated in the same manner as in the examples. The results are listed in Table 4.

<1> Ciba Japan Co., Ltd. product name of photopolymerization initiator <2> Shin-Nakamura Chemical Co., Ltd. product name NK Ester A-9300 (ethoxylated isocyanuric acid triacrylate)
<3> Product name NK ester BPE-1300 (bisphenol A EO-modified diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
<4> Product name of cresol novolac type polyfunctional epoxy resin manufactured by DIC Corporation <5> Product name of silica particles manufactured by Nippon Aerosil Co., Ltd.

(Comparative Example 4)
It is a blending amount as a non-volatile content, and is an acrylic resin, which is a copolymer of methacrylic acid, methyl methacrylate, and butyl acrylate (methacrylic acid: methyl methacrylate: butyl acrylate = 17% by weight: 62% by weight: 21 % By weight) with a weight average molecular weight of 100,000, an acid value of 110 mg KOH / g, 30 parts by weight, a polyurethane compound (manufactured by Nippon Kayaku Co., Ltd., sample name UXE-3024, weight average molecular weight: 10,000), 40 parts by weight, bisphenol A 30 parts by weight of polyoxyethylene dimethacrylate (trade name FA-321M, manufactured by Hitachi Chemical Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty)・ Chemicals, trade name “I-369”) 5 parts by weight, 1,7-bis (9-acrylic) 3 parts by weight of dinyl) heptane (trade name N-1717, manufactured by Asahi Denka Kogyo Co., Ltd.), 30 parts by weight of phosphinate (manufactured by Clariant, trade name EXOLIT OP935, phosphorus content = 23% by mass), barium sulfate ( 60 parts by weight of Sakai Chemical Industry Co., Ltd., trade name Variace B-30), 30 parts by weight of block type isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name Sumijoule BL-3175), yellow pigment (Pigment Yellow) ) 0.5 part by weight was mixed and mixed with methyl ethyl ketone as a diluent so that the non-volatile content was 50% by mass to obtain a photosensitive resin composition. The composition was defoamed completely with a defoaming apparatus, and the physical properties were evaluated in the same manner as in the examples. The results are listed in Table 5.

(Comparative Example 5)
It is a compounding amount as a non-volatile component, and 10.0 g of a phosphine oxide compound represented by the following structural formula (8), acid-modified polyfunctional bisphenol F type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: ZFR-1401H) 46 .55 g, ε-caprolactone modified dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd., trade name DPCA-60) 6.06 g, 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1- Propane (Ciba Specialty Chemicals, trade name Irg.907) 4.54 g, 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name DETX-S) 0.91 g, biphenol type epoxy resin (Japan) 18.31 g of Kayaku Co., Ltd., trade name NC-3000H), 1.00 g of melamine, 15. 5 g, 0.61 g of phthalocyanine blue, 0.39 g of leveling agent (trade name BYK-354, manufactured by Big Chemie), 0.69 g of antifoaming agent (Shin-Etsu Chemical Co., Ltd., trade name KS-66), 4.54 g of carbitol acetate By mixing, a photosensitive resin composition was obtained. The composition was defoamed completely with a defoaming apparatus, and the physical properties were evaluated in the same manner as in the examples. The results are listed in Table 5.

(Comparative Example 6)
In a flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen gas inlet tube, propylene glycol monomethyl ether 60. A mixed solution of 0 part by weight and 0.04 part by weight of toluene was added and stirred while heating to 80 ° C. while blowing nitrogen gas. To this, 20.0 parts by weight of methacrylic acid, methyl methacrylate 20. 0 part by weight, 60.0 parts by weight of diphenyl- (2-methacryloyloxyethyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name MR-260), 1.0 part by weight of azobisisobutyronitrile After the solution was mixed dropwise over 3 hours, the mixture was further stirred at 80 ° C. for 9 hours. Then, the resin solution was obtained by diluting with 45.0 parts by weight of propylene glycol monomethyl ether.

  As a compounding amount as a non-volatile content, 70 g of this resin solution, 35 g of a phosphorus-containing photopolymerizable compound (trade name HF-TMPTA, manufactured by Showa Polymer Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholino) 3 g of phenyl) -butanone-1 (product name I-369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 15 g of blocked isocyanate (product name BL3175, manufactured by Sumika Bayer Urethane Co., Ltd.) were mixed, diluted with 20 g of methyl ethyl ketone, and photosensitive. A functional resin composition was obtained. The composition was defoamed completely with a defoaming apparatus, and the physical properties were evaluated in the same manner as in the examples. The results are listed in Table 5.

(Comparative Example 7)
50 parts by weight of methyl ethyl ketone was placed in a 500 ml four-necked flask and heated to 80 ° C. with stirring under a nitrogen stream. Here, 100 parts by weight of diphenyl- (2-methacryloyloxyethyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name MR-260), 1 part by weight of azobisisobutyronitrile, and tert-butyl perbenzoate 0 A solution prepared by dissolving 1 part by weight in 50 parts by weight of methyl ethyl ketone as an organic solvent at room temperature was dropped over 4 hours, and further reacted for 2 hours to obtain a resin solution.

