JP6143090B2 - Photosensitive resin composition, photosensitive film using the same, permanent resist, and method for producing permanent resist - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive film using the same, a permanent resist, and a method for producing a permanent resist. In particular, the present invention relates to a photosensitive resin composition suitable as a solder resist used for printed wiring boards and semiconductor package substrates.

  Along with the improvement in performance of various electronic devices, the density of printed wiring boards and semiconductor package substrates has progressed, and higher resolution is required for the photosensitive solder resist used for the outermost layer. In particular, solder resists used in high-performance semiconductor packages used in the latest mobile devices such as smartphones, tablet devices, and notebook PCs are required to have finer round hole resolution with the flip-chip connection terminals. Yes. The opening diameter is decreasing year by year as the bump pitch is narrowed. In addition, there is an increasing demand for the positional accuracy of the aperture diameter, and the conventional contact exposure method cannot obtain a sufficient positional accuracy, and in recent years, the exposure method by direct imaging exposure is becoming widespread.

  Patent Documents 1 to 5 disclose examples of photosensitive resin compositions corresponding to direct imaging, and report that a sufficient opening shape can be obtained.

JP 2007-102184 A JP 2007-164126 A Japanese Patent No. 5117623 Japanese Patent No. 4827088 JP 2011-75678 A

  However, in the case of direct imaging exposure, unlike conventional contact exposure, there is a problem that throughput is lowered because exposure is performed while scanning. Recently, attempts have been made to improve throughput by increasing the output and illuminance of the exposure machine. However, in this case, the degree of cure of the solder resist is greatly affected by the base of the solder resist, and a problem has arisen that a sufficient opening shape cannot be obtained particularly at the resist opening other than the wiring.

  The present invention is excellent in resolution in direct imaging exposure without being affected by the background, and has excellent low coefficient of thermal expansion (CTE), high Tg (glass transition temperature), adhesion and crack resistance, and fine pitch. It aims at providing the photosensitive resin composition which is excellent in insulation tolerance, and which can be developed with alkali, the photosensitive film using the same, a permanent resist, and the manufacturing method of a permanent resist.

As a result of earnest research, the present inventors have
(A) Photosensitivity containing a resin having an ethylenically unsaturated group and a carboxyl group, (b) a photopolymerization initiator, (c) a thermosetting agent, (d) an inorganic filler, and (e) an organic filler having an amino group. A resin composition, wherein (d) the inorganic filler and (e) the organic filler having one or more amino groups have an average particle size of 0.05 μm or more and 1.0 μm or less, and a maximum particle size of 5 μm or less, and When the photosensitive resin composition is coated, dried, and having a thickness of 25 μm, the absorbance at a wavelength of 365 nm is 2.0 or more, the absorbance at 405 nm is 1.5 or more, and the minimum absorbance at 300 to 800 nm is It has been found that excellent resolution in direct imaging exposure can be obtained with a photosensitive resin composition of 0.2 or more.

  Furthermore, in the photosensitive resin composition of the present invention, (d) when one of the inorganic fillers is spherical fused silica, and the spherical fused silica is contained in the photosensitive resin composition in an amount of 20% by mass to 80% by mass, It has been found that characteristics such as high resolution and low CTE are satisfied.

  In the photosensitive resin composition of the present invention, the reflectance of the coated film surface after drying at 10 ° incidence is more preferably 10% or more with respect to wavelengths of 365 nm and 405 nm, and a tricyclodecane structure or a maleimide structure. It is further desirable to include a compound having a high Tg and improved HAST (super accelerated life test) property.

  Furthermore, it is preferable that the photosensitive resin composition of the present invention can be patterned by direct imaging exposure.

  Moreover, this invention relates to the photosensitive film provided with a support body and the photosensitive resin composition layer which consists of said photosensitive resin composition formed on this support body.

  Moreover, this invention relates to the permanent resist which consists of hardened | cured material of said photosensitive resin composition, and is formed on the board | substrate for printed wiring boards.

  The present invention also provides a laminating step of providing a photosensitive layer comprising the above-mentioned photosensitive resin composition on a substrate, an exposure step of pattern irradiating the photosensitive layer with actinic rays, and development for developing the photosensitive layer after the exposure step. And a process for producing a permanent resist.

  According to the present invention, in direct imaging exposure, it is excellent in resolution of fine round holes by alkali development, is excellent in low thermal expansion coefficient, adhesion crack resistance, and excellent insulation resistance even when coating fine pitch wiring. The alkali-developable photosensitive resin composition, the photosensitive film using this, the permanent resist, and the manufacturing method of a permanent resist can be provided.

It is a schematic cross section of a semiconductor package substrate. It is a schematic cross section of a flip chip type package substrate.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  First, the photosensitive resin composition which concerns on suitable embodiment is demonstrated. In this embodiment, (meth) acrylic acid means acrylic acid and methacrylic acid, and (meth) acrylate means acrylate and the corresponding methacrylate.

  First, component (a) used in the present embodiment: a resin having an ethylenically unsaturated group and a carboxyl group will be described. The component (a) of the present invention may be any resin as long as it has an ethylenically unsaturated group and a carboxyl group. For example, an ester of an epoxy resin (a1) and an unsaturated monocarboxylic acid (a2) A reaction product obtained by adding a saturated or unsaturated polybasic acid anhydride (a3) to a compound can be used.

  These can be obtained by the following two-step reaction. In the first reaction (hereinafter referred to as “first reaction” for convenience), the epoxy resin (a1) and the unsaturated monocarboxylic acid (a2) react. In the next reaction (hereinafter referred to as “second reaction” for convenience), the esterified product produced in the first reaction reacts with the saturated or unsaturated polybasic acid anhydride (a3). Although there is no restriction | limiting in particular as said epoxy resin (a1), For example, a bisphenol-type epoxy resin, a novolak-type epoxy resin, a biphenyl-type epoxy resin, a polyfunctional epoxy resin etc. are mentioned. As the bisphenol type epoxy resin, those obtained by reacting bisphenol A type, bisphenol F type, bisphenol S type and epichlorohydrin are suitable. GSF-260, GY-255, XB-2615 (trade name) manufactured by BASF Bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, amino group-containing, alicyclic or polybutadiene modified, such as Mitsubishi Chemical Corporation jER828, 1007, 807 (trade name ("jER" is a registered trademark)) An epoxy resin such as is preferably used.

