JP2009294319A - Photosensitive resin composition, photosensitive film and photosensitive permanent resist - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide photosensitive resin composition, having superior flame resistance and plating resistance, and forming a cured film having various characteristics required for solder resist, and a photosensitive film and photosensitive permanent resist using it. <P>SOLUTION: This photosensitive resin composition includes (a) binder polymer, (b) polymerized compound having ethylene series unsaturated group, (c) polymerization initiator, (d1) organic phosphorous compound, and (d2) inorganic filler. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, and a photosensitive film and a photosensitive permanent resist using the same.

  In the printed wiring board manufacturing industry, conventionally, a solder resist is formed on a printed wiring board. This solder resist has a role to prevent solder from adhering to unnecessary portions of the conductor layer of the printed wiring board in the soldering process for bonding the mounted part to the printed wiring board. When the printed wiring board is used later, it also serves as a permanent mask for preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers.

  As a method for forming a solder resist, for example, a method of screen printing a thermosetting resin on a conductor layer of a printed wiring board is known. However, since such a method has a limit in increasing the resolution of the resist pattern, it has become difficult to cope with the recent increase in the density of printed wiring boards.

  Therefore, in order to achieve high resolution of the resist pattern, the photoresist method has been actively used. In this photoresist method, a photosensitive resin composition layer made of a photosensitive resin composition is formed on a substrate, the photosensitive resin composition layer is cured by exposure of a predetermined pattern, and unexposed portions are removed by development. Thus, a cured film having a predetermined pattern is formed.

  In addition, the photosensitive resin composition used in such a method is mainly an alkali development type that can be developed with a dilute aqueous alkali solution such as an aqueous sodium carbonate solution from the viewpoint of conservation of the working environment and global environment. .

  As such a photosensitive resin composition, a liquid resist ink composition (for example, refer to Patent Document 1), a photosensitive thermosetting resin composition (for example, refer to Patent Document 2), and the like are known.

  On the other hand, solder resists generally have developability, high resolution, insulation, solder heat resistance, plating resistance, thermal shock resistance against temperature cycle test (TCT), super accelerated high temperature high humidity life test ( HAST tolerance between fine wirings for HAST) is demanded.

  Further, recently, as a method of directly drawing a pattern created by CAD (Computer-Aided Design) without using a mask with a laser beam, it is strongly desired to support an LDI (Laser Direct Imaging) method. However, the LDI method cannot be used as a method for forming a solder resist because the LDI method requires an ultrasensitive photosensitive resin composition from the viewpoint of throughput improvement as compared with a general batch exposure method.

  By the way, in recent years, regulations on flame retardancy of various industrial products against fire have become stricter, and materials used for printed wiring boards and the like are no exception. As an effective flame retarding method, a method of adding a halogen-based compound, an antimony-based compound or the like to a material is generally known.

Recently, however, it has been desired to respond to environmental problems. In addition to being difficult to burn, there is a need for flame retardant printed wiring board materials that do not use halogen compounds or antimony compounds to reduce environmental impact. .
JP-A 61-243869 Japanese Patent Laid-Open No. 01-141904

  However, when a cured film is formed using a conventional photosensitive resin composition as described in Patent Documents 1 and 2 on a substrate that does not use a halogen-based compound or an antimony-based compound, sufficient flame retardancy is achieved. The present inventors have found out that (preferably UL94 V-0 level) cannot be secured.

  Moreover, the cured film formed using the conventional photosensitive resin composition has insufficient plating resistance, and there is a problem that the designed plating pattern cannot be obtained due to the resist floating or peeling that occurs during the plating process. is there.

  The present invention has been made in view of the above circumstances, and is a photosensitive resin composition that is excellent in flame retardancy and plating resistance and can form a cured film having various properties required for a solder resist, and the same. It aims at providing the photosensitive film and photosensitive permanent resist which used this.

  In order to achieve the above object, the present invention provides (a) a binder polymer, (b) a polymerizable compound having an ethylenically unsaturated group, (c) a polymerization initiator, (d1) an organic phosphorus compound, and (d2) an inorganic material. A photosensitive resin composition containing a filler is provided.

  According to this photosensitive resin composition, by having the said structure, while having the outstanding alkali developability, the cured film can obtain the outstanding flame retardance and plating resistance. Therefore, the said photosensitive resin composition can be used suitably for manufacture of the printed wiring board etc. in which a flame retardance and plating resistance are requested | required.

［式（１）中、Ａ及びＢは各々独立に、直鎖状又は分枝状の炭素数１〜６のアルキル基又はアリール基を示し、ＭはＭｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ及びＫからなる群より選択される少なくとも一種の金属を示し、ｍは１〜４の整数を示す。］ Moreover, in the photosensitive resin composition of this invention, it is preferable that the said (d1) organophosphorus compound contains the phosphinic acid salt represented by following General formula (1).

[In Formula (1), A and B each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and M represents Mg, Ca, Al, Sb, Sn, Ge. , Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K represent at least one metal selected from the group consisting of 1 to 4; ]

  When the photosensitive resin composition contains the phosphinic acid salt represented by the general formula (1), the flame retardancy of the obtained cured film can be further improved.

  Moreover, in the photosensitive resin composition of this invention, it is preferable that the said (a) binder polymer contains the polymerizable prepolymer which has (a1) a carboxyl group and an ethylenically unsaturated group. Thereby, the alkali developability of the photosensitive resin composition and the plating resistance and thermal shock resistance of the resulting cured film can be further improved.

  In the photosensitive resin composition of the present invention, the polymerizable prepolymer having (a1) a carboxyl group and an ethylenically unsaturated group is an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups; It is preferably a compound obtained by reacting a diisocyanate compound with a diol compound having a carboxyl group. Thereby, the sensitivity of the photosensitive resin composition and the thermal shock resistance of the resulting cured film can be further improved.

  In the photosensitive resin composition of the present invention, the (a) binder polymer is a vinyl copolymer compound obtained by using (a2) (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component. It is preferable to include. Thereby, the alkali developability of the photosensitive resin composition can be further improved.

  Moreover, it is preferable that the photosensitive resin composition of this invention further contains (e) thermosetting agent. When the photosensitive resin composition contains (e) a thermosetting agent, the photosensitive resin composition is photocured and then further thermoset to further improve the insulation reliability of the resulting cured film. Can do.

