TW200832059A - Photosensitive resin composition and photosensitive element using the same - Google Patents

Abstract

A photosensitive resin composition comprising (A) a novolac-type acid-modified, vinyl-group-containing epoxy resin having a biphenyl skeleton, (B) a phosphorus-containing compound, c a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule, and (D) a photopolymerization initiator.

Description

[Technical Field] The present invention relates to a photosensitive resin composition and a photosensitive member using the same. [Prior Art] In the printed wiring board manufacturing industry, conventionally, a solder resist is formed on a printed wiring board. The solder resist is used in the soldering step for the printed wiring board, and the function of preventing the unnecessary soldering of the conductor layer of the printed wiring board, and when the printed wiring board is used after the mounting of the mounted component is used, It also functions as a permanent film to prevent corrosion of the conductor layer and to maintain electrical insulation between the conductor layers. As a method of forming a solder resist, a method of screen printing a thermosetting resin is known as a conductor layer of a printed wiring board. However, such a method has its limit in the high resolution of the photoresist pattern, and it has become difficult to increase the density of the printed wiring board in recent years. Here, in order to achieve high resolution of the photoresist pattern, the use of the photoresist method has prospered. In the photoresist method, a photosensitive resin composition layer made of a photosensitive resin composition is formed on a substrate, and the photosensitive resin composition layer is cured by exposure to a specific pattern, and the unexposed portion is removed by development. 'A person who forms a hardened film of a specific pattern. In addition, the photosensitive resin composition used in the related method is considered to be environmentally safe, and the environmental safety of the earth has become the mainstream by the use of a dilute alkali aqueous solution such as an aqueous solution of sodium carbonate. In the case of the photosensitive resin composition, a liquid photoresist composition as disclosed in Patent Document 1 below, and a photosensitive thermosetting resin composition of Patent Document 2 below are known. [Patent Document 1] JP-A-61-243869 [Patent Document 2] Japanese Unexamined Patent Publication No. JP-A No. Hei No. Hei. The flame retardation limit is tightened, and materials used for printed wiring boards and the like are no exception. As a method of incombustibility, a method of adding a halogen compound, an anthraquinone compound, a phosphorus compound, a boron compound, an inorganic chelating agent, and the like is generally known. Recently, however, with regard to environmental issues, the focus on human safety issues has increased, while the focus has shifted to non-nuisance, low toxicity, safety, not only flame retardance, but also the reduction of harmful gases and smoky substances. Therefore, a flame-retardant substrate which does not use a halogen compound or a lanthanoid compound has been developed and put into practical use. However, the present inventors have found that when the cured film is formed using the conventional photosensitive resin composition of Patent Documents 1 and 2 on the flame-retardant substrate, sufficient flame retardancy (desired to be UL94VTM-0) is not ensured. In view of the above, the present invention has an object of providing a photosensitive resin composition which has excellent alkali developability and can form a cured film having excellent flame retardancy. Further, the present invention has an object of providing a photosensitive element having a photosensitive resin composition layer formed of the photosensitive resin composition. -6 - 200832059 [Means for Solving the Problem] As a result of intensive research to achieve the above object, the present inventors have found that the above-mentioned resin and phosphorus-containing compound having a specific structure can be used in the photosensitive resin composition. Purpose, the present invention has been completed. That is, the present invention provides an epoxy resin containing a (A) biphenyl skeleton-containing novolac type acid-modified vinyl group, and (B) a phosphorus-containing compound, and (C) having at least one ethyl group in the molecule. A photopolymerizable compound of an unsaturated group; and (D) a photosensitive resin composition of a photopolymerization initiator. According to the related photosensitive resin composition, in addition to the above-described configuration, in addition to excellent alkali developability, the cured film can have excellent flame retardancy. Therefore, the above-mentioned photosensitive resin composition can be suitably used for manufacturing applications such as a printed wiring board which requires flame retardancy. Further, in the photosensitive resin composition of the present invention, the (A) epoxy resin contains (A) an epoxy resin represented by the following general formula (1) and (b) an unsaturated group-containing monocarboxylic acid ( C) An acid-modified vinyl epoxy resin which is a reaction product of a polycarboxylic acid anhydride is preferred. [Chemical 1]

[In the formula (1), R1 and R2 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 200832059 to 8, or an aryl group, and 11 is an integer of 〇 50. Further, in the formula, most of R1 and R2 may be the same or different. (Α) In terms of epoxy resin, the photosensitive resin composition containing the above-mentioned specific acid-containing modified vinyloxy resin may be used. It has excellent imageability and can form a hardened film with more excellent flame retardancy.

Further, the photosensitive resin composition of the present invention preferably contains (E) a hardening agent. In the photosensitive resin composition, the photosensitive resin composition is photocured by the (E) thermal curing agent, and then thermally cured, whereby the insulating reliability of the obtained hardened film can be further improved. Further, in the photosensitive resin composition of the present invention, the phosphorus-containing compound (B) preferably contains a phosphonate represented by the following general formula (2). [Chemical 2] 〇

Mm+ (2)