  As the novolac type epoxy resin, those obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenols and alkylphenols with formaldehyde in the presence of an acidic catalyst and epichlorohydrin are suitable. Nippon Steel & Sumikin Chemical Co., Ltd. YDCN-701, 704, YDPN-638,602 (trade name) manufactured by company, DEN-431, 439 (trade name) manufactured by Dow Chemical Company, EPN-1299 (trade name) manufactured by BASF Corporation, N- manufactured by DIC Corporation 730, 770, 865, 665, 673, VH-4150, 4240 (trade name), Nippon Kayaku Co., Ltd. EOCN-120, BREN, etc. (trade name (“EOCN” is a registered trademark)).

  Examples of other epoxy resins include salicylaldehyde-phenol or cresol type epoxy resins (EPPN502H, FAE2500, etc. (trade name ("EPPN" is a registered trademark)) manufactured by Nippon Kayaku Co., Ltd.), Dow Chemical DER-330,337,361 (trade name) manufactured by Daicel Corporation, Celoxide 2021 (trade name ("Celoxide" is a registered trademark)) manufactured by Daicel Corporation, TETRAD-X, C (trade name, "TETRAD" manufactured by Mitsubishi Gas Chemical Co., Ltd.) "Can be used as a registered trademark), EPB-13,27 (trade name) manufactured by Nippon Soda Co., Ltd., and the like. These may be used alone or in combination of two or more, and a mixture or a block copolymer may be used.

  Examples of the unsaturated monocarboxylic acid (a2) include (meth) acrylic acid, crotonic acid, cinnamic acid, and saturated or unsaturated polybasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule. Or the reaction material of the half-ester compound of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound is mentioned. Examples of the reactant include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and tris (hydroxyethyl) isocyanurate. Examples thereof include reactants obtained by reacting di (meth) acrylate, glycidyl (meth) acrylate and the like in an equimolar ratio by a conventional method. These unsaturated monocarboxylic acids can be used alone or in combination. Among these, acrylic acid is preferable.

  Examples of the saturated or unsaturated polybasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa Examples include hydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and trimellitic anhydride.

  In the first reaction, a hydroxyl group is generated by an addition reaction between the epoxy group of the epoxy resin (a1) and the carboxyl group of the unsaturated monocarboxylic acid (a2). In the first reaction, the ratio of the epoxy compound (a1) to the unsaturated monocarboxylic acid (a2) is such that the unsaturated monocarboxylic acid (a2) is 0.001 equivalent to 1 equivalent of the epoxy group of the epoxy resin (a1). The ratio is preferably 7 to 1.05 equivalent, and more preferably 0.8 to 1.0 equivalent.

  In the second reaction, the hydroxyl group formed in the first reaction and the hydroxyl group originally present in the epoxy resin (a1) undergo a half-ester reaction with the acid anhydride group of the saturated or unsaturated polybasic acid anhydride (a3). Inferred. Here, 0.1 to 1.0 equivalent of polybasic acid anhydride (a3) can be reacted with 1 equivalent of hydroxyl group in the resin obtained by the first reaction. By adjusting the amount of the polybasic acid anhydride (a3) within this range, the acid value of the component (a) can be adjusted.

  Examples of the resin having an ethylenically unsaturated group and a carboxyl group include CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, ZFR-1185, and ZCR- 1569H (above, Nippon Kayaku Co., Ltd., trade name), UE-EXP-2810PM, UE-EXP-2827 (above, DIC Corporation, trade name) and the like are commercially available.

  As the component (a) of this embodiment, 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 is used. It may be used. Such a polyurethane compound is commercially available as, for example, UXE-3011, UXE-3012, UXE-3024 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like.

  (A) component used by this embodiment is used individually or in combination of 2 or more types. The refractive index of the resin varies depending on the structure of the resin to be used. When the resin having the structure described above is used, the refractive index is 1.4 to 1.7, and most of the refractive index is the refractive index of the bisphenol A type epoxy resin. The effect of the present invention is most exerted when a value of 1.57 to 1.6 is used.

  The acid value of the component (a) is preferably 20 to 180 mgKOH / g, more preferably 30 to 150 mgKOH / g, and still more preferably 40 to 120 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 by the following method. First, after precisely weighing about 1 g of the measurement resin solution, 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. 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 phenolphthalein, Wp represents the measurement resin solution mass (g), and I represents the non-volatileity of the measurement resin solution. The ratio (mass%) of minutes is shown.

  Moreover, (a) The weight average molecular weight of the resin having an ethylenically unsaturated group and a carboxyl group is preferably 3000 to 30000, more preferably 5000 to 20000, from the viewpoint of coating properties, and 7000 to 15000 is particularly preferable.

  In addition, a weight average molecular weight (Mw) can be calculated | required from the standard polystyrene conversion value by a gel permeation chromatography (GPC).

  Next, regarding (b) the photopolymerization initiator of this embodiment, for example, benzophenone, N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1,4,4′-bis (dimethylamino) benzophenone (Miherer ketone), 4 , 4′-bis (diethylamino) benzophenone, aromatic ketones such as 4-methoxy-4′-dimethylaminobenzophenone, quinones such as alkylanthraquinone and phenanthrenequinone, benzoin compounds such as benzoin and alkylbenzoin, benzoin alkyl ethers, Benzoin ether compounds such as benzoin phenyl ether , Benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer , 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) ) -5-phenylimidazole dimer, 2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, N-phenylglycine, N-phenylglycine derivatives, acridine derivatives such as 9-phenylacridine, 1,2-octanedione, 1- [4- (phenylthio)- Oxime esters such as 2- (O-benzoyloxime)], coumarin compounds such as 7-diethylamino-4-methylcoumarin, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2 , 4-dichlorothioxanthone, 2,4-diethylthioxanthone, thioxanthone compounds such as 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -Acylphosphine oxide compounds such as phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 9-phenylacridine, 9-aminoa Lysine, 9-pentylaminoacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) butane, 1,5-bis ( 9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9- Acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, bis (9-acridinyl) alkane such as 1,12-bis (9-acridinyl) dodecane, 9 -Phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 9-monopentylaminoacridine, 1,3-bis (9-acridine Compounds having an acridine ring such as (lydinyl) -2-oxapropane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5-bis (9-acridinyl) -3-thiapentane, (2- (acetyl Oxyiminomethyl) thioxanthen-9-one), (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6 A compound having an oxime ester such as-(2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)) can be used in combination.