  Moreover, this invention provides a photosensitive film provided with a support body and the layer which consists of the said photosensitive resin composition of this invention formed on this support body. According to such a photosensitive film, a dry film type solder resist made of the photosensitive resin composition of the present invention can be easily formed, and the cured film of the formed photosensitive resin composition layer has flame retardancy and Excellent plating resistance.

  Furthermore, this invention provides the photosensitive permanent resist which consists of a photocured material of the said photosensitive resin composition of this invention apply | coated on the board | substrate for printed wiring boards. Since this permanent resist is formed from the photosensitive resin composition of the present invention, it has excellent flame retardancy and plating resistance.

  According to the present invention, a photosensitive resin composition having excellent alkali developability, excellent flame retardancy and plating resistance, and capable of forming a cured film having various properties required for a solder resist, and the same The photosensitive film and photosensitive permanent resist using can be provided.

  The photosensitive resin composition of the present invention has the above-described configuration, so that development with a dilute alkaline aqueous solution is possible, and the flame retardancy and plating resistance of a cured film obtained by curing the photosensitive resin composition. Can be satisfied at a high level. Therefore, according to the photosensitive resin composition of the present invention, it is possible to efficiently form a cured film having sufficient flame retardancy and plating resistance with high resolution.

  Moreover, the board | substrate which formed the cured film which consists of the photosensitive resin composition of this invention on flexible base materials, such as a glass epoxy base material or a polyimide, has the outstanding flame retardance. Since the photosensitive resin composition of the present invention can make the cured film sufficiently high in flame retardancy without containing a halogen compound or an antimony compound, for example, reducing the environmental load of a printed wiring board. Is possible.

  Moreover, since the photosensitive resin composition of this invention can form the cured film which has sufficient flame retardance and metal-plating resistance with high resolution, it is preferably used for permanent mask formation of a printed wiring board.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (a) a binder polymer (hereinafter sometimes referred to as “component (a)”), (b) a polymerizable compound having an ethylenically unsaturated group (hereinafter sometimes referred to as “(b ) Component ”), (c) polymerization initiator (hereinafter sometimes referred to as“ (c) component ”), (d1) organophosphorus compound (hereinafter sometimes referred to as“ (d1) component ”), and (d2) It contains an inorganic filler (hereinafter referred to as “component (d2)” in some cases). Moreover, it is preferable that the photosensitive resin composition of this invention further contains (e) thermosetting agent (henceforth "(e) component").

  Hereinafter, each component contained in the photosensitive resin composition of the present invention will be described.

[(A) component: binder polymer]
Examples of the component (a) include acrylic resin, polyurethane, vinyl group-containing epoxy resin, epoxy resin, phenoxy resin, polyester, polyamide, polyimide, polyamideimide, polyesterimide, polycarbonate, melamine resin, polyphenylene sulfide, and polyoxybenzoyl. And known acid-modified resins such as those having a carboxyl group in the molecule. These can be used alone or in combination of two or more.

  The component (a) preferably contains a polymer having a carboxyl group in the molecule from the viewpoint of further improving alkali developability.

  From the viewpoint of further improving the plating resistance and thermal shock resistance of the cured film obtained as the polymer having a carboxyl group in the molecule, (a1) a polymerizable prepolymer having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as “polymeric prepolymer”) In some cases, it is also preferable to include “(a1) component”), and (a2) a vinyl copolymer compound (hereinafter referred to as “copolymer component”) obtained from (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component. In some cases, it is also preferable to include “(a2) component”. (A1) component and (a2) component can be used individually by 1 type or in combination of 2 or more types. Hereinafter, the component (a1) and the component (a2) will be described.

[(A1) component: polymerizable prepolymer having carboxyl group and ethylenically unsaturated group]
The component (a1) is not particularly limited as long as it is a polymerizable prepolymer having a carboxyl group and an ethylenically unsaturated group in the molecule. However, the sensitivity of the photosensitive resin composition is increased, that is, less active light energy is used. A polyurethane compound obtained by reacting an epoxy acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group, a diisocyanate compound, and a diol compound having a carboxyl group from the viewpoint of curing in terms of quantity preferable. Examples of preferable polyurethane compounds include UXE-3011, UXE-3012, and UXE-3024 (above, Nippon Kayaku Co., Ltd., sample name). An example of such a polyurethane compound is a compound having a structure represented by the following general formula (2).

ここで、一般式（２）中、Ｒ^１１はエポキシアクリレートの残基、Ｒ^１２はジイソシアネートの残基、Ｒ^１３は炭素数１〜５のアルキル基、Ｒ^１４は水素原子又はメチル基を示す。なお、残基とは、原料成分から結合に供された官能基を除いた部分の構造をいう。また、式中に複数ある基は、それぞれ同一でも異なっていてもよい。

Here, in the general formula (2), R ¹¹ is an epoxy acrylate residue, R ¹² is a diisocyanate residue, R ¹³ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁴ is a hydrogen atom or a methyl group. In addition, a residue means the structure of the part remove | excluding the functional group used for the coupling | bonding from the raw material component. In addition, a plurality of groups in the formula may be the same or different.

  The acid value of the polyurethane compound is preferably 20 to 130 mgKOH / g, more preferably 40 to 110 mgKOH / g, and still more preferably 50 to 100 mgKOH / g. Thereby, the developability with the alkaline aqueous solution of the photosensitive resin composition becomes good, and an excellent resolution can be obtained.

Here, the acid value can be measured as follows. That is, first, about 1 g of a resin solution whose acid value is to be measured is precisely weighed, and then 30 g of acetone is added to this resin solution to dissolve it uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
A = 10 × Vf × 56.1 / (Wp × I)

  In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of 0.1N KOH aqueous solution, Wp represents the weight (g) of the measured resin solution, and I was measured. The ratio (mass%) of the non volatile matter in a resin solution is shown.

  In addition, the weight average molecular weight of the polyurethane compound is preferably 3000 to 200000 from the viewpoint of obtaining good coating properties with the photosensitive resin composition and good crack resistance and HAST resistance of the cured film. It is more preferable that it is 7000-50000. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene).