II

A - P - 0 B [In the formula (2), A and B are each independently, and represent a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group, and lanthanum is Mg, Ca, Al. At least one metal selected from the group consisting of Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li' Na and K, m is an integer of 1 to 4] Since the resin composition contains the phosphonate represented by the above general formula (2), the flame retardancy of the obtained cured film can be further enhanced. Further, in the photosensitive resin composition of the present invention, the phosphorus-containing compound (B) is preferably a phosphate-containing compound. The photosensitive resin composition can improve the flame retardancy and flexibility of the obtained cured film due to the phosphate ester -8-200832059. Further, in the photosensitive resin composition of the present invention, as the (B) phosphorus-containing compound, it is preferred to contain both the phosphonate represented by the above formula (2) and the above phosphate, whereby the resulting product can be obtained. The cured film is excellent in both flame retardancy and flexibility. Further, in the photosensitive resin composition of the present invention, the phosphorus-containing compound (B) preferably contains a phenoxyphosphazene compound. The photosensitive resin composition contains a phenoxyphosphazene compound, which further improves the flame retardancy and flexibility of the obtained cured film, and at the same time makes the exudation (bleeding of the photosensitive resin composition) better. Further, the photosensitive resin composition of the present invention preferably contains both the phosphonate represented by the above formula (2) and the phenoxyphosphazene compound as the (B) phosphorus-containing compound, whereby the resulting hardening can be obtained. The flame retardancy, flexibility and exudation of the film are particularly excellent. Further, the photosensitive resin composition of the present invention is preferably used for forming a cured film which is a permanent film on a flexible substrate. Further, the present invention provides a photosensitive element comprising a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention formed on the support. According to the photosensitive resin element, the photosensitive resin composition layer formed of the photosensitive resin composition can provide a cured film having excellent flame retardancy in addition to excellent alkali developability. [Effect of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition which has excellent alkali developability and can form a cured film excellent in flame retardancy, and a photosensitive element using the same. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a suitable embodiment of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and the repeated description is omitted. Further, in the present invention, (meth)acrylic means acrylic acid and methacrylic acid corresponding thereto, (meth)acrylate means acrylate and methacrylate corresponding thereto, and (meth)acryloyl group means propylene A mercapto group and a corresponding methacrylic acid group. (Photosensitive Resin Composition) The photosensitive resin composition of the present invention contains (A) a novolac type acid-modified vinyl epoxy resin having a biphenyl skeleton (hereinafter, referred to as "(A) component" depending on the situation. And (B) a phosphorus-containing compound (hereinafter, referred to as "(B) component") and (C) a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule (hereinafter, referred to as "(C) ) "Component") and (D) Photopolymerization initiator (hereinafter, "(D) component"). Further, the photosensitive resin composition of the present invention contains (E) a heat curing agent (hereinafter, referred to as "(E) component"). The photosensitive resin composition of the present invention contains the above (A)~ The component (D) can be developed in a dilute aqueous alkali solution, and at the same time, the flame retardancy of the cured film obtained by curing the photosensitive resin composition can satisfy a high level. Further, according to the photosensitive resin composition of the present invention, it is possible to form a cured film having sufficient flame retardancy with an efficiency of -10- 200832059. Further, the photosensitive resin composition of the present invention can contain a halogen-based compound and an anthraquinone-based compound, and the flame retardancy of the cured film is sufficiently high, so that environmental load and toxicity such as a printed wiring board can be reduced. In particular, when the photosensitive resin composition of the present invention is used for a non-halogen-based or non-fluorene-based flame-retardant substrate, the above effects can be further attained. Hereinafter, each component contained in the photosensitive resin composition of the present invention will be described. <(A) component: acid-modified vinyl epoxy resin> (A) component of a novolac type-containing acid-modified The vinyl epoxy resin is preferably obtained by (a) an epoxy resin represented by the following general formula (1) and (b) an unsaturated group-containing monocarboxylic acid and (c) a reaction product with a polycarboxylic acid anhydride. . [Chemical 3]

In the formula (1), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and η is an integer of 0 to 50. Further, in the formula (1), most of R1 and R2 which are present may be the same or different. -11 - 200832059 (A) Epoxy resin is contained in a photosensitive resin composition, and is compatible with both flame retardancy and flame retardancy. The acid-modified vinyl epoxy resin constituting the component (A) &amp; the specific example of the unsaturated-bonded monocarboxylic acid, such as acrylic acid, acrylic, methacrylic acid, fluorene-styrene acrylic acid, /3 -fluorenyl group a half ester of a reaction of crotonic acid, α-cyano cinnamic acid, cinnamic acid, and a saturated or unsaturated anhydride with a (meth) acrylate having 1 hydroxyl group in one molecule, or saturated or saturated A half ester of a reactant of a monobasic acid and a compound containing not only a glycidyl compound. Semi-esters such as succinic anhydride, maleic anhydride, phthalic anhydride phthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic acid tetrahydrophthalic anhydride, itaconic anhydride, methyl end A saturated or unsaturated dibasic acid anhydride such as methyltetrahydroanhydride, and a hydroxyethyl group (methyl ester, hydroxypropyl (meth) acrylate, hydroxybutyl (methacrylate), polyethylene glycol mono Acrylate, glycerol di(acrylate), trimethylolpropane di(meth)acrylate, quaternary (meth) acrylate, dipentaerythritol penta(methyl) propylene phenyl glycidyl ether a (meth) acrylate derivative of a hydroxyl group in one molecule such as acrylate, or a half ester in a molar ratio, or a saturated or unsaturated dibasic acid (such as succinic acid, adipic acid, benzene) Formic acid, tetrahydrophthalic acid, hexahydrophthalic acid, fumaric acid, etc.), combined with unsaturated monoglycidyl glycidyl (meth) acrylate, etc. Ester, etc. Alkali imaging J (b) acid dienoic acid, and binary derivative a saturated base, tetrahydroanhydride, toluene, propylene) propylmethyl) pentaerythritol ester, one of which should be obtained from acid, and clothing (if it should be obtained -12-200832059, etc. (b The monocarboxylic acid may be used singly or in combination of two or more kinds. Particularly preferably, (b) the monocarboxylic acid is acrylic acid. (c) The acid-modified vinyl epoxy resin (A) component (c) specific example of the polycarboxylic acid anhydride In terms of, for example, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. The acid value of the component (A) is 60 to 150 mgKOH. / g is preferably 80 to 12 mg KOH / g. The acid value is less than 60 mg KOH / g, and the appearance of ij ij is difficult to develop with a dilute aqueous solution, and the insulation reliability of the obtained cured film is more than 150 mg KOH / g. In addition, the acid value of the (A) component can be measured by the following method. First, after weighing about lg of the resin solution of the component (A), acetone is added to the resin solution. 0g, the resin solution is uniformly dissolved. Then, an appropriate amount of the indicator is added to the phenolphthalein The liquid was titrated with a 0.1 N KOH aqueous solution. The acid value was calculated from the titration result by the following formula: [A1] A = l〇xVfx56.1 / (WpxI) Further, in the formula, A is an acid value (mgKOH/g) Vf is the titer (mL) of phenolphthalein, Wp is the mass (g) of the resin solution as the component (A), and I is the ratio (% by mass) of the nonvolatile matter of the resin solution as the component (A). The weight average molecular weight of the component is not particularly limited, but from the viewpoint of film properties and resolution, it is preferably from 1,000 to 50,000, more preferably from 2000 to 30,000 -13 to 200832059, and particularly preferably from 3,000 to 15,000. The novolac type acid-modified vinyl epoxy resin having a biphenyl skeleton (A) may be commercially available, and may be used, for example, ZCR-1 5 69H, ZCR-1596H, ZCR-1611H, ZCR-1610H (all Made by Nippon Kayaku Co., Ltd., trade name). Further, the photosensitive resin composition of the present invention may be added with a phenol novolac type acid-modified vinyl epoxy resin, a cresol novolac type acid-modified vinyl epoxy resin, and a bisphenol A type acid-modified vinyl compound. Acid-modified vinyl epoxy resin, acrylic resin other than acid-modified vinyl epoxy resin, such as epoxy resin, bisphenol F type acid-modified vinyl epoxy resin, etc. A styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, or a phenol resin. Among them, it is preferred to use an acrylic resin from the viewpoint of imparting film properties. In terms of the above acrylic resin, a resin containing (meth)acrylic acid and (meth)acrylic acid ester as a constituent monomer is preferred, and a constituent monomer containing (meth)acrylic acid and (meth)acrylic acid ester may be free radical. Manufactured by polymerization. In the above (meth) acrylate, for example, a compound represented by the following general formula (3) and an alkyl group of the compound may be substituted with a hydroxyl group, an epoxy group, a halogen or the like. H2C=C—C—0—R12 (3) 2 ι”ιι R11 Ο -14- 200832059 In the above general formula (3), R11 is a hydrogen atom or a methyl group, and R12 is a carbon number of 1 to 12. An alkyl group, an alicyclic hydrocarbon group having 5 to 10 carbon atoms or a benzyl group. Further, an alkyl group represented by R12, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. , mercapto, decyl, undecyl, dodecyl, and the structural isomers thereof. The novolac type acid-modified vinyl epoxy having a biphenyl skeleton as the above (A) component In the case of the resin and the above acrylic resin, the weight average molecular weight of the acrylic resin is preferably from 3,000 to 300,000, more preferably from 40,000 to 200,000, and particularly preferably from 50,000 to 150,000, from the viewpoint of improving film properties. (B) Component: phosphorus-containing compound &gt; The phosphorus-containing compound of the component (B) is preferably a phosphonate represented by the following general formula (2).