  As the (b) photopolymerization initiator of the present embodiment, α-cleavage having an alkylphenone structure in the molecule is used from the viewpoint of high sensitivity, high resolution, and a rectangular opening shape regardless of the base material. It is desirable to include a photopolymerization initiator having a type photopolymerization initiator, an oxime ester structure, and an acylphosphine structure. Examples of such a photopolymerization initiator include those having an alkylphenone structure, such as IRGACURE 651, IRGACURE 184, IRGACURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, and IRGACURE 379EG. Moreover, IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF, trade name (“IRGACURE” is a registered trademark)), N-1919 (manufactured by ADEKA Co., Ltd.) IRGACURE 819 and LUCIRIN TPO (both manufactured by BASF, trade name (“LUCIRIN” is a registered trademark)) can also be used. In order to satisfy the requirements for sensitivity and resolution, it is more desirable to use not only one type of photopolymerization initiator but also several types of sensitizers in combination.

  (C) component of this embodiment: As a thermosetting agent, an epoxy resin is mentioned as a typical thing. For example, bisphenol A type epoxy resin such as bisphenol A diglycidyl ether, bisphenol F type epoxy resin such as bisphenol F diglycidyl ether, bisphenol S type epoxy resin such as bisphenol S diglycidyl ether, and biphenol type epoxy such as biphenol diglycidyl ether Resins, bixylenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, and dibasic acid-modified diglycidyl ether type epoxy resins and biphenyl aralkyl type epoxies thereof Examples thereof include resin and tris (2,3-epoxypropyl) isocyanurate. These may be used alone or in combination of two or more.

  Commercially available compounds can be used as these compounds. For example, examples of bisphenol A diglycidyl ether include jER828, jER1001, and jER1002 (all are trade names, manufactured by Mitsubishi Chemical Corporation). Examples of bisphenol F diglycidyl ether include jER807 (trade name, manufactured by Mitsubishi Chemical Corporation), YSLV-80 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and EBPS-200 as bisphenol S diglycidyl ether. (Nippon Kayaku Co., Ltd., trade name) and Epicron EXA-1514 (DIC Corporation, trade name ("Epicron" is a registered trademark)). Examples of biphenol diglycidyl ether include YL6121 (trade name, manufactured by Mitsubishi Chemical Corporation), and examples of bixylenol diglycidyl ether include YX4000H (trade name, manufactured by Mitsubishi Chemical Corporation). .

  Furthermore, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade names), and the like. As the above-mentioned dibasic acid-modified diglycidyl ether type epoxy resin Are ST-5100 and ST-5080 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade names), and biphenyl aralkyl type epoxy resins are NC-3000 and NC-3000H (both manufactured by Nippon Kayaku Co., Ltd., trade names). Tris (2,3-epoxypropyl) isocyanurate includes TEPIC-S, TEPIC-VL, TEPIC-PASB26 (manufactured by Nissan Chemical Industries, Ltd., trade name ("TEPIC" is a registered trademark)), Araldite PT810 ( Huntsman Advanced Materials, product name (“A Rudaito "can be given a registered trademark)), and the like. In addition, bisphenol A novolac type epoxy resin jER 157S (trade name, manufactured by Mitsubishi Chemical Corporation), tetraphenylolethane type epoxy resin jER YL-931 (trade name, manufactured by Mitsubishi Chemical Corporation), Araldite 163 (Trade name) (manufactured by Huntsman Advanced Material Co., Ltd.), ZX-1063 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), a tetraglycidylxylenoylethane resin, ESN-190, ESN-360 (Nippon Steel) HP-7200, HP-7200H (DIC) of epoxy resins having a dicyclopentadiene skeleton, such as Sumikin Chemical Co., Ltd., trade name), HP-4032, EXA-4750, EXA-4700 (DIC Corporation, trade name). Product name), etc. Rate-copolymerized epoxy resins such as CP-50S and CP-50M (trade name) manufactured by NOF Corporation, epoxy-modified polybutadiene rubber derivatives such as PB-3600 and PB-4700 (trade name, manufactured by Daicel Corporation), etc. , CTBN (terminal carboxylated butadiene-acrylonitrile copolymer) -modified epoxy resin YR-102, YR-450 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), and the like, are not limited thereto. These epoxy resins can be used alone or in combination of two or more.

  As other (c) thermosetting agent components, for example, oxetane compounds, benzoxazine compounds, oxazoline compounds, cyclic carbonate compounds, blocking agent isocyanates, melamine derivatives, polyfunctional maleimides, and the like can be used. These are used alone or in combination of two or more.

In particular, the photosensitive resin composition of the present embodiment preferably includes a tricyclodecane structure or a maleimide structure. As the thermosetting component, it is desirable to use a polyfunctional maleimide in combination with an epoxy resin. Such a compound contains at least two maleimide groups in the molecule. For example, 1-methyl- 2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4 '-Biphenylene bismaleimide, N, N'-4,4'-[3,3'-dimethyl-biphenylene] bismaleimide, N, N'-4,4 '-[3,3'-dimethyldiphenylmethane] bismaleimide N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′- Phenylpropane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, 2 , 2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-s -Butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-methyl-4- (4-maleimidophenoxy) ) -5-tert-butylphenyl] -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) ) -2- (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4 , 4'-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2 -Cyclohexylbenzene], 4,4'-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 '-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2,6- Bis (1,1-dimethylethyl) benzene], 4,4 '-(2-ethylhexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4'-(1-methylheptylidene) ) -Bis [1- (maleimidophenoxy) -benzene], 4,4'-cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene], 2,2-bis [4- (4-maleimidophenoxy) ) Phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2 -Bis [3-methyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- 4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl- (4-maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl]- Tricyclo- [5.2.1.0 ^2,6 ] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1.0 ^2,6 ] decane, 3 , 9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1.0 ^2,6 ] decane, 4,9-bis [4- ( 4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1.0 ^2,6 ] decane, 1,8 bis [4- (4-maleimidophenoxy) phenyl] menthane, 1,8 bis [3-methyl- 4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] menthane and the like can be mentioned. These can be used alone or in combination.