  By using the polyurethane compound as the component (a1), it is possible to achieve high sensitivity while maintaining high flame retardancy and thermal shock resistance. From the viewpoint of flame retardancy, thermal shock resistance, and solder heat resistance, it is most preferable to use UXE-3024 (manufactured by Nippon Kayaku Co., Ltd., sample name) as the component (a1).

  As the component (a1), an addition reaction product obtained by adding a saturated or unsaturated polybasic acid anhydride to an esterified product of an epoxy compound and an unsaturated monocarboxylic acid can also be used. As the epoxy compound, for example, a bisphenol A type, a bisphenol type epoxy compound obtained by reacting bisphenol F type and epichlorohydrin is suitable, bisphenol A type such as GY-260, 255, XB-2615 manufactured by Ciba Geigy, Epoxy compounds such as bisphenol F type, hydrogenated bisphenol A type, amino group-containing, alicyclic or polybutadiene-modified are preferably used. Also suitable are novolak-type epoxy compounds obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenols and alkylphenols with formaldehyde in the presence of an acidic catalyst and epichlorohydrin. YDCN-manufactured by Toto Kasei Co., Ltd. 701,704, YDPN-638,602, DEN-431,439 manufactured by Dow Chemical Company, EPN-1299 manufactured by Ciba Geigy Co., Ltd., N-730, 770, 865, 665, 673 manufactured by Dainippon Ink & Chemicals, Inc., VH -4150, 4240, Nippon Kayaku Co., Ltd. EOCN-120, BREN and the like.

  In addition to bisphenol type and novolac type epoxy compounds, for example, salicylaldehyde-phenol or cresol type epoxy compounds (Nippon Kayaku Co., Ltd. EPPN502H, FAE2500, etc.) are preferably used. Further, for example, Epicoat 828, 1007, 807 manufactured by Japan Epoxy Resin Co., Epiklone 840, 860, 3050 manufactured by Dainippon Ink & Chemicals, DER-330, 337, 361 manufactured by Dow Chemical Co., Celoxide 2021 manufactured by Daicel Chemical Industries, Mitsubishi Gas Chemical Co., Ltd. TETRAD-X, C, Nippon Soda Co., Ltd. EPB-13, 27, etc. can be used. Mixtures or block copolymers of these can also be used.

  Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, cinnamic acid, saturated or unsaturated polybasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule, or saturated or unsaturated. Reactions of half-ester compounds of saturated dibasic acids with unsaturated monoglycidyl compounds, eg phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and hydroxyethyl (meth) acrylate, hydroxypropyl Examples thereof include reactants obtained by reacting (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, and glycidyl (meth) acrylate at an equimolar ratio by a conventional method. These unsaturated monocarboxylic acids can be used alone or in combination. Of these, acrylic acid is preferred.

  Examples of the saturated or unsaturated polybasic acid anhydride include anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, and trimellitic acid.

  Examples of the commercially available polymerizable prepolymer having a carboxyl group and an ethylenically unsaturated group include ZAR-1035, CCR-1171H, and PCR-1050 (all of which are sample names) manufactured by Nippon Kayaku Co., Ltd.

[(A2) component: vinyl copolymer compound obtained by using (meth) acrylic acid and (meth) acrylic acid alkyl ester as copolymerization component]
The component (a2) can be obtained by radical polymerization using, for example, (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid. Examples include pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, and (meth) acrylic acid 2-ethylhexyl ester.

  As said vinyl type copolymer compound, you may use the compound obtained by copolymerizing the vinyl monomer which can be copolymerized with these with (meth) acrylic-acid alkylester and (meth) acrylic acid. Examples of such vinyl monomers include acrylamides such as diacetone acrylamide, esters of vinyl alcohols such as acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid tetrahydrofurfuryl ester, and (meth) acrylic acid dimethylaminoethyl. Ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α -(Meth) acrylic monomers such as bromo (meth) 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 can be used alone or in combination of two or more.

  Moreover, the copolymer which introduce | transduced the ethylenically unsaturated bond into the side chain and / or terminal of the vinyl monomer copolymer which can be copolymerized with (meth) acrylic-acid alkylester and (meth) acrylic acid is also suitable. Examples of vinyl monomer copolymers include vinyl polymerizable monomers having a carboxyl group such as acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, and itaconic acid, and methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate. , N-propyl methacrylate, n-propyl acrylate, butyl methacrylate, butyl acrylate, lauryl methacrylate, lauryl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, vinyl toluene, N-vinyl pyrrolidone, α-methyl styrene, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate Use vinyl polymerizable monomers such as those obtained by general solution polymerization using polymerization initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, and benzoyl peroxide in an organic solvent. Can do.

  The acid value of the binder polymer (a) according to this embodiment is preferably 40 to 170 mgKOH / g in the case of an acrylic or acid-modified polyester binder polymer, for example, from the viewpoint of improving alkali developability. 50-150 mgKOH / g, more preferably 60-120 mgKOH / g.

  The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 to 200,000, more preferably 10,000 to 200,000 from the viewpoint of improving the coating properties and alkali developability of the photosensitive resin composition. Preferably, it is 20000-200000.

  In said (a) binder polymer, it is preferable to use a component (a1) and a component (a2) together from a viewpoint of a sensitivity, a flame retardance, a coating-film property, and heat resistance.

  The content of the component (a) is preferably 20 to 70% by mass, more preferably 30 to 50% by mass based on the total amount of non-volatile organic compounds in the photosensitive resin composition.

  Moreover, 20-100 mass% is preferable in the total amount of (a) component, and, as for the content rate of (a1) component in the case of using (a1) component and (a2) component together, 40-100% is more preferable. Moreover, 5-40 mass% is preferable on the basis of the organic compound non volatile matter whole quantity in the photosensitive resin composition, and, as for the content rate of (a2) component, 10-30 mass% is more preferable.

[Component (b): Polymerizable monomer having an ethylenically unsaturated group]
The polymerizable monomer which is the component (b) of the present invention is a compound having one or more ethylenically unsaturated groups in the molecule. Examples of such polymerizable monomers include bisphenol A-based (meth) acrylate compounds, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, and glycidyl group-containing compounds with α, β-unsaturated compounds. Examples include compounds obtained by reacting saturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond in the molecule, or urethane oligomers. Besides these, nonylphenoxy polyoxyethylene acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxy Examples thereof include phthalic acid compounds such as alkyl-o-phthalate, (meth) acrylic acid alkyl esters, and EO-modified nonylphenyl (meth) acrylate. These may be used alone or in combination of two or more.