Mm+ (2)

II A—P—Ο

I

B [In the formula (2), A and B are each independently, and represent a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group, and yttrium is Mg, Ca, Al, Sb, Sn, Ge. At least one metal selected from the group consisting of Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K, and m is an integer of 1 to 4. Here, in the specific examples of A and B in the formula (2), for example, methyl-15-200832059, ethyl, II-propyl, isopropyl, η-butyl, tert-butyl, η- Pentyl, phenyl, and the like. Further, 80% by mass or more of the phosphonate represented by the above general formula (2) is based on the viewpoint of reliability when used for a photosensitive resin composition and a photosensitive element, and the particle size of the phosphonate particles is 1 〇// m. The following is better, 5 / m or less is better, 3 / zm or less is particularly good. When the particle size exceeds 1 〇 // m, the appearance of the coating film of the photosensitive resin composition tends to be deteriorated, and the production of the high-resolution printed wiring board tends to be difficult. The above phosphonates may be used alone or in combination of two or more. Further, the phosphonate may be commercially available, and may be, for example, EXOLIT OP 93 0, EXOLIT OP 935, EXOLIT OP 940 (all manufactured by Clariant in Japan, trade name). The photosensitive resin composition contains the above-mentioned phosphonate as the component (B), and the cured film obtained by curing the photosensitive resin composition can obtain more sufficient flame retardancy. Further, the phosphonate represented by the above general formula (2) is a structure which is not easily hydrolyzed, and can effectively prevent generation of ionic impurities which have reduced electrical insulating properties, and the cured film can have excellent insulation reliability. Further, the phosphorus-containing compound of the component (B) is preferably a phosphate-containing ester. Specific examples of phosphate esters, such as triphenyl phosphate, tricresol phosphate, trixylene phosphate, cresol diphenyl phosphate, xylene diphenyl phosphate, 1,3-dihydroxybenzene • trichloro A phenol condensate of a phosphine polycondensate, a phenol condensate of a polycondensate of 2,2-bis(P-hydroxyphenyl)propane·trichlorophosphine oxide, and the like. These can be obtained from commercially available products such as TPP, TCP, TXP, CDP, XDP, CR-73 3 S, CR-74 1, CR-747 (all are manufactured by Daiha Chemical Co., Ltd. -16-200832059, trade name). PFR, FP-600 and FP-700 (all manufactured by ADEKA Corporation, trade name). The photosensitive resin composition contains a phosphate ester as the component (B), and the flame retardancy of the cured film obtained by curing the photosensitive resin composition can be further improved. Further, since the phosphate ester is used as a plasticizer, the flexibility of the cured film can be further improved. Further, the phosphorus-containing compound of the component (B) is preferably a compound containing phenoxyphosphazene. In the case of the phenoxyphosphazene compound, a compound having a chain structure t ft#% &amp; / or a chain structure as shown in the following general formula (5) is shown in the following general formula (4). [Chemical 6]

[In formula (4), r is! An integer of ~2〇. 〕 -17- (5) (5) 200832059 [Chemistry 7]