  Next, (d) component used by this embodiment: An inorganic filler is demonstrated. In the present embodiment, it is desirable to use an inorganic filler having at least (d-1) an average particle diameter of 0.05 μm to 1 μm and a refractive index of 1.3 to 1.7. Several kinds of inorganic fillers may be used in combination, such as fused spherical silica, fumed silica, sol-gel silica, etc., such as aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, water Examples include inorganic fillers derived from mine such as magnesium oxide, talc and mica. These are pulverized by a pulverizer, classified according to circumstances, and dispersed in the resin with an average particle size of 0.05 μm to 1 μm and a maximum particle size of 5 μm or less.

  When the average particle size of the filler is small and the particle size distribution is sharp, the absorbance is low and the apparent light transmittance is high. On the other hand, the light intensity changes at the top and bottom of the resin layer, and the pattern shape is good. The problem that cannot be obtained occurs. In the present embodiment, the absorbance at a wavelength of 365 nm in a dry coating film having a thickness of 25 μm is 2.0 or more, the absorbance at 405 nm is 1.5 or more, and the minimum absorbance at 300 nm to 800 nm is within the above filler particle size range. A filler having a value of 0.2 or more is used.

  When measuring the particle size of the inorganic filler, it is desirable to use a known particle size distribution meter. For example, particle size distribution using laser diffraction scattering type particle size distribution meter, frequency analysis by dynamic light scattering method, which irradiates particles with laser light and obtains particle size distribution by calculation from intensity distribution pattern of diffracted / scattered light emitted from it Examples thereof include a particle size distribution meter of nanoparticles for which distribution is obtained. In addition, what was formed into a film is dissolved in a predetermined organic solvent, and if necessary, a dispersant is added, and the average particle size and the maximum particle size are measured with the particle size distribution analyzer or the like.

  The filling amount of the inorganic filler is 20% by mass or more and 80% by mass or less in the total mass, and the filling amount is preferably 30% by mass or more and 60% by mass or less.

  The photosensitive resin composition of the present embodiment contains (e) component having at least one amino group in the molecule: an organic filler, and the average particle size of the organic filler is 0.05 μm or more like the inorganic filler, It is desirable that it is 1 μm or less and the maximum particle size is 2 μm or less and is dispersed in the composition. Examples of the compound having at least one amino group in the molecule include melamine, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, dicyandiamide, triazine compound, ethyldiamino-S-triazine, and 2,4-diamino-S. -Additives such as triazine derivatives such as triazine and 2,4-diamino-6-xylyl-S-triazine, imidazole series, thiazole series and triazole series, and silane coupling agents. 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK (both manufactured by Shikoku Kasei Kogyo Co., Ltd.) are available as commercially available products. These compounds can improve not only the adhesion between the photosensitive resin composition layer and the metal but also properties such as PCT resistance and electrolytic corrosion resistance. These are also dispersed in the resin composition using a predetermined pulverizer, disperser, and classifier. The content thereof is desirably 0.1 to 20 parts by mass or less, more desirably 0.5 to 15 parts by mass or less with respect to 100 parts by mass of the total solid content. This organic filler exhibits an anti-oxidation effect on the underlying wiring metal, but if it is less than 0.1 parts by mass, no effect is observed, and if it exceeds 20 parts by mass, the resolution tends to deteriorate and the plating bath tends to be contaminated. is there.

  In the present embodiment, it is preferable in terms of sensitivity and resolution to contain a photopolymerizable monomer having two or more ethylenically unsaturated groups in the molecule. Although it is desirable to contain a tricyclodecane structure or a maleimide structure, it is particularly desirable to use a compound having a tricyclodecane structure as the photopolymerizable monomer.

  For example, the photopolymerizable monomer having a tricyclodecane structure includes dimethylol tricyclodecane di (meth) acrylate or tricyclodecanediol di (meth) acrylate. Tricyclodecanediol dimethacrylate is NK ester DCP (made by Shin-Nakamura Chemical Co., Ltd., trade name), and tricyclodecane dimethanol diacrylate is NK ester A-DCP (made by Shin-Nakamura Chemical Co., Ltd., trade name). ) Commercially available. In addition, the compound containing the tricyclodecane structure of this embodiment is not limited to the said example.

  In addition, the photopolymerizable monomer is used singly or in combination of two or more, and particularly contains at least one polyfunctional photopolymerized monomer having three or more ethylenically unsaturated groups in one molecule. Is desirable. Among them, a polyfunctional photopolymerized monomer having 6 or more ethylenically unsaturated groups in one molecule is effective for improving crack resistance during reflow mounting. Such compounds include those of dipentaerythritol hexaacrylate and its similar structures. Commercially, KAYARAD DPHA, KAYARAD D-310, KAYARAD D-330, KAYARADP DPCA-20, 30, KAYARADP DPCA- 60, 120 (both manufactured by Nippon Kayaku Co., Ltd., trade names (“KAYARAD” is a registered trademark)) are available. Trimethylolpropane triethoxytriacrylate (SR-454, trade name, manufactured by Nippon Kayaku Co., Ltd.) is commercially available as a polyfunctional photopolymerized monomer having three or more ethylenically unsaturated groups in one molecule. Is possible.

There is no restriction | limiting in particular as another photopolymerizable monomer component which can be used for the photosensitive resin composition of this embodiment, The following can be used.
For example, it can be obtained by reacting a bisphenol A (meth) acrylate compound, a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid. Examples thereof include urethane monomers such as compounds and (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.

The photosensitive resin composition of this embodiment uses a pigment component as needed. For example, colorants or dyes such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, malachite green, crystal violet, titanium oxide, carbon black, naphthalene black, and azo organic pigments can be used.
Furthermore, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, nitroso compounds, thixotropic agents such as benton, montmorillonite, aerosil, amide wax, silicones, fluorines, polymers, etc. An antifoaming agent, a leveling agent, etc. may be included in the range which does not affect the desired characteristic of the photosensitive resin composition.