  The component (b) preferably contains a bisphenol A (meth) acrylate compound from the viewpoint of improving alkali developability. Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Is mentioned.

  It is more preferable that the component (b) includes 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane. Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl), 2,2- Bis (4-((meth) acryloxydodecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl), 2,2-bis (4-((meth) acrylic) Loxytetradecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl), and 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) Etc. You may use these individually or in combination of 2 or more types. In addition, it is preferable to use a halogen-free component among the above-described component (b) from the viewpoint of impediment reduction to the environment.

  Among the above compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.) or BPE-500 (Shin Nakamura Chemical Co., Ltd.). ), Commercially available as trade name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) It is commercially available.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl), 2,2-bis (4- ( (Meth) acryloxytetradecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl), and 2,2-bis (4-((meth) acryloxyhexadeca) Propoxy) phenyl) and the like. These may be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. . These can be used alone or in combination of two or more.

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) A Examples thereof include acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.
“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH ₂ —CH _{2). -O -, - CH 2 (CH} 3) means having a block structure of CH 2 -O-).

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl and the like. Examples of the α, β-unsaturated carboxylic acid for obtaining the above compound include (meth) acrylic acid.

Examples of urethane monomers include (meth) acrylic monomers having an OH group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Examples include addition reaction products with diisocyanate compounds, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO or PO-modified urethane di (meth) acrylate.
Furthermore, examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester. Can be mentioned. These (b) components can be used individually by 1 type or in combination of 2 or more types.

  The component (b) preferably contains FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.) from the viewpoint of further improving sensitivity and resolution.

  The content of the component (b) is preferably 7 to 45% by mass based on the total amount of non-volatile organic compounds in the photosensitive resin composition from the viewpoint of resolution and flame retardancy, and 10 to 30% by mass. % Is more preferable. There exists a tendency for resolution to become more favorable by making content of (b) component 7 mass% or more, and there exists a tendency for a flame retardance to become more favorable by setting it as 45 mass% or less.

[(C) component: polymerization initiator]
Specific examples of the polymerization initiator (c) include, for example, benzophenone, 4,4′-bis (dimethylamino) benzophenone (Michler ketone), 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4 '-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1,2-ethylanthraquinone, phenanthrenequinone and other aromatic ketones, alkylanthraquinone and other quinones, benzoin methyl ether, benzoin Benzoin ethers such as ethyl ether and benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyldimethyl ketal, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane And acridine derivatives such as N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds. These can be used individually by 1 type or in combination of 2 or more types.

  For example, when the photosensitive resin composition is cured by exposure to actinic rays having a wavelength region near 405 nm, 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1 and 1,7-bis When (9,9′-acridinyl) heptane is used in combination, sensitivity is improved and curing can be performed with a smaller amount of exposure, and 9-phenylacridine is preferably 1,7-bis (9,9′-). It is likewise preferred to use it instead of (acridinyl) heptane.

The content of the component (c) is preferably 0.1 to 10% by mass based on the total amount of organic compound nonvolatile components of the photosensitive resin composition from the viewpoint of photosensitivity, and is 0.2 to 5% by mass. More preferably.
[(D1) component: organophosphorus compound]
The organophosphorus compound as component (d1) preferably contains a phosphinic acid salt represented by the following general formula (1) from the viewpoint of further improving the flame retardancy of the cured film.

ここで、一般式（１）中、Ａ及びＢは各々独立に、直鎖状又は分枝状の炭素数１〜６のアルキル基又はアリール基を示し、中でも直鎖状又は分枝状の炭素数１〜６のアルキル基であることが好ましく、直鎖状又は分枝状の炭素数１〜４のアルキル基であることがより好ましく、直鎖状又は分枝状の炭素数１〜３のアルキル基であることが特に好ましい。ＭはＭｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ及びＫからなる群より選択される少なくとも一種の金属を示し、中でもＡｌであることが好ましい。ｍは１〜４の整数を示す。

Here, in General Formula (1), A and B each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and among them, linear or branched carbon It is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched alkyl group having 1 to 3 carbon atoms. Particularly preferred is an alkyl group. M represents 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; Al is preferred. m shows the integer of 1-4.

  Here, specific examples of A and B in the general formula (1) include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, Examples thereof include a phenyl group, and among them, a methyl group or an ethyl group is preferable.

  In addition, 80% by mass or more of the phosphinic acid salt represented by the general formula (1) has a particle diameter of from the viewpoint of coating film appearance and thermal shock resistance when used for the photosensitive resin composition and photosensitive film. Is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less. By reducing the particle size, the resolution of the photosensitive resin composition is improved, and the appearance and impact resistance of the coating film tend to be improved. This effect tends to be remarkable particularly in a thin-film photosensitive resin composition.

  Said phosphinic acid salt can be used individually by 1 type or in combination of 2 or more types. Moreover, the said phosphinic acid salt can also be purchased as a commercial item, for example, EXOLIT OP 930, EXOLIT OP 935, EXOLIT OP 940 (all are the brand names made by Clariant) can also be used. In particular, from the viewpoint of thermal shock resistance, it is preferable to use a product obtained by pulverizing the commercially available phosphinate using a bead mill or the like.

  When the photosensitive resin composition contains the phosphinate as the component (d1), a cured film obtained by curing the photosensitive resin composition can obtain more sufficient flame retardancy. In addition, the phosphinate represented by the general formula (1) has a structure that is difficult to hydrolyze, and can effectively prevent the generation of ionic impurities that reduce electrical insulation, so that the cured film is excellent. It can have insulation reliability.

  Further, the organophosphorus compound as the component (d1) may contain a phosphate ester. Specific examples of the phosphate ester include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, phenol of 1,3-dihydroxybenzene / trichlorophosphine polycondensate Examples include condensates and phenol condensates of 2,2-bis (p-hydroxyphenyl) propane / trichlorophosphine oxide polycondensate. These are commercially available, for example, TPP, TCP, TXP, CDP, XDP, CR-733S, CR-741, CR-747 (all are trade names manufactured by Daihachi Chemical Co., Ltd.), PFR, FP -600 and FP-700 (both manufactured by Adeka, trade names) and the like.