[In the formula (5), s is an integer of 1 to 20. 〕 The photosensitive resin composition contains a phenoxyphosphazene compound as the component (B), and the photosensitive resin composition is cured, whereby the flame retardancy of the obtained cured film can be further improved. Further, the phenoxyphosphazene compound is preferable in that the flexibility and exudation of the cured film (bleeding of the photosensitive resin composition) are better. (B) In terms of a component, at least one of the above-mentioned phosphate ester and phenoxyphosphazene compound may be used alone as the phosphonate represented by the above formula (2), but at least the phosphonate represented by the above general formula (2) is used. Preferably, the phosphonate represented by the above general formula (2) is particularly preferably used with the above phosphate or phenoxyphosphazene compound. Further, in the case of the component (B), a phosphorus-containing compound known in the art may be used. &lt;(C) component: a compound having at least one ethylenically unsaturated bond&gt; (C) Specific examples of a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule, such as a bisphenol A system ( a methyl acrylate compound; a compound obtained by reacting a polyol with an α, Θ-unsaturated carboxylic acid; -18- 200832059 a compound obtained by reacting a glycidyl compound with an α,/3 -unsaturated carboxylic acid; having a urethane bond a urethane monomer or a urethane oligomer such as a (meth) acrylate compound, and the like, a nonyl phenoxy polyoxyethylene acrylate; r-chloro-mono-hydroxypropyl-/3 '1-(Methyl)acryloyloxyethyl-hydrazine-phthalate, /3-hydroxyalkyl-anthracene-(meth)propenyloxyalkyl-fluorene-phthalate Dicarboxylic acid compound; alkyl (meth)acrylate, EO-modified mercaptophenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. In terms of biguanide A-based (meth) acrylate compounds, such as 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, 2,2 bis(4-( (Meth)propenyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)oxy)phenyl)propane and 2,2-bis( 4-((meth)acryloxypolyethoxypolypropyloxy)phenyl)propane or the like. 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, such as 2,2-bis(4-((meth)propenyloxy)diethoxy Phenyl)propane, 2,2-bis(4-((meth)propenyloxy)triethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy) Tetraethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentaethoxy)phenyl)propane, 2,2-bis(4-((methyl)) Propylene decyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy)ethoxy)phenyl)propane, 2,2-bis(4- ((Meth)propenyloxy octaethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)hexyloxy)phenyl)propane, 2,2- 19- 200832059 A double (4-((meth)propenyloxy-l-ethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy eleven ethoxy)) Phenyl)propane, 2,2-bis(4-((meth)propenyloxydodecyloxy)phenyl)propane, 2,2-bis(4) One ((meth)propenyloxytridecylethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetradecyloxy)phenyl)propane, 2 ,2-bis(4-((meth)propenyloxypentadecane)ethoxy)phenyl)propane and 2,2-bis(4-((meth)propenyloxy)hexadecyloxy) Phenyl)propane, etc. Among them, 2,2 double (4-(methacryloxypentapentaethoxy)phenyl)propane can be obtained commercially from BPE-500 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2, 2— Bis(4-(methacryloxylpentadecane)ethoxy)phenyl)propane is commercially available as BPE_ 1 300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more. 2,2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane, such as 2,2-bis(4-((methyl)propenyloxydipropoxy)) Phenyl)propane, 2,2-bis(4-((meth)propenyloxytripropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy) Propyl)phenyl)propane, 2,2-bis(4-((methyl)propenyloxypentapropyloxy)phenyl)propane, 2,2-bis(4-((meth)propene)醯oxyhexapropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy)-propenyloxy)phenyl)propane, 2,2-bis (4 (( Methyl)propenyloxy octapropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy pentoxy)phenyl)propane, 2,2 bis ( 4-((Meth)propenyloxydapoxy)phenyl)propane-20- 200832059, 2,2-bis(4-((methyl)propenyloxy eleven propoxy)phenyl ) propane, 2,2-bis(4-((meth)propenyloxy-t-dodecyloxy)phenyl)propane, 2,2-bis(4-((methyl) Acryloxytridecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetradecyloxy)phenyl)propane, 2,2-bis ( 4-((meth)acrylomethoxypentadecapropoxy)phenyl)propane and 2,2-bis(4-((meth)propenyloxyhexadecane)phenyl)propane, etc. . These may be used alone or in combination of two or more. 2,2-bis(4-((meth)propenyloxypolyethoxypolypropoxy)phenyl)propane, such as 2,2-bis(4-((methyl)propenyloxy) Ethoxy octapropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxytetraethoxytetrapropoxy)phenyl)propane and 2,2 a pair ( 4-((meth)acryloxycarbonylhexaethoxyhexapropoxy)phenyl)propane or the like. These may be used alone or in combination of two or more. The compound obtained by reacting the α,θ-unsaturated carboxylic acid in the polyol, such as polyethylene glycol di(meth)acrylate having a vinyl number of 2 to 14, and polypropylene glycol di(methyl) having a propylene number of 2 to 14 ) acrylate, vinyl group having 2 to 14 and polypropylene group having 2 to 14 polyethylene/polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trishydroxypropylpropane (Meth) acrylate, hydrazine-modified trimethylolpropane tri(meth) acrylate, hydrazine-modified trimethylolpropane tri(meth) acrylate, ΕΟ · ΡΟ modified trimethylolpropane III (Meth) acrylate 'tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and - 21 - 200832059 pentaerythritol (Meth) acrylate, etc. These may be used alone or in combination of two or more. Further, "EO" means "ethylene oxide" and "PO" means "propylene oxide". Further, "Ε Ο modified" means a block structure having an ethylene oxide unit (-CHidO-), and Γρ〇 modified means a structure having a propylene oxide unit (-CH2CH(CH3)〇-) block structure. Compounds obtained by reacting a glycidyl group-containing compound with an αΘ-unsaturated carboxylic acid, such as trimethylolpropane triglycidyl ether tri(meth)acrylate and 2,2-bis(4-(meth)propene Alkyloxy-2-hydroxyl-propyloxy)phenyl and the like. The above α, /3 - unsaturated citric acid, such as (meth)acrylic acid. These may be used alone or in combination of two or more kinds of a hydrazine monomer or a urethane oligomer, such as a (meth)acrylic monomer having a mercapto group in the oxime group and isophorone diisocyanate, 2, Addition reaction with diisocyanate compound, such as 6-toluene diisocyanate, 2,4-tolyl diisocyanate, 1,6-hexamethylene diisocyanate, tris((meth) propylene methoxy tetraethylene glycol isocyanate Hexamethylene isocyanurate, hydrazine-modified urethane di(meth) acrylate, hydrazine or hydrazine modified urethane di(meth) acrylate, containing carboxyl urethane (meth) acrylate, etc. . These may be used alone or in combination of two or more. Further, examples of the alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethyl (meth)acrylate Hexyl ester and the like. These may be used alone or in combination of two or more. -22- 200832059 The photosensitive resin composition is based on the viewpoint of improving the photosensitivity and the flexibility of the cured film. The component (C) is preferably 1) an acrylate compound containing A-type di(meth)acrylate. The compound is better. &lt;Component (D): Photopolymerization initiator> (D) Component Photopolymerization initiator Specific example 4,4'-bis(dimethylamino)benzophenone (m-bis(diethyl) Amino) benzophenone, 4-methoxybenzophenone, 2-benzyl- 2-dimethylamine 3)-butanone-1,2-ethylfluorenone, phenanthrene and other aromatic benzene a benzyl derivative such as a hydrazine, a benzoin methyl ether or a benzoin ethyl group, a benzyl derivative such as a methyl benzoin or an ethyl benzoin methyl ketal, and a 9-phenyl acridine acridine. An acridine derivative such as heptane, an N-phenylglycine derivative, a coumarin compound or the like. More than one of these combinations are used. &lt;Component (E): Thermosetting agent&gt; Specific examples of the thermosetting agent of the component (E): thermosetting oxygen resin such as resin, urea resin or melamine resin, such as bisphenol A type tertiary fatty acid; Diglycidyl esters such as glycidyl esters and tetrahydrobenzene diesters, and diglycidyl resin composition composition resolution bisphenol A (methyl bisphenolic bisphenol surface, such as benzophenone, Benzene), 4,4'-yl- 4'-dimethylamine S-1 monomorpholone ketone ketone, alkyl fluorenone ether, benzoin phenyl ether and other benzoin, benzyl Base 2, 1, 7-bis (9,9'-glycine, N-phenyl, etc. may be used alone or in combination with 2, such as epoxy resins, phenolating compounds, etc. Ring-modified polyol epoxy resin formic acid Diglycidyl aniline, diglycidyl -23-200832059 diglycidylamine such as toluidine, etc. These may be used alone or in combination of two or more. In addition, in the case of the (E) component heat hardener, Blocked isocyanate compounds with latent heat hardeners can be used. For block isocyanate compounds, such as alcohol compounds, phenols Polyisocyanate compound blocked by a blocker such as ε-caprolactam, an anthracene compound or an active methylene compound. In the case of a blocked polyisocyanate compound, 454-diphenylmethane bis isocyanate , 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene 1,5-diisocyanate, oxime-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene dimer, etc. Alicyclic polyisocyanate such as polyisocyanate, hexamethylene diisocyanate, 4,4-monomethylene bis(cyclohexyl isocyanate) or isophorone diisocyanate, or alicyclic polyisocyanate such as bicycloheptane triisocyanate, which is heat resistant The aromatic polyisocyanate is preferred, and the aliphatic polyisocyanate or the alicyclic polyisocyanate is preferred from the viewpoint of preventing coloration. • In order to make the photosensitive resin composition have good flame retardancy, the photosensitive resin composition (A) The content of the component is preferably 35 to 70% by mass, more preferably 40 to 65% by mass based on the total amount of the solid content of the photosensitive resin composition. (A) Component content When the content is 35% by mass, the flame retardancy of the cured film tends to decrease, and when it exceeds 70% by mass, the development of the diluted aqueous solution tends to be difficult. Further, in order to obtain good flame retardancy, the phosphorus in the photosensitive resin composition is contained. The amount is preferably from 1.5 to 5.0% by mass, more preferably from 2.0 to 4.5% by mass, based on the total amount of the solid content of the photosensitive resin composition. The phosphorus content is less than 1.5 - 24 -