  Moreover, it is desirable to use a diluent as needed. Examples of the diluent include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol, hydrocarbons such as benzyl alcohol and cyclohexane, diacetone alcohol, Aliphatic ketones such as 3-methoxy-1-butanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, ethylene glycol, diethylene glycol, tri Ethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, pro Ethylene glycol alkyl ethers such as lenglycol diacetate, propylene glycol monoethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate And its acetate, diethylene glycol monoalkyl ether and its acetate diethylene glycol dialkyl ether, triethylene glycol alkyl ether, propylene glycol alkyl ether and its acetate, dipropylene glycol alkyl ether, and toluene, petroleum ether, petroleum naphtha, Hydrogenated petroleum naphtha Or petroleum solvents such as solvent naphtha, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, etc. Acid esters, amines, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dioxane, tetrahydrofuran, cyclohexanone, γ-butyrolactone, 3- Solvents such as hydroxy-2-butanone, 4-hydroxy-2-pentanone, and 6-hydroxy-2-hexanone can be used alone or in combination of two or more.

  In addition, when using the photosensitive resin composition with a liquid form, it is preferable that content of the diluent used for this embodiment is 5-40 mass% in the total mass.

  Next, the photosensitive film of suitable embodiment is demonstrated.

  The photosensitive film which concerns on this embodiment is provided with a support body and the photosensitive resin composition layer which consists of a photosensitive resin composition of the said this embodiment formed on this support body. On the photosensitive resin composition layer, you may further provide the protective film which coat | covers this photosensitive resin composition layer.

  As said support body, the polymer film which has heat resistance and solvent resistance, such as a polyethylene terephthalate, a polypropylene, polyethylene, polyester, can be used, for example. The thickness of the support (polymer film) is preferably 5 to 25 μm. If the thickness is less than 5 μm, the support film 10 tends to be broken when the support film 10 is peeled off before development, and the thickness is 25 μm. If it exceeds, the resolution tends to decrease. In addition, you may use the said polymer film by laminating | stacking on the both surfaces of the photosensitive resin composition layer by using one as a support body and another as a protective film.

  As the protective film, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Examples of commercially available products include, for example, product names “Alphan MA-410” and “E-200C” (“Alphan” is a registered trademark) manufactured by Oji F-Tex Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd. A polyethylene terephthalate film such as a PS series such as a product name “PS-25” manufactured by Teijin Ltd. may be mentioned, but is not limited thereto. The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. If this thickness is less than 1 μm, the protective film tends to be broken during lamination, and if it exceeds 100 μm, the cost tends to be inferior. The protective film preferably has a smaller adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support, and is preferably a low fisheye film. . Fisheye is a material in which foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are incorporated into the film when the material is melted and kneaded, extruded, biaxially stretched, or casted to produce a film. It is.

  The photosensitive resin composition layer is prepared by dissolving the photosensitive resin composition of the present embodiment in a solvent as described above to obtain a solution (coating solution) having a solid content of about 30 to 70% by mass. It is preferable to form by applying (coating liquid) on a support and drying. The application can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater or the like. Moreover, the said drying can be performed at 70-150 degreeC and about 5 to 30 minutes. The amount of the remaining organic solvent in the photosensitive resin composition is preferably 3% by mass or less with respect to the total amount of the photosensitive resin composition from the viewpoint of preventing diffusion of the organic solvent in the subsequent step. The thickness of the photosensitive layer 14 varies depending on the application, but is preferably 3 to 100 μm, more preferably 5 to 60 μm, and particularly preferably 10 to 50 μm after drying. If this thickness is less than 3 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the sensitivity and resolution inside the photosensitive resin composition layer tend to decrease.

  The photosensitive film may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. Moreover, the obtained photosensitive film can be wound up and stored in a sheet form or a roll around a core. In addition, it is preferable to wind up so that a support body may become the outermost part in this case. An end face separator is preferably installed on the end face of the roll-shaped photosensitive film roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

  Next, a method for forming a resist pattern using the photosensitive film of this embodiment will be described.

First, a photosensitive layer made of the above-described photosensitive resin composition is formed on a substrate on which a resist is to be formed. The protective film of the photosensitive film is peeled from the photosensitive resin composition layer, and the exposed surface is adhered by a laminate or the like so as to cover the conductor layer having a circuit pattern formed on the substrate. A method of laminating under reduced pressure is also preferable from the viewpoint of improving adhesion and followability. In addition, the photosensitive resin composition can also be apply | coated on a board | substrate by well-known methods, such as the method of apply | coating the varnish of the photosensitive resin composition with a screen printing method or a roll coater.
Next, if necessary, a removal process for removing the protective film from the photosensitive film described above is performed, and a predetermined part of the photosensitive resin composition layer is irradiated with actinic rays through the mask pattern, and the photosensitive resin composition of the irradiated part is irradiated. An exposure step for photocuring the layer is performed.

Further, when a support is present on the photosensitive layer, after removing the support, by removing a portion that has not been photocured by wet development or dry development (unexposed portion) and developing, A resist pattern can be formed.
In the case of the above-described wet development, as the developer, an alkaline aqueous solution, an aqueous developer, an organic solvent, or the like that is safe and stable and has good operability is used according to the type of the photosensitive resin composition. Further, as a developing method, a known method such as spraying, rocking dipping, brushing, scraping or the like is appropriately employed.

  Examples of the base of the alkaline aqueous solution include alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide which are hydroxides of lithium, sodium and potassium, carbonates or bicarbonates such as alkali metals and ammonium. Alkaline carbonate or bicarbonate, alkali metal phosphate sodium phosphate, potassium phosphate, etc., alkali metal pyrophosphate sodium pyrophosphate, potassium pyrophosphate etc., safe and stable, operability The one with good is used.

  Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, and a dilute solution of 0.1 to 5% by mass of sodium hydroxide. A solution, a dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred, and the pH is preferably in the range of 9 to 11. The temperature of the alkaline aqueous solution is adjusted according to the developability of the photosensitive layer 14 and is preferably 20 to 50 ° C. Furthermore, a small amount of an organic solvent such as a surfactant or an antifoaming agent may be mixed in the alkaline aqueous solution in order to promote development.

  As the aqueous developer, one comprising water and an alkaline aqueous solution or one or more organic solvents is used. Here, as the base of the alkaline aqueous solution, in addition to those described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3- Examples include propanediol, 1,3-diaminopropanol-2, and morpholine. The pH of such an aqueous developer is preferably as small as possible within a range where development processing can be sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.

  Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. . The concentration of such an organic solvent is usually preferably 2 to 90% by mass. Moreover, the temperature of such an organic solvent can be adjusted according to developability. Such organic solvents can be used alone or in combination of two or more. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. Furthermore, a small amount of an organic solvent such as a surfactant or an antifoaming agent may be mixed in the alkaline aqueous solution in order to promote development.