  As the component (d1), one of the phosphinic acid salt represented by the general formula (1) and the phosphoric acid ester may be used alone, but at least the phosphine represented by the general formula (1). It is preferable to use an acid salt. In addition, as the component (d1), known organic phosphorus compounds other than these can also be used.

  In order for the photosensitive resin composition to obtain good flame retardancy, the phosphorus content in the photosensitive resin composition is 1.5 to 8.0 mass based on the total amount of non-volatile organic compounds in the photosensitive resin composition. %, And more preferably 2.0 to 4.5% by mass. If the phosphorus content is 1.5% by mass or more, the flame retardancy of the cured film tends to be good, and if it is 8.0% by mass or less, the folding resistance of the cured film, insulation reliability, thermal shock resistance, etc. Tends to be good.

  Further, the component (d1) is preferably contained so that the phosphorus content falls within the above range.

  Moreover, when using the phosphinic acid salt represented by the said General formula (1) as a (d1) component, the content is 5-25 mass% on the basis of the organic compound non volatile matter whole quantity of the photosensitive resin composition. It is preferable. There exists a tendency for the flame retardance of a cured film to become more favorable by making content of (d1) component 5 mass% or more, and the thermal shock tolerance of a cured film becomes more favorable by setting it as 30 mass% or less. Tend.

  Moreover, when using phosphate ester in combination with a phosphinate as (d1) component, content of the phosphate ester is 1-20 mass% on the basis of the organic compound non volatile matter whole quantity of the photosensitive resin composition. It is preferable. When this content exceeds 20% by mass, the electrolytic corrosion property and the bleed-out property (peeling of the photosensitive resin composition) tend to be deteriorated.

[(D2) component: inorganic filler]
Examples of the inorganic filler (d2) include barium sulfate, barium titanate, powdered silicon oxide, amorphous silica, talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Among them, barium sulfate is preferable.

  These are also commercially available, for example, Variace B-30 (trade name, manufactured by Sakai Chemical Industry Co., Ltd.) for barium sulfate, and Hydrite H-42M (trade name, manufactured by Showa Denko KK) for aluminum hydroxide. In silica, there is SFP-30M (product name, manufactured by Denki Kagaku Kogyo Co., Ltd.). These inorganic fillers may be kneaded directly in the resin, or may be dispersed in a solvent or the like and added to the resin.

  80% by mass or more of the inorganic filler is preferably 10 μm or less, more preferably 1 μm or less, from the viewpoint of reliability when used in the photosensitive resin composition and the photosensitive film. More preferably, it is 0.2 μm or less. Refinement of the particle diameter tends to improve resolution, appearance with a thinner coating, and thermal shock resistance.

  In the present invention, the content of the inorganic filler (d2) is preferably 5 to 70% by mass, and preferably 10 to 40% by mass based on the total amount of non-volatile organic compounds in the photosensitive resin composition. Is more preferable. By including 5-70 mass% inorganic filler, a flame retardance can be improved, keeping the thermal shock resistance of a cured film. From the viewpoint of plating resistance, it is preferable to use a dispersion of Variace B-30 using a bead mill or the like as the component (d2).

[(E) component: thermosetting agent]
Specific examples of the thermosetting agent as the component (e) include thermosetting compounds such as epoxy resins, phenol resins, urea resins, and melamine resins. Examples of epoxy resins include bisphenol A type tertiary fatty acid-modified polyol epoxy resins, diglycidyl esters such as diglycidyl phthalate and diglycidyl tetrahydrophthalate, and diglycidyl amines such as diglycidyl aniline and diglycidyl toluidine. Etc. You may use these individually by 1 type or in combination of 2 or more types.

  Moreover, the block isocyanate compound which is a latent thermosetting agent can also be used as a thermosetting agent which is (e) component. Examples of the blocked isocyanate compound include polyisocyanate compounds blocked with a blocking agent such as an alcohol compound, a phenol compound, ε-caprolactam, an oxime compound, and an active methylene compound. Examples of blocked polyisocyanate compounds include 4,4-diphenylmethane disissocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene 1,5-diisocyanate, o-xylene diisocyanate, m-xylene. Aromatic polyisocyanates such as diisocyanates and 2,4-tolylene dimers, aliphatic polyisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate, and alicyclic polyisocyanates such as bicycloheptane triisocyanate An aromatic polyisocyanate is preferable from the viewpoint of heat resistance, and an aliphatic polyisocyanate or an alicyclic polyisocyanate is preferable from the viewpoint of preventing coloring.

  From the viewpoints of storage stability and HAST resistance, it is most preferable to use Sumidur BL-3175 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.) as the component (e).

  When the photosensitive resin composition contains the component (e), the content is 5 to 40% by mass based on the total amount of non-volatile organic compounds in the photosensitive resin composition from the viewpoint of flame retardancy and insulation reliability. It is preferable that it is 10-20 mass%. (E) By making content of a component into 5 mass% or more, there exists a tendency for the insulation reliability of the photosensitive resin composition to become more favorable, and flame retardance is more favorable by setting it as 40 mass% or less. Tend to be.

  In addition, the photosensitive resin composition of the present invention includes a dye such as malachite green, a photochromic agent such as leuco crystal violet, a plasticizer such as a thermochromic inhibitor or p-toluenesulfonamide, phthalocyanine blue, if necessary. Such as organic pigments such as phthalocyanine and azo, or inorganic pigments such as titanium dioxide, fillers made of inorganic pigments such as silica, alumina, talc, calcium carbonate or barium sulfate, and the above-mentioned fillers and organic pigments, inorganic Wetting and dispersing agents such as pigments, antifoaming agents, stabilizers, adhesion-imparting agents, leveling agents, antioxidants, perfumes or imaging agents can be included. These components are each preferably contained in an amount of about 0.01 to 70% by mass based on the total amount of nonvolatile organic compounds in the photosensitive resin composition. Moreover, said component can be used individually by 1 type or in combination of 2 or more types.

  Furthermore, the photosensitive resin composition of the present invention may contain a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or the like, if necessary. It can melt | dissolve in a mixed solvent and can apply | coat as a solution of about 30-70 mass% of non volatile matters.