200832059% by mass, the flame retardancy of the cured film tends to decrease, and when it exceeds 5 · 0, the cured film has a folding resistance, and the insulation reliability tends to decrease. In addition, when the (Β) component is contained in the above range, the salt of the above formula (2) is used in the above-mentioned range, and the content of the component is based on the total amount of the solid content of the photosensitive resin composition. 5 to 20% by mass is preferred. When the content is less than 5% by mass, the flame retardancy tends to be lowered, and when it exceeds 20% by mass, the cured film tends to be lowered. Further, the (Β) component is a combination of a phosphate ester and a phosphonate, and the phosphate ester content is preferably from 1 to 20% by mass, more preferably from 3 to 10% by mass, based on the total amount of the solid content of the photosensitive resin composition. . When the amount of the uranium is more than 20% by mass, the uranium property and the exudation property (the photosensitive resin composition exudation) tend to deteriorate. In addition, when the phenoxyphosphazene is used in combination with the phosphonate as the (Β) component, the phenoxyphosphazene content is preferably 20% by mass based on the total solid content of the photosensitive resin composition, and 3 to 15% by mass. good. When the content exceeds a certain amount, the electric corrosion property and the exudation property (the bleed out of the photosensitive resin composition) tend to be formed. The content of the component (C) is more preferably 7 to 30% by mass and 10 to 25% by mass based on the total amount of the solid content of the resin composition, from the viewpoint of resolution and flame retardancy. When the content of the component (C) is less than 7 mass, the image quality tends to be deteriorated, and when it exceeds 30 mass%, the cured film tends to be difficult to be lowered. [Quantity% Η圭. : phosphonic acid ^ reference Μ匕 film "flexibility [time t is based on the amount of matter 〖 compound of the compound: compound [1 ~ 20 quality has a bad light $ $ good, 丨 解 solution $ sex -25-