  In the resist pattern forming method of this embodiment, two or more kinds of development methods described above may be used in combination as necessary. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is most suitable for improving resolution. For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

Next, a preferred embodiment of the photosensitive permanent resist of the present invention using the photosensitive film of the present embodiment will be described.
After the development step, it is preferable to perform ultraviolet irradiation or heating with a high-pressure mercury lamp for the purpose of improving solder heat resistance and chemical resistance. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, and for example, irradiation can be performed at an irradiation amount of about 0.05 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out for about 15 to 90 minutes in the range of about 130-200 degreeC.

  Both ultraviolet irradiation and heating may be performed. In this case, both may be performed at the same time, and after either one is performed, the other may be performed. When performing ultraviolet irradiation and heating simultaneously, it is preferable to heat to 60-150 degreeC from a viewpoint of providing solder heat resistance and chemical resistance more favorably.

The photosensitive permanent resist formed in this way also serves as a protective film for the wiring after soldering the substrate, and has various characteristics of a solder resist, for printed wiring boards, for semiconductor package boards, flexible wiring boards It can be used as a solder resist.
The solder resist, for example, is used as a plating resist or an etching resist when plating or etching is performed on a substrate, and is also left on the substrate as it is to protect a wiring or the like (photosensitive permanent). Resist).

  Moreover, in the above-described exposure step, when exposure is performed using a mask or drawing data having a pattern in which a predetermined portion of the conductor layer is unexposed, the unexposed portion is removed by developing this, and the substrate A resist having an opening pattern in which a part of the conductor layer formed thereon is exposed is obtained. Thereafter, it is preferable to perform a treatment necessary for forming the above-described photosensitive permanent resist.

  The substrate provided with the photosensitive permanent resist of the present embodiment is then mounted with a semiconductor element or the like (for example, wire bonding, C4 solder connection) and then mounted on an electronic device such as a personal computer.

  The present invention has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the invention.

[Semiconductor package]
The photosensitive resin composition of this embodiment can be used suitably for formation of the permanent resist film of the printed wiring board for semiconductor packages. That is, this invention provides the semiconductor package which has a permanent resist layer which consists of a hardened | cured material of the above-mentioned photosensitive resin composition. FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor package. The semiconductor package 10 includes a semiconductor chip mounting substrate 50 and a semiconductor chip 120 mounted on the semiconductor chip mounting substrate 50. The semiconductor chip mounting substrate 50 and the semiconductor chip 120 are bonded with an adhesive 117 made of a die bond film or a die bond paste. The semiconductor chip mounting substrate 50 includes an insulating substrate 100. On one surface of the insulating substrate 100, a wire bonding wiring terminal 110 and a permanent resist layer in which an opening from which a part of the wiring terminal 110 is exposed is formed. 90 is provided, and a permanent resist layer 90 and solder connection terminals 111 are provided on the opposite surface. The permanent resist layer 90 is a layer made of a cured product of the photosensitive resin composition of the present embodiment. Solder connection terminals 111 have solder balls 114 mounted thereon for electrical connection with the printed wiring board. The semiconductor chip 120 and the wire bonding wiring terminal 110 are electrically connected using a gold wire 115. The semiconductor chip 120 is sealed with a semiconductor sealing resin 116. The photosensitive resin composition of the present embodiment can also be applied to flip chip type semiconductor packages.

FIG. 2 is a schematic cross-sectional view showing a flip chip type semiconductor package substrate. The flip chip type semiconductor package substrate 20 includes a semiconductor chip mounting substrate 50 and a semiconductor chip 120 mounted on the semiconductor chip mounting substrate 50. The semiconductor chip mounting substrate 50 and the semiconductor chip 120 are filled with an underfill agent 118. The semiconductor chip mounting substrate 50 has a configuration in which an insulating substrate 100b, an insulating substrate 100a, and a permanent resist layer 90 are stacked in this order. The permanent resist layer 90 is a layer made of a cured product of the photosensitive resin composition of the present embodiment. The insulating substrate 100b has a patterned copper wiring 80 on the surface on the insulating substrate 100a side, and the insulating substrate 100a has a patterned copper wiring 80 on the surface on the permanent resist layer 90 side. The copper wiring 80 on the insulating substrate 100b and at least a part of the copper wiring 80 on the insulating substrate 100a are electrically connected by the solder connection terminal 111 formed so as to penetrate the insulating substrate 100a and the insulating substrate 100b. It is connected. Further, the permanent resist layer 90 is formed so as to cover the copper wiring 80 on the insulating substrate 100a, but the copper wiring 80 is exposed on the copper wiring 80 corresponding to the connection terminal 111 for solder connection. An opening 112 is formed. The copper wiring 80 on the insulating substrate 100 a is electrically connected via the copper wiring 80 formed on the surface of the semiconductor chip 120 facing the semiconductor chip mounting substrate 50 and the solder ball 114 provided in the opening 112. It is connected.
The substrate provided with the permanent resist is then mounted on an electronic device such as a personal computer.

(Examples 1-5 and Comparative Examples 1-4)
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  First, about Examples 1-5 and Comparative Examples 1-4, the photosensitive resin composition was obtained by mixing each component shown in Table 1 with the compounding quantity (mass part) shown to the same table, respectively.

(A) Component: Resin EXP-2810 having an ethylenically unsaturated group and a carboxyl group: Acid-modified cresol novolac epoxy acrylate (manufactured by DIC Corporation, trade name)
ZAR-1753: Acid-modified bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., sample name)
UXE-3024: Urethane-modified bisphenol A type epoxy acrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.)
The weight average molecular weight was about 5000 to 10,000, and the acid value was about 70 mgKOH / g. Measurement conditions in GPC are as follows.
<GPC measurement conditions>
Model: Hitachi, Ltd., product name: L6000
Detection: manufactured by Hitachi, Ltd., RI-monitor, product name: L3300RI
Column: manufactured by Hitachi Chemical Co., Ltd., Gelpack GL-R440 + GL-R450 + GL-R400M (trade name, column specification: diameter 10.7 mm × 300 mm (“Gelpack” is a registered trademark))
Solvent: THF (tetrahydrofuran)
Sample concentration: Collecting 120 mg of NV (non-volatile) 40% by mass of resin solution in 5 mL of THF Injection amount: 200 μL
Pressure: 49Kgf / cm ²
Flow rate: 2.05 mL / min