  The photosensitive resin composition of the present invention as described above is applied as a liquid resist on a metal surface such as copper, a copper-based alloy, iron, and an iron-based alloy, and then dried, and a protective film is provided as necessary. It can be used by coating or in the form of a photosensitive film described later.

(Photosensitive film)
Next, a photosensitive film (photosensitive element) using the above-described photosensitive resin composition of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive film of the present invention. The photosensitive film 1 shown in FIG. 1 includes a support 10 and a photosensitive resin composition layer 20 provided on the support 10. The photosensitive resin composition layer 20 is a layer made of the above-described photosensitive resin composition of the present invention. Moreover, the photosensitive film 1 of this invention may coat | cover the surface on the opposite side to the support body 10 on the photosensitive resin composition layer 20 with the protective film 30. FIG.

  The photosensitive resin composition layer 20 is prepared by dissolving the photosensitive resin composition of the present invention in the above solvent or mixed solvent to obtain a solution having a nonvolatile content of about 30 to 70% by mass, and then applying the solution onto the support 10. Is preferably formed.

  Although the thickness of the photosensitive resin composition layer 20 varies depending on the use, it is preferably 10 to 100 μm and more preferably 20 to 60 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. preferable. When the thickness of the photosensitive resin composition layer 20 is 10 μm or more, industrial coating tends to be easier, and when the thickness is 100 μm or less, the above-described effect produced by the present invention is increased. There tends to be better flexibility and resolution.

  Examples of the support 10 provided in the photosensitive film 1 include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

  The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. When the thickness is 5 μm or more, the support tends to be hardly broken when the support is peeled off before development, and when the thickness is 100 μm or less, the resolution and flexibility tend to be better. is there.

  The photosensitive film 1 consisting of two layers of the support 10 and the photosensitive resin composition layer 20 as described above or the photosensitive film consisting of three layers of the support 10, the photosensitive resin composition layer 20 and the protective film 30. For example, they may be stored as they are, or may be wound around a roll core in the form of a roll with the protective film 30 interposed therebetween and stored.

  The method for forming a resist pattern using the photosensitive film according to the present invention includes a removing step of removing the protective film from the photosensitive film as necessary, a photosensitive resin composition layer, and a support. A lamination step of laminating on the circuit forming substrate in this order, and an actinic ray is irradiated to a predetermined portion of the photosensitive resin composition layer through a support, if necessary, to form a photocured portion on the photosensitive resin composition layer. And an exposure step for removing the photosensitive resin composition layer other than the photocured portion. The circuit-forming substrate is an insulating layer and a conductor layer (copper, copper-based alloy, iron-based alloy such as nickel, chromium, iron, stainless steel, preferably copper, copper-based alloy) formed on the insulating layer. , Made of an iron-based alloy).

  Examples of the laminating method in the laminating step after the removing step of removing the protective film as necessary include a method of laminating by pressing the photosensitive resin composition layer on the circuit forming substrate while heating. The atmosphere during the lamination is not particularly limited, but the lamination is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually the surface of the conductor layer of the circuit forming substrate, but may be a surface other than the conductor layer.

  The heating temperature of the photosensitive resin composition layer is preferably 50 to 130 ° C., the pressure bonding pressure is preferably about 0.1 to 1.0 MPa, and the ambient pressure is more preferably 4000 Pa or less. These conditions are not particularly limited. In addition, if the photosensitive resin composition layer is heated to 50 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance, but in order to further improve the laminating property, Pre-heat treatment of the substrate can also be performed.

  After the lamination is completed in this manner, a photocured portion is formed by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays in the exposure step. Examples of the method for forming the photocured portion include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork. Further, exposure by a direct drawing method having no mask pattern such as an LDI method or a DLP (Digital Light Processing) exposure method is also possible. At this time, when the support present on the photosensitive resin composition layer is transparent, it can be irradiated with actinic rays as it is, but when opaque, the photosensitive resin composition is removed after removing the support. Irradiate the layer with actinic rays.

  As the active light source, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a YAG laser, a semiconductor laser, or the like that emits ultraviolet rays effectively is used. it can. Moreover, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can also be used.

  Next, after exposure, when a support is present on the photosensitive resin composition layer, after removing the support, in the development process, a photosensitive resin other than the photocured portion by wet development, dry development, or the like. The composition layer is removed and developed to form a resist pattern.

  In the case of wet development, development is performed using a developer such as an alkaline aqueous solution by a known method such as spraying, rocking immersion, brushing, or scraping. As the developer, a developer that is safe and stable and has good operability is used. For example, a dilute solution (1 to 5% by mass aqueous solution) of sodium carbonate at 20 to 50 ° C. is used.

  For example, when the resist pattern obtained by the above-described forming method is used as a solder resist for a printed wiring board, a high pressure is used for the purpose of improving solder heat resistance, chemical resistance, etc. as the solder resist after completion of the development process. It is preferable to perform ultraviolet irradiation with a mercury lamp or heating with an oven.

In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, the irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . Moreover, when heating, it is preferable to carry out for about 15 to 90 minutes in the range of about 100-170 degreeC. Furthermore, both ultraviolet irradiation and heating may be performed, and after one of them is performed, the other can be performed.

  The resist pattern obtained by the above-described forming method is preferably used as a photosensitive permanent resist (permanent mask) formed on a printed wiring board. Since the cured film formed from the photosensitive resin composition of the present invention has excellent flame retardancy and plating resistance, it also serves as a protective film for wiring after soldering to the substrate. It is effective as a permanent resist.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

(Examples 1-8, Comparative Examples 1-4)
[Preparation of photosensitive film]
First, the components (1) to (12) shown in Table 1 are mixed with the non-volatile content (parts by weight) shown in the table so that the non-volatile content is 50% by mass with methyl ethyl ketone as a diluent. Thus, a solution of the photosensitive resin composition was obtained.
In the table, the resin (1) in the component (1) is an acrylic resin, and is a copolymer of methacrylic acid, methyl methacrylate and butyl acrylate (methacrylic acid: methyl methacrylate: butyl acrylate = 17 wt. %: 62% by weight: 21% by weight) and a weight average molecular weight of 100,000 and an acid value of 110 mgKOH / g, which corresponds to the component (a2) of the above-mentioned embodiment.