200832059 The content of the component (D) is preferably 0.1 to 0.2 to 5% by mass based on the total amount of the solid content of the composition of the light sensitivity. In the case where the photosensitive resin composition contains the component (E), the flammability and the insulating reliability are preferably 5 to 20% by mass based on the photosensitive resin, and 8 to 4, and the photosensitive resin composition of the present invention is green or the like. Photochromic agents such as dyes, leuco crystal violets, plasticizers such as hot toluene sulfonamide, phthalocyanines such as phthalocyanine blue, or inorganic pigments such as titanium dioxide, inorganic pigments such as cerium oxide, calcium oxide or barium sulfate. The component such as the agent, the adhesion imparting agent, the leveling agent, the antioxidant, and the fragrance is preferably 0.01 to 20% by mass based on the total solid content of the photosensitive resin composition. Further, the above components may be used in combination. Further, the photosensitive resin composition of the present invention is in a solid solvent of methanol, ethanol, acetone, methyl ethyl ketone, methylcellulose, toluene, N,N-dimethylformamide, propionate or the like. Apply 30~70. The metal surface such as the photosensitive tree alloy, the iron or the iron-based alloy of the present invention described above is applied in the form of a protective film optical element as needed after application drying. The photosensitive resin / 1 〇 mass% is preferable, and the content thereof is more preferably 5 mass% from the solid content of the hard component. If necessary, it may contain a peacock hair color preventive agent or an organic pigmented aluminum such as P-azo or a talc, a carbonic acid defoaming agent, a stabilizer, a material or a developer. This amount is based on a single or two or more kinds of solutions which can be dissolved in a solution of a cellosolve or an ethyl solvate monomethyl ether. The composition can be used in copper or copper. The photoresist is used, or the sensation described later -26-200832059. Further, the substrate formed on a flexible substrate such as a hard polyimine obtained by the photosensitive resin composition of the present invention has excellent flammability and sensitization. Since the resin composition does not contain a halogen compound and the lanthanide system is a cured film, the flame retardancy is extremely high, so that the environmental load and toxicity such as printing can be reduced. Further, the photosensitive resin composition of the present invention can form a sufficient cured film with high resolution, and can form a sufficiently hardenable film, which is suitable for use in a printed wiring board, particularly for flexible printing with permanent film formation. . (Photosensitive Element) Next, a photosensitive element using the photosensitive resin of the present invention described above will be described. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. The photosensitive element 1 of Fig. 1 is a photosensitive resin composition layer 14 which is provided on the support 1 in the support I. The photosensitive resin composition layer 14 is a layer of the photosensitive resin of the present invention. Further, the photosensitive element 1 of the present invention may be a surface F 1 on the opposite side of the support 10 on the photosensitive composition layer 14 to be protected. The photosensitive resin composition layer 14 is a solution in which the photosensitive product of the present invention is dissolved in the solvent or the mixed solvent to obtain a solid content of 30% by weight, and then the solution is applied to the support 1 to form a crucible. The thickness of the photosensitive resin composition layer 14 is different depending on the use. The composition of the present invention, the flame-retardant flexible wire plate of the wire plate is implemented as a 110'. The compositional physical resin film is preferably made of a resin group 70, and the dried thickness of the solvent is removed by heating and/or hot air blowing from -27 to 200832059, preferably 1 ο to 100//m, 20 to 60. #m is better. If the thickness is less than 10/m, the industrial coating work tends to be difficult. When the thickness exceeds 10 〇〇//m, the above-mentioned effects achieved by the present invention tend to be small, and in particular, the flexibility and the resolution are lowered. The support member 10 included in the photosensitive element 1 is, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene or polyester. The thickness of the support 10 is preferably 5 to 100 / / m, more preferably 10 to 30 / zm. When the thickness is less than 5 // m, the support tends to be easily broken when the support is peeled off before development, and the resolution and flexibility tend to decrease when it exceeds 100 m. The photosensitive element 1 or the support 10 and the photosensitive resin composition layer 14 and the protective film are formed of two layers of the support 1 and the photosensitive resin composition layer 14 For example, it can be stored directly or placed in a roll shape with a protective film. The method for forming a photoresist pattern using the photosensitive element of the present invention optionally includes a step of removing the protective film by the photosensitive element, and sequentially laminating the photosensitive element with a photosensitive resin composition layer and a support. The step of laminating on the substrate for formation, and the step of irradiating the specific portion of the photosensitive resin composition layer with the support by the support, and exposing the photocurable portion to the photosensitive resin composition layer, and removing the photo-cured portion The development step of the photosensitive resin composition layer. Further, the circuit-forming substrate is provided with an insulating layer and a conductor layer formed on the insulating layer (copper, copper-28-200832059 alloy, iron-based alloy such as nickel, chromium, iron, stainless steel, alloy or iron-based alloy). The substrate of the person). In the method of laminating the step of removing the protective film as needed, there is a method of laminating by heating the photosensitive resin composition forming substrate while pressing. There is no particular limitation, and it is preferable from the viewpoints of adhesion and followability. The laminated surface is usually a circuit forming substrate, but may be a surface other than the conductor layer. The heating temperature of the photosensitive resin composition layer is preferably 7 Torr to 15 MPa, and the ambient pressure is more preferably, but the conditions are not particularly limited. Further, the resultant layer is heated at 70 to 130 ° C as described above, and the pre-heat treatment of the circuit is not necessary, and the pre-heat treatment of the substrate for formation is performed in order to improve the lamination property. After the lamination is completed, in the exposure step, the photocured portion is formed after the active light is irradiated to the photosensitive specific portion. In terms of photometry, there is a method of passing a negative or positively-like active light called a post-photograph. In this case, when the support of the photosensitive resin group is transparent, the active light can be directly irradiated, and the support can be removed and then irradiated on the photosensitive resin composition layer. In terms of the active light source, a known light source such as a silver vapor arc lamp can be used. Ultra high pressure mercury lamp, high pressure mercury lamp, and ultraviolet light. In addition, it is also possible to use a planar light for photographing to efficiently emit visible light. Preferably, in the copper and copper lamination step, the environment of the layer formed during the electrical lamination is preferably a conductor layer of the laminate under reduced pressure / 130 ° C, and the substrate for forming the photosensitive resin group below 4000 Pa The circuit resin pattern layer hardening portion may be formed to form a square film pattern to illuminate the active layer when the image layer is opaque. Use a carbon arc lamp, a water lamp, etc. to effectively discharge the lamp, the sun lamp, etc. -29-200832059 Then, 'after exposure, when there is a support on the photosensitive resin composition layer', after removing the support, the development step is wet. For example, a photosensitive resin composition layer other than the photocured portion is removed after dry development, and then developed to form a photoresist pattern. In the case of wet development, a developing solution such as an alkaline aqueous solution is used, and development is carried out by a known method such as spraying, shaking immersion, brushing, or brushing. The developing liquid surface can be used safely and stably, and if it has good workability, a thin solution of sodium carbonate (1 to 5 mass% aqueous solution) such as 20 to 50 C can be used. When the photoresist pattern obtained by the above-described formation method is used as a solder resist for a printed wiring board, for the purpose of improving solder heat resistance and chemical resistance as a solder resist after the development step is completed, Ultraviolet irradiation by a high pressure mercury lamp and heating of the oven are preferred. When the ultraviolet ray is irradiated, the amount of irradiation may be adjusted as needed. For example, it may be irradiated with an amount of 0.2 to 1 (U/cm 2 ). Further, when heating, it is preferably carried out at a temperature of 100 to 170 ° C for 15 to 90 minutes. Alternatively, both ultraviolet irradiation and heating may be performed, and after performing either of them, the other may be carried out. Further, the photoresist pattern obtained by the above-described forming method is used as a permanent film formed on a printed wiring board. The cured film formed of the photosensitive resin composition of the present invention is excellent in flame retardancy and has a protective film for wiring after soldering on a substrate, and can be effectively used as a permanent film for a printed wiring board. EMBODIMENT -30-200832059 [Examples] Hereinafter, the invention will be more specifically described by way of Examples and Comparative Examples. The invention is not limited to the following examples. (Examples 1 to 7, Comparative Examples 1 to 4) First, Table 1 The components shown in the figure are obtained on the basis of the solid-separated mass quality shown (but, methyl ethyl ketone is the mass basis of the liquid), and a photosensitive resin composition solution is obtained. In addition, in Table 1, the component (A-1) is a biphenyl type epoxidized propylene (manufactured by Nippon Kayaku Co., Ltd., trade name "ZCR-1569H", and the phenolic varnish type acid-modified vinyl ring Oxygen resin, acid value = 9 8 = 4500), (A-2) component is bisphenol A type epoxy acrylate (manufactured by Chemical Pharmaceutical Co., Ltd., trade name "ZAR-200 1 H", acid value = 1〇3,