  As a compounding amount of the nonvolatile component, 50 g of this resin solution, 45 parts by weight of a cresol novolac type epoxy resin (ESCN-195 manufactured by Sumitomo Chemical Co., Ltd.), 15 weights of bisphenol A type epoxy resin (EP-1001 manufactured by Yuka Shell Co., Ltd.) Part, phenol novolak resin (Dai Nippon Ink Co., Ltd. TD-2131) 40 parts by weight, 2-phenylimidazole 0.2 parts by weight were mixed and diluted with 50 parts by weight of methyl ethyl ketone to obtain a photosensitive resin composition. The composition was defoamed completely with a defoaming apparatus, and the physical properties were evaluated in the same manner as in the examples. The results are listed in Table 5.

(Comparative Example 8)
50 parts by weight of methyl ethyl ketone was placed in a 500 ml four-necked flask and heated to 80 ° C. with stirring under a nitrogen stream. Here, 79 parts by weight of diphenyl- (2-methacryloyloxyethyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name MR-260), 16 parts by weight of acrylic acid, 5 parts by weight of methyl methacrylate, azobisisobutyronitrile A solution obtained by dissolving 1 part by weight and 0.1 part by weight of tert-butyl perbenzoate in 50 parts by weight of methyl ethyl ketone, which is an organic solvent, at room temperature is dropped over 4 hours, and further reacted for 2 hours to obtain a resin solution. Obtained.
As a compounding amount of the nonvolatile component, 40 parts by weight of this resin solution, epoxy acrylate anhydride (manufactured by Nippon Kayaku Co., Ltd., trade name: ZFR-1158): 30 parts by weight, urethane bond-containing monomer (Shin Nakamura Chemical Industry ( Co., Ltd., trade name: UA-11) 30 parts by weight, photopolymerization initiator (Ciba Geigy Co., Ltd., trade name: Irgacure 651), 5 parts by weight, thermal polymerization initiator (Nippon Yushi Co., Ltd., trade name) : Perhexine 25B): 2 parts by weight, 10 parts by weight of 2,2-bis [4- (4-N-maleimidinylphenoxy) phenyl] propane mixed, diluted with 20 parts by weight of methyl ethyl ketone, and photosensitive resin composition Got. The composition was defoamed completely with a defoaming apparatus, and the physical properties were evaluated in the same manner as in the examples. The results are listed in Table 5.

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

Claims (17)

A phosphine oxide containing at least (A) a binder resin, (B) a photosensitive resin, and (C) a photopolymerization initiator, wherein the (A) binder resin is at least (a) represented by the following general formula (1): A photosensitive resin composition obtained by copolymerizing a compound and (b) a carboxyl group and a compound having a double bond copolymerizable with the above (a).

  The photosensitive resin composition according to claim 1, wherein (b) is a compound having (meth) acrylic acid and / or a (meth) acryloyl group and a carboxyl group.   The photosensitive resin composition according to claim 1, wherein the (b) is (meth) acrylic acid.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the (A) binder resin is a copolymer obtained by further copolymerizing (c) (meth) acrylic acid alkyl ester. .   The photosensitive resin composition according to any one of claims 1 to 4, wherein the phosphorus element content of the (A) binder resin is 2.0 to 9.5 wt%.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the acid value of the (A) binder resin is 40 to 200 mgKOH / g.   The said (C) photoinitiator is an oxime ester type compound, The photosensitive resin composition of any one of Claims 1-6 characterized by the above-mentioned.   The (A) binder resin, (B) photosensitive resin, and (C) photopolymerization initiator in the above photosensitive resin composition are 10 (B) photosensitive resin with respect to 100 parts by weight of the binder resin. The photosensitive resin according to any one of claims 1 to 7, wherein the photopolymerization initiator is blended so that the amount of the photopolymerization initiator is 0.1 to 50 parts by weight. Composition.   Furthermore, (D) a flame retardant is contained, The photosensitive resin composition of any one of Claims 1-7 characterized by the above-mentioned.   The photosensitive resin composition according to claim 1, wherein a phosphorus element content in the photosensitive resin composition is 1 to 7% by weight.   Furthermore, (E) thermosetting resin is contained, The photosensitive resin composition of any one of Claims 1-10 characterized by the above-mentioned.   The photosensitive resin composition according to claim 11, wherein the (E) thermosetting resin is an epoxy resin.   The blending ratio of the (E) thermosetting resin is 0.5 to 100 parts by weight of the total of (A) binder resin, (B) photosensitive resin, and (C) photopolymerization initiator. The photosensitive resin composition according to claim 11 or 12, which is blended so as to be 100 parts by weight.   The photosensitive resin composition solution obtained by melt | dissolving the photosensitive resin composition of any one of Claims 1-13 in an organic solvent.   A resin film obtained by applying at least the photosensitive resin composition according to any one of claims 1 to 13 or the photosensitive resin composition solution according to claim 14 to a substrate surface and then drying the substrate. .   An insulating film obtained by curing the resin film according to claim 15.   The printed wiring board with an insulating film which coat | covered the insulating film of Claim 16 on the printed wiring board.

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