  UXE-3024 in component (2) is a polyurethane compound (manufactured by Nippon Kayaku Co., Ltd., sample name UXE-3024, weight average molecular weight: 10,000), and CCR-1171H in component (3) is a carboxyl group-containing cresol. It is a novolak-type epoxy acrylate compound (manufactured by Nippon Kayaku Co., Ltd., sample name CCR-1171H, weight average molecular weight: 7000), and all correspond to the component (a1) of the above-described embodiment.

  FA-321M in component (4) is bisphenol A polyoxyethylene dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name FA-321M), and corresponds to component (b) in the above-described embodiment.

  N-1717 in component (5) is 1,7-bis (9-acridinyl) heptane (trade name N-1717, manufactured by Asahi Denka Kogyo Co., Ltd.), and I-369 in component (6) is 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name “I-369”, manufactured by Ciba Specialty Chemicals Co., Ltd.), both of which are the component (c) of the above-described embodiment It corresponds to.

  OP-935 in the component (7) is a phosphinate (trade name EXOLIT OP935, phosphorus content = 23% by mass, manufactured by Clariant), and corresponds to the component (d1) of the above-described embodiment.

  B-30 in component (8) is barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name Variace B-30), and H-42M in component (9) is aluminum hydroxide (manufactured by Showa Denko KK) SFP-30M in the component (10) is spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name SFP-30M), both of which are (d2) of the above-described embodiment. Corresponds to the ingredients.

  BL-3175 in the component (11) is block type isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name Sumijour BL-3175) and corresponds to the component (e) in the above-described embodiment.

  Component (12) is a yellow pigment (Pigment Yellow).

  In Examples and Comparative Examples using both component (4) and component (7), the slurry obtained by bead milling after mixing component (4) and component (7) is used. did. The particle size of OP-935 in the slurry was 80% by mass or more and 1 μm or less. The particle size distribution was measured using a particle size distribution meter (LS-230) manufactured by COULTER.

  Next, these photosensitive resin composition solutions were uniformly applied onto a 16 μm polyethylene terephthalate film (product name: G2-16, manufactured by Teijin Limited) as a support, and a hot air convection dryer was used. The photosensitive resin composition layer was formed on the support by using and drying at 100 ° C. for 10 minutes. The film thickness after drying of the photosensitive resin composition layer was 30 μm.

  Subsequently, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: NF-15), which is a protective film, is bonded to the surface of the photosensitive resin composition layer on the side opposite to the side in contact with the support layer. A film was obtained.

[Characteristic evaluation]
Using the photosensitive films prepared in Examples 1 to 8 and Comparative Examples 1 to 4, the following tests were performed, respectively, and sensitivity, plating resistance, solder heat resistance, thermal shock resistance, HAST resistance, resolution, and Flame retardancy was evaluated. The results are summarized in Table 2.

(sensitivity)
First, an evaluation substrate was prepared as follows using each photosensitive film. That is, first, the copper surface of a printed wiring board substrate (E-679, manufactured by Hitachi Chemical Co., Ltd., trade name) in which a 12 μm thick copper foil is laminated on a glass epoxy substrate is polished with an abrasive brush and washed with water. And then dried. Using a continuous press type vacuum laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho) on this printed wiring board substrate, the press hot plate temperature is 70 ° C., the evacuation time is 20 seconds, the lamination press time is 30 seconds, and the atmospheric pressure is 4 kPa. Hereinafter, the polyethylene film of the photosensitive film was peeled and laminated under the condition of a pressure bonding pressure of 0.4 MPa to obtain a laminate for evaluation.

The laminate for evaluation after laminating was allowed to stand at room temperature (25 ° C.) for 1 hour, and then a direct-drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., product name “DE-” 1AH "), and using the drawing data having a grid pattern from above the evaluation laminate, the stowage 21-step tablet is exposed with an energy amount of 14 after development. went. The amount of energy (mJ / cm ² ) irradiated to each evaluation laminate is shown in Table 2 as sensitivity. In addition, a sensitivity is so high that the numerical value of energy amount (mJ / cm < ² >) is low.

(Plating resistance)
After the exposure, the polyethylene terephthalate film on the evaluation laminate is peeled off and sprayed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 1.5 times the minimum development time (minimum time during which the unexposed area is developed). Development was performed. Thereby, the pattern formed by hardening the photosensitive resin composition layer was formed.

Subsequently, ultraviolet irradiation is performed with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., and further heat treatment is performed at 160 ° C. for 60 minutes on the printed wiring board substrate. An evaluation substrate on which a solder resist was formed was obtained.

  The substrate for evaluation is subjected to electroless nickel plating (trade name Nimden NPR-4, manufactured by Uemura Kogyo Co., Ltd.) (treatment for 15 minutes), and further electroless gold plating (trade name, Goblite, manufactured by Uemura Kogyo Co., Ltd.). TAM-54) was applied (10 minutes treatment).

  For the evaluation substrate thus plated, the plating solution soaks into the bottom of the solder resist, and the solder resist floats and peels from the substrate is observed with a 100-fold metal microscope. evaluated. That is, the case where no penetration into the bottom of the solder resist was observed and the solder resist was not lifted or peeled off was indicated as “◯”, and the case where any of them was recognized as “X”. In addition, “△” indicates that a slight penetration into the bottom of the solder resist was observed but there was no practical problem.

(Solder heat resistance)
Using the evaluation substrate having a solder resist obtained in the same manner as in the “plating resistance” test, the solder heat resistance was evaluated as follows. That is, after applying a rosin flux (trade name MH-820V, manufactured by Tamura Kaken Co., Ltd.) to the substrate for evaluation, a soldering treatment was performed in which the substrate was immersed in a solder bath at 288 ° C. for 30 seconds.
The state of occurrence of cracks in the solder resist on the evaluation substrate subjected to solder plating in this way, and the degree to which the solder resist floated from the substrate and peeling were observed with a 100-fold metal microscope. The results were evaluated according to the following criteria. In other words, “O” indicates that no cracking of the solder resist was observed and no solder resist was lifted or peeled off, and “X” indicates that any of them was recognized.