(B) Component: Photopolymerization initiator I907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “IRGACURE 907” manufactured by BASF)
DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name “Kayacure DETX-S” (“Kayacure” is a registered trademark))

(C) Component: Thermosetting agent NC-3000H: Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., trade name)
YSLV-80: Bisphenol F type epoxy resin (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)

(D) Ingredient: Inorganic filler barium sulfate A: Barium sulfate having an average particle size of 184 nm and a maximum particle size of 0.58 μm or less (trade name “ASA”, manufactured by Nippon Solvay Co., Ltd.)
Silica A: sol-gel nanosilica and sample 2-N coupled with methacrylic silane 3-methacryloxypropyltrimethoxysilane as silane coupling agent (average particle size is 50 nm, maximum particle size is 1 μm or less, refractive index 1.45, manufactured by Admatechs, sample name)
Silica B: SC slurry (spherical fused silica) (average particle size is 300 nm, maximum particle size is 5 μm or less, refractive index is 1.45, manufactured by Admatechs Co., Ltd., sample name) was used.
Silica C: High-purity fused silica filler FLB-1 “silica” (trade name, manufactured by Tatsumori Co., Ltd.) was used, and the average particle size was 520 nm, the refractive index was 1.45, and the maximum particle size was 15.2 μm.
The dispersion state is a dynamic light scattering nanotrack particle size distribution meter “UPA-EX150” or a laser diffraction scattering type microtrack particle size distribution meter “MT3000” (both manufactured by Nikkiso Co., Ltd., trade names (“Nanotrack” and “ "Microtrack" was measured using a registered trademark)).

  Note that melamine and dicyandiamide used as the component (e) were also pulverized and dispersed in the same manner as the inorganic filler (d-1), and the maximum particle size was confirmed to be 2.0 μm or less. It was. The following other components were used. As a photopolymerizable monomer having an ethylenically unsaturated group, KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epolide PB3600, which is a butadiene elastomer (trade name (“Epolide” is a registered trademark) manufactured by Daicel Corporation) ), Polymerization inhibitor Antage 500 (trade name, manufactured by Kawaguchi Chemical Co., Ltd.), pigment HCP-PM-5385 (trade name, manufactured by Toyo Ink Co., Ltd.).

  Next, the photosensitive resin composition solution is uniformly coated on a 16 μm-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name) as a support layer to form a photosensitive resin composition layer. It was dried at 100 ° C. for about 10 minutes using a hot air convection dryer. The film thickness after drying of the photosensitive resin composition layer was 25 μm.

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

[Evaluation of sensitivity and resolution]
The copper surface of a printed wiring board substrate (E-679, manufactured by Hitachi Chemical Co., Ltd., trade name) in which a copper foil having a thickness of 12 μm was laminated on a glass epoxy substrate was polished with an abrasive brush, washed with water, and dried. On this printed wiring board substrate, a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name ("MVLP" is a registered trademark)) is used. Second, lamination press time 30 seconds, atmospheric pressure 4 kPa or less, pressure bonding pressure 0.4MPa, the protective film of the photosensitive film was peeled off and laminated to obtain a laminate for evaluation.

  Thereafter, after standing at room temperature for 1 hour or longer, a 41-step step tablet (manufactured by Hitachi Chemical Co., Ltd.) is brought into close contact with the support of the obtained laminate for evaluation, and direct imaging exposure using an ultrahigh pressure mercury lamp as a light source. Exposure was performed using apparatus DXP-3512 (manufactured by Oak Manufacturing Co., Ltd.).

After exposure, the film was allowed to stand at room temperature for 30 minutes, and then the polyethylene terephthalate on the support was removed, and the photosensitive resin composition in the unexposed area was spray-developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds. After development, the exposure energy amount at which the number of remaining gloss steps of the 41-step tablet was 10.0 was defined as the sensitivity (unit: mJ / cm ² ) of the photosensitive resin composition layer. The photosensitive resin composition layer was evaluated using the pattern exposed with this sensitivity.

The evaluation of sensitivity is the amount of exposure energy at which the number of steps is 10.0, 200 mJ / cm ² or less is set to “3”, 200 mJ / cm ² to 300 mJ / cm ^{2 is set} to “2”, and greater than 300 mJ / cm ^2. It was set to “1”. The results are shown in Table 2. Note that the smaller the exposure energy amount, the shorter the time required for exposure with higher sensitivity, and in particular, the throughput in direct imaging exposure is improved.

  In addition, the resolution is evaluated by exposing and spray developing with an exposure energy amount that the number of step steps is 10.0, and when the resist pattern is observed using an optical microscope after the development processing, the line that remains without peeling or twisting. Evaluation was made by measuring the smallest width among the widths (unit: μm). The smaller the value of the line width (μm) remaining as line and space, the better the value. It calculated | required as resolution (micrometer). The results are shown in Table 2.

[Evaluation of resist shape]
The cross section of the permanent resist pattern obtained above was observed, and the shape was evaluated according to the following criteria. The results are shown in Table 2.
“3”: Straight to taper shape “1”: Overhang and undercut are observed

[Measurement of reflectance]
A photosensitive element was formed on a substrate MCL-E679, and the reflectance of the surface was measured using a spectrocolorimeter CM-512m3 (manufactured by MINOLTA). A reflectance of 50 or higher was determined as “3”, and a reflectance smaller than 50 was determined as “1”.

[Measurement of absorbance of photosensitive layer]
The protective film was peeled off from the photosensitive element, this was placed on the measurement side of a 228A type W beam UV spectrophotometer manufactured by Hitachi, Ltd., and a support film was placed on the reference side. And the range of 700-300 nm was continuously measured by the absorbance mode, and the absorption spectrum was obtained. The absorbance values at 365 nm and 405 nm and the minimum absorbance values at 300 to 800 nm were read from the obtained absorption spectrum. “3” when the absorbance at a wavelength of 365 nm is 2.0 or more, the absorbance at 405 nm is 1.5 or more, and the minimum absorbance at 300 to 800 nm is 0.2 or more, and does not satisfy the above condition Was evaluated as “1”. The results are shown in Table 2.

