JP4254699B2 - Photocurable resin composition and photosensitive element using the same - Google Patents

Description

  The present invention relates to a photocurable resin composition, and more specifically, in the field of electronic materials such as a printed wiring board solder resist, a high-density multilayer board interlayer insulating film, a solder resist for semiconductor packages, and the like. The present invention relates to a photocurable resin composition used as a permanent mask resist having excellent properties, mechanical properties, chemical resistance, electrical properties, and the like.

  The present invention also relates to a photosensitive element using the photocurable resin composition.

  Conventionally, permanent mask resists in the production of printed wiring boards have been produced by a method of screen printing with heat or ultraviolet curable resist ink. In recent years, along with the high integration of electronic devices, it has become necessary to increase the definition of wiring patterns and insulating patterns in printed wiring boards, but in conventional resist forming methods by screen printing, bleeding occurs during printing, Since sagging or the like occurs, it is difficult to form a high-definition resist image. Therefore, a resist image forming method by photolithography has been developed. Specifically, a dry film type photosensitive resist is thermocompression-bonded on a base material, or a liquid photosensitive resist is curtain-sprayed on a base material, and actinic rays such as ultraviolet rays are irradiated through a negative mask, A resist image is formed by development. In the case of a dry film type photosensitive resist, air is easily entrapped at the time of thermocompression bonding to the base material, and bubbles are likely to be generated.

  On the other hand, liquid photosensitive resists are classified into a solvent development type and an alkali development type, but the alkali development type is mainly used from the viewpoint of working environment preservation and global environment preservation. As such a thing, what is shown by Unexamined-Japanese-Patent No. 61-243869, Unexamined-Japanese-Patent No. 1-1141904 is known, and in order to improve the heat resistance of a coating film, chemical resistance, and an electrical property, it is further Ultraviolet exposure and heating are performed to promote the crosslinking reaction.

  However, the conventional liquid photosensitive resist still has a problem in terms of wet heat resistance and heat resistance in practical characteristics. That is, an alkali development type liquid photosensitive resist is mainly composed of a hydrophilic group in order to enable alkali development. Therefore, a chemical solution, water, etc. are easily penetrated, and the resist film has practical characteristics. It is guessed that

  As electronic devices become smaller, lighter, and have higher performance, semiconductor packages have become smaller and have more pins, and mass production is progressing. For example, in a semiconductor package such as a BGA (ball grid array) and a CSP (chip size package), PCT resistance (pressure cooker resistance), which is also called moisture and heat resistance, is particularly required from the viewpoint of high reliability. However, under such severe conditions, the conventional liquid photosensitive resist has only a few hours to a few dozen hours. Furthermore, when the mounting method is changed from insertion mounting to surface mounting, the temperature applied to the package at the time of mounting tends to increase. Specifically, in the case of surface mounting, cream solder is printed in advance on the necessary parts, the whole is heated with infrared rays, and the solder is reflowed and fixed, so that the temperature reached inside and outside the package is extremely high at 220 to 240 ° C. In the conventional liquid photosensitive resist, there is a problem of so-called reflow resistance deterioration, in which the coating film is cracked by thermal shock or peeled off from the substrate or the sealing material, and improvement thereof is required. .

INDUSTRIAL APPLICABILITY The present invention can obtain a high-performance cured film excellent in heat resistance, heat and humidity resistance, adhesion, mechanical properties, and electrical properties, and is suitably used for manufacturing printed wiring boards, high-density multilayer boards, semiconductor packages, and the like. An object of the present invention is to provide a photocurable resin composition.
The present invention also provides a photosensitive element from which a cured film having excellent heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical insulation obtained by laminating a layer of the photocurable resin composition on a support is obtained. The purpose is to provide.

  The present invention comprises an acid-modified vinyl group-containing epoxy resin (A), an elastomer (B), a photopolymerization initiator (C), a diluent (D), and a curing agent (E) as essential components. A curable resin composition is provided.

The present invention also provides a photocurable resin composition characterized in that the elastic modulus of a cured film of the composition is 1 to 100 MPa by dynamic viscoelasticity measurement in a 200 to 220 ° C. region.
This invention also provides the photosensitive element formed by laminating | stacking the layer of said photocurable resin composition on a support body.

  According to the present invention, a high-performance cured film excellent in heat resistance, moisture and heat resistance (shear adhesion), adhesion, mechanical properties, and electrical properties can be obtained, such as printed wiring boards, high-density multilayer boards, and semiconductor packages. A photocurable resin composition and a photosensitive element that are suitably used for production were obtained.

  As the acid-modified vinyl group-containing epoxy resin used in the present invention, a resin obtained by modifying an epoxy resin with a vinyl group-containing monocarboxylic acid is used. Preferably, the novolak type epoxy resin represented by the general formula (I) is represented by the general formula: At least one epoxy resin (a) selected from the group consisting of a bisphenol エ ポ キ シ type epoxy resin or bisphenol F type epoxy resin represented by (II) and a salicylaldehyde type epoxy resin represented by the general formula (III) and a vinyl group A resin obtained by reacting the contained monocarboxylic acid (b) is used.