(Heat shock resistance)
For the evaluation substrate having a solder resist obtained in the same manner as in the above “plating resistance” test, after being exposed to the atmosphere of −55 ° C. for 15 minutes, the temperature was increased at a temperature increase rate of 180 ° C./min. Next, after being exposed to the atmosphere at 125 ° C. for 15 minutes, a test was performed in which a thermal cycle in which the temperature was lowered at a rate of 180 ° C./min was repeated 200 times.

  After the test, cracks and peeling of the solder resist (permanent resist film) on the evaluation substrate were observed with a 100-fold metal microscope and evaluated according to the following criteria. That is, those that could not observe cracks and peeling of the solder resist were marked with “◯”, and those that could confirm any of them were marked with “x”.

(HAST resistance)
First, a copper surface of a printed wiring board substrate (trade name E-679, manufactured by Hitachi Chemical Co., Ltd.) in which a 12 μm thick copper foil is laminated on a glass epoxy base material is etched to have a line / space of 50 μm / 50 μm. It was processed into a comb-type electrode. This was used as an evaluation wiring board.

  A solder resist made of a cured product of a resist was formed on the comb-shaped electrode of this evaluation wiring board in the same manner as in the “plating resistance” test, and this was used as an evaluation substrate. This evaluation substrate was exposed to a super accelerated high temperature high humidity life test (HAST) bath for 100 hours under the conditions of 130 ° C./85%/5V. After the test, the degree of migration in each evaluation substrate was observed with a 100-fold metal microscope and evaluated according to the following criteria. That is, the solder resist (permanent resist film) where migration did not occur was marked with “◯” and the migration where migration occurred was marked with “x”. Migration is a phenomenon in which discoloration of the solder resist around the electrode and a decrease in insulation resistance occur when copper is eluted and deposited from the copper electrode to the solder resist.

(Resolution)
The evaluation laminate obtained in the same manner as in the above “Plating Resistance” test was allowed to stand at room temperature for 1 hour, and then a direct drawing exposure machine using a 405 nm blue-violet laser diode as a light source (Hitachi Via Mechanics Co., Ltd.) Using product data “DE-1AH”), drawing data having a wiring pattern having a line width / space width of 6/6 to 47/47 (unit: μm) is used from above the evaluation laminate. Then, exposure was carried out with an energy amount at which the number of remaining step steps after development of the stove 21-step step tablet was 14.

  The polyethylene terephthalate on the evaluation laminate after exposure is peeled off and spray-developed with a 1% by weight aqueous sodium carbonate solution at 30 ° C. for 1.7 times the minimum development time (minimum time for removing unexposed areas). Then, the unexposed part was removed and the resolution was evaluated. The value of the resolution is represented by the smallest value among the space widths (μm) in which the unexposed portions can be completely removed by the development processing, and the smaller the numerical value, the higher the resolution.

(Flame retardance)
The copper foil of the halogen-free copper foil-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name MCL-BE67G) was removed by etching to obtain a glass epoxy substrate having a thickness of 0.15 mm. Next, using a continuous press type vacuum laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho) on both sides of the glass epoxy base material, press hot plate temperature 70 ° C., evacuation time 20 seconds, laminating press time 30 seconds, atmospheric pressure The polyethylene film of the photosensitive film was peeled off and laminated under conditions of 4 kPa or less and a pressure bonding pressure of 0.4 MPa.

  The laminate for evaluation after laminating was allowed to stand at room temperature (25 ° C.) for 1 hour, and then a direct-drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., product name “DE-” 1AH "), and using the drawing data having a grid pattern from above the evaluation laminate, the stowage 21-step tablet is exposed with an energy amount of 14 after development. went.

After the exposure, the polyethylene terephthalate film on the evaluation laminate is peeled off, and irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., and further heated at 160 ° C. for 60 minutes. By performing the treatment, an evaluation substrate in which a solder resist was formed on the printed wiring board substrate was obtained.

  Using this substrate, a flame retardancy test was performed in accordance with the vertical method defined in the UL94V method. The results are shown in Table 2 based on the criteria of UL94V method. However, NG means that the flame retardancy was less than 94V-2 according to the criteria of UL94.

  As shown in Table 2, when the photosensitive resin composition of the present invention containing all of the components (a), (b), (c), (d1) and (d2) was used (Examples 1 to 8) In addition to excellent flame retardancy and plating resistance, it was confirmed that sufficient solder heat resistance, thermal shock resistance, HAST resistance, and resolution can be obtained. On the other hand, in Comparative Examples 1-4, flame retardancy and / or plating resistance were insufficient.

It is a figure which shows typically the cross-sectional structure of the photosensitive film of suitable embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive film, 10 ... Support body, 20 ... Photosensitive resin composition layer, 30 ... Protective film.

Claims (8)

  A photosensitive resin composition comprising (a) a binder polymer, (b) a polymerizable compound having an ethylenically unsaturated group, (c) a polymerization initiator, (d1) an organic phosphorus compound, and (d2) an inorganic filler. The photosensitive resin composition of Claim 1 in which the said (d1) organophosphorus compound contains the phosphinic acid salt represented by following General formula (1).

[In Formula (1), A and B each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group, and M represents Mg, Ca, Al, Sb, Sn, Ge. , Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K represent at least one metal selected from the group consisting of 1 to 4; ]   The photosensitive resin compound according to claim 1 or 2, wherein the (a) binder polymer includes (a1) a polymerizable prepolymer having a carboxyl group and an ethylenically unsaturated group.   (A1) The polymerizable prepolymer having a carboxyl group and an ethylenically unsaturated group is an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group. The photosensitive resin composition of Claim 3 which is a compound obtained by making it react.   The said (a) binder polymer contains the vinyl-type copolymer compound obtained by using (a2) (meth) acrylic acid and a (meth) acrylic-acid alkylester as a copolymerization component in any one of Claims 1-4. The photosensitive resin composition as described.   (E) The photosensitive resin composition as described in any one of Claims 1-5 which further contains a thermosetting agent.   A photosensitive film provided with a support body and the layer which consists of a photosensitive resin composition as described in any one of Claims 1-6 formed on this support body.   The photosensitive permanent resist which consists of a photocured material of the photosensitive resin composition as described in any one of Claims 1-6 apply | coated on the board | substrate for printed wiring boards.

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