[Evaluation of CTE]
By exposing the entire surface of the photosensitive laminate to development, ultraviolet irradiation, and heat treatment, a photosensitive resin is formed on a polyethylene terephthalate film (G2-16, trade name, manufactured by Teijin Limited) with a thickness of 16 μm. A cured product of the composition was formed, and then cut with a cutter knife into a width of 3 mm and a length of 30 mm, and then the polyethylene terephthalate on the cured product was peeled off to obtain a permanent resist for thermal expansion coefficient evaluation.
Using a TMA (thermomechanical analysis) device SS6000 (manufactured by Seiko Instruments Inc.), the coefficient of thermal expansion in the tensile mode was measured. The tensile load is 2 gf, the span (distance between chucks) is 15 mm, and the heating rate is 10 ° C./min. First, the sample was attached to the apparatus, heated from room temperature (25 ° C.) to 160 ° C., and left for 15 minutes. Then, it cooled to -60 degreeC and measured on conditions with a temperature increase rate of 10 degree-C / min from -60 degreeC to 250 degreeC. The inflection point seen in the range from 25 ° C to 200 ° C was defined as Tg.
CTE used the inclination of the tangent of the curve obtained at the temperature below Tg. With the CTE value obtained in Example 1 as a reference value, a value that is less than 30% greater than this reference value is “3”, a value that is greater than 30% but less than 50% is “2”, and a value that is greater than 50% 1 ”. The results are shown in Table 2.

[Evaluation of HAST resistance]
Substrate for printed wiring board (MCL-E-679FG, manufactured by Hitachi Chemical Co., Ltd., trade name (“MCL” is a registered trademark)), semi-additive wiring formation, with 12 μm thick copper foil laminated on glass epoxy base material as core material A comb-type electrode having a line / space of 8 μm / 8 μm was prepared using a build-up material (AS-ZII, manufactured by Hitachi Chemical Co., Ltd., trade name), and this was used as an evaluation substrate.

A solder resist made of a cured product of a resist is formed on the comb electrode on this evaluation substrate in the same manner as in the above “evaluation of resolution” (exposure is performed so that the solder resist remains in the comb electrode portion, development, ultraviolet rays Then, the film was exposed to 130 ° C., 85% RH, 6V for 200 hours. Thereafter, the resistance value was measured and the degree of migration was observed with a 100-fold metal microscope, and evaluated according to the following criteria. That is, a resistance value of 1.0 × 10 ¹⁰ Ω or more is maintained, and “3” is given when no migration occurs in the solder resist film, and a resistance value of 1.0 × 10 ¹⁰ Ω or more is maintained. However, it was “2” when a slight migration occurred, and “1” when a resistance value was less than 1.0 × 10 ¹⁰ Ω and a large migration occurred. The results are shown in Table 2.

[Evaluation of crack resistance]
After the evaluation laminate substrate on which the solder resist was formed in the same manner as in the above-mentioned “production of the evaluation substrate” was exposed to the air at −65 ° C. for 15 minutes, the temperature was increased at a temperature increase rate of 180 ° C./min. After being exposed to the atmosphere at 150 ° C. for 15 minutes, a thermal cycle in which the temperature was lowered at a rate of 180 ° C./min was repeated 1000 times. After being exposed to such an environment, cracks and peeling of the permanent resist film of the evaluation laminate substrate were observed with a 100-fold metal microscope and evaluated according to the following criteria. In other words, “3” means that the cracks and peeling of the permanent resist film were not observed at all after confirming 10 places of the 2 mm square openings, and those where cracks and peeling were observed in 2 or less of the 10 places. “2” and those in which cracking and peeling were observed at 3 or more of 10 locations were designated as “1”. The results are shown in Table 2.

  As described above, the photosensitive resin composition of the present embodiment has excellent resolution in direct imaging exposure, and the permanent resist made of the cured product has excellent low CTE, high Tg, HAST resistance, and crack resistance. Was confirmed.

  DESCRIPTION OF SYMBOLS 10 ... Semiconductor package, 20 ... Flip chip type semiconductor package substrate, 50 ... Semiconductor chip mounting substrate, 80 ... Copper wiring, 90 ... Permanent resist layer, 100, 100a, 100b ... Insulating substrate, 110 ... Wire bonding wiring terminal 111 ... Solder connection terminal, 112 ... Opening, 114 ... Solder ball, 115 ... Gold wire, 116 ... Semiconductor sealing resin, 117 ... Adhesive, 118 ... Underfill agent, 120 ... Semiconductor chip.

Claims (8)

(A) a resin having an ethylenically unsaturated group and a carboxyl group,
(B) a photopolymerization initiator,
(C) a thermosetting agent,
(D) an inorganic filler,
(E) a photosensitive resin composition containing an organic filler having an amino group,
(D) The inorganic filler and (e) the organic filler having one or more amino groups have an average particle size of 0.05 μm or more and 1.0 μm or less, and a maximum particle size of 5 μm or less,
When the photosensitive resin composition is coated on a substrate, dried, and having a thickness of 25 μm, the absorbance at a wavelength of 365 nm is 2.0 or more, the absorbance at 405 nm is 1.5 or more, and the minimum absorbance at 300 to 800 nm A photosensitive resin composition having a value of 0.2 or more.   (D) One of the inorganic fillers is spherical fused silica, The photosensitive resin composition of Claim 1 which contains the said spherical fused silica in 20 to 80 mass% in the photosensitive resin composition.   The photosensitive resin composition according to claim 1 or 2, wherein a reflectance of the coating film surface after drying by 10 ° incidence is 10% or more with respect to wavelengths of 365 nm and 405 nm.   The photosensitive resin composition in any one of Claims 1-3 containing the compound which has a tricyclodecane structure or a maleimide structure.   The photosensitive resin composition according to claim 1, wherein a pattern can be formed by direct imaging exposure.   A photosensitive film provided with a support body and the photosensitive resin composition layer which consists of a photosensitive resin composition in any one of Claims 1-5 formed on this support body.   The permanent resist which consists of a hardened | cured material of the photosensitive resin composition in any one of Claims 1-5, and is formed on the board | substrate for printed wiring boards. A lamination step of providing a photosensitive layer made of the photosensitive resin composition according to any one of claims 1 to 5 on a substrate,
An exposure step of pattern irradiating actinic rays to the photosensitive layer;
A development step of developing the photosensitive layer after the exposure step;
A method for producing a permanent resist.

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