1 3 000 ) , (A-3 ) is a bisphenol F type epoxy acrylate (manufactured by E Pharmaceutical Co., Ltd., trade name "ZFR-1516", acid value = 7 3, Mw = ) ° (B-1) It is a phosphonate (Clariant in Japan company name "EXOLITOP 935", phosphorus content = 23% by mass), and 2) is a phosphate ester (trade name "ADEKASTABFP-600", manufactured by ADEKA CORPORATION, phosphorus content = 8·9 The mass%), the component is a phenoxyphosphazene compound (Otsuka Chemical Co., Ltd. product name "SPB-100", phosphorus content = 13% by mass). The component (C) is bisphenol A polyoxyethylene dimethacrylate (manufactured by Murakami Chemical Co., Ltd., trade name "BPE-10"). But this

3 ratio (! line mixed ¥ ester 骨架 skeleton, M w : 曰本 M w = I localized 11000 system, quotient (Β- (Β-3 f, 商:新中-31 - 200832059 (D) component is 2 —Benzylmono-2-dimethylamino-1—(4-morpholinylphenyl)-butanone-1 (manufactured by Ciba Specialty Chemicals, trade name “1-3 69”). (E) Ingredients are Hexamethylene diisocyanate is a 75 mass % methyl ethyl ketone solution of a methyl ethyl ketone oxime block of isocyanurate of benzoisocyanate (manufactured by Bayer Urea Co., Ltd., trade name " BL3 175 j ) ° In addition, in the table, acrylic resin is copolymerized with methacrylic acid/ethyl acrylate/methyl methacrylate/styrene in toluene/methyl cellosolve (mass ratio = 2/3) The solution was polymerized in a usual manner to a copolymer having an acid value of 80 mgKOH/g and a weight average molecular weight of 100,000. [Table 1] Example Comparative Example 1 2 3 4 5 6 7 1 2 3 4 (A-1) 90 90 90 90 90 90 70 - 90 - (A-2戚分 - - - - - - - 90 - - 90 (A-3 ratings • 90 (B-1 points 15 15 10 10 - 15 15 15 15 - - (B-2 points - 15 25 5 30 - - - - - 30 (B-3戚 • - 15 15 - - - - (C Cheng 20 20 20 20 20 20 20 20 20 20 20 (D戚3 3 3 3 3 3 3 3 3 3 3 Φ戚20 20 20 20 20 20 20 20 20 20 20 Acrylic Resin • 丨 Round 丨 • 20 • 丨 - - Methyl ethyl ketone 20 20 20 20 20 20 20 20 20 20 20

Note) In Table 1, 値 is the solid content ratio of each component (except methyl ethyl ketone) • 32- 200832059 In addition, the symbol “-” in the table indicates that the component is not included. [Production of Photosensitive Element] A polyethylene terephthalate film having a thickness of 1 6 /zm thick of the support was applied by uniformly applying the photosensitive resin composition solutions of Examples 1 to 7 and Comparative Examples 1 to 4, respectively. A photosensitive resin composition layer was formed on (manufactured by Teijin Co., Ltd., trade name "G2-16"), and dried by a hot air convection dryer at 100 ° C for 1 minute. The film thickness after drying of the photosensitive resin composition layer was 3 8 /am. Then, a polyethylene film (trade name "NF-1 3", manufactured by Tamapoly Co., Ltd.) was bonded to the back surface on the side in contact with the support of the photosensitive resin composition layer to obtain a photosensitive member. [Production of laminate for evaluation] A substrate for a flexible printed wiring board obtained by laminating a 18//m thick copper foil on a polyimide substrate (manufactured by NIKKAN INDUSTRIES Co., Ltd., trade name "F30VC1" The copper surface was acid washed with hydrochloric acid, washed with water, and dried. In the flexible printed wiring board substrate, a continuous vacuum laminator (trade name "HLM-V570", manufactured by Hitachi Chemical Co., Ltd.) was used, and the laminating speed was 55 m/cm at a hot pressing temperature of 10 °C. In the case where the pressure was 3,000 Pa or less and the pressure was 0.3 MPa, the obtained photosensitive element was laminated on the side of the polyethylene foil, and the photosensitive resin composition layer was used as the copper foil side to obtain a laminate for evaluation. -33-200832059 [Evaluation of Light Sensitivity] On the laminate for evaluation described above, an optical device having a stepped plate of a StaUffer 21 step as a negative film was attached, and an HMW-201GX type exposure machine manufactured by Ouke Industries Co., Ltd. was used to make Stauffer 21 steps. After the ladder plate is developed, the number of remaining step segments is 8·0, and the exposure is performed. Subsequently, the film was allowed to stand at room temperature for 1 hour, and after peeling off the PET film, it was developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C for 40 seconds, and heating (drying) at 80 ° C for 10 minutes. The light sensitivity is used as the evaluation number, and the above energy amount at the time of exposure is used. The lower the number, the higher the light sensitivity. The results are shown in Table 2. [Evaluation of the resolution] The optical device having the Stauffer 2 step plate and the wiring pattern having the line width/space width of 30/30 to 200/200 (unit: //m) as the film for resolution evaluation are provided. The evaluation laminate was adhered to each other, and the exposure machine was used to expose the Stauffedl step plate after the image was developed and the number of remaining step segments was 8.0. Subsequently, the film was allowed to stand at room temperature for 1 hour, and after peeling off the PET film, it was developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C for 40 seconds, and heating (drying) at 80 ° C for 1 〇 minutes. Here, the resolution is evaluated by the minimum 値 (unit: m) of the width of the line width of the rectangular photoresist shape obtained by the development processing. The smaller the flaw, the better the resolution. The results are shown in Table 2. -34-200832059 Manufacture of FPC for evaluation] On the laminate for evaluation, the optical device having a stepper plate of a Stauffer 21 step is attached to an optical device having a wiring pattern as a film for reliability evaluation of a cover layer, and the above exposure is used. After the machine, the amount of energy remaining after the step of the Staiiffedl step plate is 8.0 is exposed. Then, after standing at room temperature for 1 hour, the polyethylene terephthalate on the laminate is peeled off, and the light sensitivity is In the evaluation, the same developing solution and developing conditions were subjected to spray development, and the film was heated (dried) at 80 ° C for 10 minutes. Then, ultraviolet irradiation was performed at an energy of 1 J/cm 2 using an ultraviolet irradiation device manufactured by Ouke, Ltd. The heat treatment was carried out at 160 ° C for 60 minutes to obtain an FPC for evaluation for forming a coating layer. [Flexibility (Folding Resistance Evaluation)] The above-mentioned evaluation FPC was repeatedly subjected to 18 0° bending by a fixed joint. The number of times until the coating layer was cracked was determined and evaluated by the following criteria. Further, whether the crack was generated or not was confirmed by a microscope. The results are shown in Table 2. A: Even if the bending is 5 times If there is no crack in the coating layer, B: the number of times of bending to the crack is 3 to 4 times, and C: to the number of times the crack is generated is less than 2 times. [Erosion evaluation] Let the above evaluation be evaluated by FPC. Using a 3 01 hand press (manufactured by Toyo Seiki Seisakusho Co., Ltd.), pressurizing temperature of 160 ° C, pressurizing pressure of -35 - 200832059 2 Okgf for 30 minutes in the thickness direction. The composition of the photosensitive resin composition which was oozing from the coating layer was evaluated based on the following criteria. In other words, it was not confirmed that the photosensitive resin composition component was bleed out from the coating layer, and it was confirmed that a small amount of the photosensitive resin composition component was observed. The exudation is "B", and the osmosis of the photosensitive resin composition component is "C". The results are shown in Table 2. [Evaluation of flame retardancy] Copper-clad laminate (manufactured by Nippon Steel Chemical Co., Ltd., product) The copper foil of the "Espanex MB series" was removed by etching to obtain a PI film having a thickness of 25/m. Then, a continuous vacuum laminator (manufactured by Toray Chemical Industry Co., Ltd., trade name "HLM" was used on both sides of the PI film. -V570"), hot pressing The temperature is 10 ° C, the laminating speed is 0.5 m / min, the air pressure is 4,000 Pa or less, and the photosensitive element is peeled off from the polyethylene film under the pressure of 3 MPa to laminate the photosensitive resin composition layer to the PI film. The side was subjected to lamination, and the exposure of the photosensitive resin composition layer of the photosensitive element was performed using an HNW-201GX type exposure machine manufactured by Ouke, Ltd., so that the number of steps remaining after the Stauffer 21 step plate was developed was 8.0. Then, the amount of energy was increased. Then, the polyethylene terephthalate film was peeled off from the laminate at room temperature for 1 hour, and then sprayed at 30 ° C with a 1 mass% sodium carbonate aqueous solution in a laminate for 40 seconds for development. Heat (dry) at 〇 °C for 10 minutes. Next, the photosensitive resin composition layer of the laminate was irradiated with ultraviolet rays of 1⁄4/cm 2 at an energy amount of 1 J/cm 2 , and 60 minutes by 1 60 ° C using an ultraviolet irradiation device manufactured by Ouke Industries Co., Ltd. Heat treatment was performed to obtain a sample for evaluation of flame retardancy in which a coating layer was formed. Regarding this sample for flame retardancy evaluation, the vertical burning test of the thin material was carried out in accordance with the UL94 standard. The evaluation is based on the UL94 specification and is expressed as VTM-0, VTM-1, or VTM-2. The results are shown in Table 2. In addition, "NOT" in Table 2 means that the samples for flame retardancy evaluation in the combustion test are not VTM-0, VTM-1, and VTM-2.

[Table 2] Example Comparative Example 1 2 3 4 5 6 7 1 2 3 4 Light sensitivity (mJ/cm2) 180 180 200 200 200 180 190 200 200 160 200 Resolution μ m 70 70 70 70 70 70 70 70 80 60 70 Flexibility (Fold-resistant) BAABAAABBBA Exudative ABCACAAAAAC Flame retardant VTM-0 VTM-0 VTM-0 VTM-0 VTM-1 VTM-0 VTM-0 NOT NOT NOT NOT As understood from the results of Table 2, according to the embodiment The photosensitive resin composition of 1 to 7 was confirmed to have sufficient light sensitivity and resolution. Further, the laminate having the cured film formed of the photosensitive resin compositions of Examples 1 to 7 has sufficient flame retardancy. Further, the cured film formed of the photosensitive resin compositions of Examples 2, 3 and 5 to 7 has excellent flexibility (folding resistance) -37-200832059 [Industrial Applicability] As described above, according to the above description, According to the present invention, it is possible to provide a photosensitive resin composition which has excellent alkali developability and can form a cured film excellent in flame retardancy, and a photosensitive element using the same. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive film of the present invention. [Explanation of main component symbols] 1 : Photosensitive element 1 〇 : Support 1 4 : Photosensitive resin composition layer

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Claims (1)

200832059 X. Patent Application No. 1 · A photosensitive resin composition characterized by (A) a novolac type acid-modified vinyl epoxy resin having a biphenyl skeleton, and (B) a phosphorus-containing compound, and (C) a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule, and (D) a photopolymerization initiator. 2. The photosensitive resin composition of claim 1, wherein the (A) epoxy resin comprises (A) an epoxy resin represented by the following formula (1) and (B) an unsaturated group-containing An acid-modified vinyl epoxy resin obtained by reacting monodecanoic acid with (C) with a polyanthracene anhydride, [Chemical Formula 1] [In the formula (1), 'R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and η is an integer of 〇 50 50. Further, in the formula (丨), a plural number exists. R1 and R2 may be the same or each. 3. A photosensitive resin composition of the first or second aspect of the patent application, which further contains a (b) thermal hardener. 4. The photosensitive resin composition of the above-mentioned item in the first to third paragraphs of the patent application, wherein the (Β) phosphorus-containing compound is a phosphonic acid containing the underarm of the formula (2) and not -39-200832059 Salt [Chemical 2] Ο Mm+ (2) II A—P—0 B [In the formula (2), A and B are each independently, and represent a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group. , Μ denotes at least one metal selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K, 1 is 1 The photosensitive resin composition according to any one of claims 1 to 4, wherein the (B) phosphorus-containing compound contains a phosphate. The photosensitive resin composition according to any one of claims 1 to 5, wherein the (B) phosphorus-containing compound comprises a phenoxyphosphazene compound 7. 7. 7. Patent Application Nos. 1 to 6 A photosensitive resin composition according to any one of the preceding claims, which is formed on a flexible substrate to form a cured film as a permanent film. And a photosensitive resin composition comprising a support and a photosensitive resin composition according to any one of claims 1 to 7 formed on the support. Floor. -40-