（式中、Ｘは水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）、Ｒは水素原子又はメチル基であり、ｎは１以上の整数であり、好ましくは２〜１００の整数である）
本発明の光硬化性樹脂組成物において、酸変性ビニル基含有エポキシ樹脂（Ａ）は、紫外線や熱により橋架け反応（硬化反応）が進行することで、硬化収縮して樹脂内部に歪み（内部応力）が加わり、可とう性や接着性が低下するという問題がある。そこで、柔軟性を持つエラストマー（Ｂ）を添加することで、硬化膜の応力を緩和し、硬化塗膜の改質を行った。本発明においては、酸変性ビニル基含有エポキシ樹脂（Ａ）にエラストマー（Ｂ）を併用し、ポリマーアロイ化することで、硬化膜の硬化収縮、可とう性が改質され、リフロー時の温度とされる２００〜２２０℃の温度領域における動的粘弾性測定で、弾性率が１〜１００MPaと低減でき、封止材とのせん断接着性を改良することができる。すなわち、弾性率が１MPa未満であると機械強度が低下し、１００MPaを超えるとせん断接着力が低下する。

(In the formula, X is a hydrogen atom or a glycidyl group (where hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), R is a hydrogen atom or a methyl group, and n is an integer of 1 or more. And preferably an integer from 2 to 100)
In the photo-curable resin composition of the present invention, the acid-modified vinyl group-containing epoxy resin (A) is cured and contracted by a crosslinking reaction (curing reaction) by ultraviolet light or heat, and is distorted inside the resin (internal There is a problem that flexibility and adhesiveness are reduced due to the application of stress. Therefore, by adding a flexible elastomer (B), the stress of the cured film was relaxed and the cured coating film was modified. In the present invention, by using the acid-modified vinyl group-containing epoxy resin (A) together with the elastomer (B) and polymer alloying, the curing shrinkage and flexibility of the cured film are modified, and the temperature during reflow In the dynamic viscoelasticity measurement in the temperature range of 200 to 220 ° C., the elastic modulus can be reduced to 1 to 100 MPa, and the shear adhesiveness with the sealing material can be improved. That is, when the elastic modulus is less than 1 MPa, the mechanical strength decreases, and when it exceeds 100 MPa, the shear adhesive strength decreases.

  The acid-modified vinyl group-containing epoxy resin (A) used in the present invention includes the reaction product in addition to the reaction product (A ′) of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). A reaction product (A ″) obtained by reacting (A ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c) is also used. In these reaction products, specifically, In this reaction, a hydroxyl group is formed by the addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b), and the hydroxyl group formed in the next reaction (in the epoxy resin (a) It is presumed that a half-ester reaction occurs between a certain original hydroxyl group and the acid anhydride group of the saturated or unsaturated group-containing polybasic acid anhydride (c).

  The novolak type epoxy resin represented by the general formula (I) includes a phenol novolak type epoxy resin and a cresol novolak type epoxy resin, and can be obtained by reacting a phenol novolak resin or a cresol novolak resin with epichlorohydrin by a known method.

であるビスフェノールΑ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂は、例えば、一般式（IV）で示されるビスフェノールΑ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂の水酸基とエピクロルヒドリンを反応させることにより得ることができる。水酸基とエピクロルヒドリンとの反応を促進するためには、反応温度５０〜１２０℃でアルカリ金属水酸化物存在下、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等の極性有機溶剤中で反応を行うのが好ましい。反応温度が５０℃未満では反応が遅くなり、反応温度が１２０℃では副反応が多く生じてしまい好ましくない。 In addition, in the general formula (II), X is a glycidyl group.

The bisphenol-Α type epoxy resin and bisphenol F-type epoxy resin can be obtained, for example, by reacting the hydroxyl groups of the bisphenolΑ-type epoxy resin and bisphenol F-type epoxy resin represented by the general formula (IV) with epichlorohydrin. In order to promote the reaction between the hydroxyl group and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. When the reaction temperature is less than 50 ° C, the reaction is slow, and when the reaction temperature is 120 ° C, many side reactions occur, which is not preferable.

（Ｒは、水素原子又はメチル基、ｎは１以上の整数である）
一般式（III）で示されるサリチルアルデヒド型エポキシ樹脂としては、具体的にはＦΑＥ−２５００、ＥＰＰＮ−５０１Ｈ、ＥＰＰＮ−５０２Ｈ（以上、日本化薬(株)製、商品名）等が挙げられる。

(R is a hydrogen atom or a methyl group, and n is an integer of 1 or more)
Specific examples of the salicylaldehyde type epoxy resin represented by the general formula (III) include FΑE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) and the like.

  Examples of the vinyl group-containing monocarboxylic acid (b) in the present invention include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α -Cyanocinnamic acid, etc., and saturated with half ester compounds, vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters, which are reaction products of hydroxyl group-containing acrylates with saturated or unsaturated dibasic acid anhydrides Or the half-ester compound which is a reaction product with an unsaturated dibasic acid anhydride is mentioned. These half ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids (b) can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) include hydroxyethyl acrylate, hydroxyethyl Methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol tris Methacrylate, dipentaerythritol pentaacrylate, Data dipentaerythritol methacrylate, glycidyl acrylate, glycidyl methacrylate and the like.

  Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) in the present invention, the vinyl group-containing monocarboxylic acid (b) is 0.8 per 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to make it react by the ratio used as -1.05 equivalent, More preferably, it is 0.9-1.0 equivalent.

  The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) are dissolved and reacted in an organic solvent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, toluene, xylene, tetramethylbenzene and the like. Aromatic hydrocarbons, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, aliphatic hydrocarbons such as octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, sorbet Petroleum solvents such as Tonafusa like.

  Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, and triphenylphosphine. The usage-amount of a catalyst becomes like this. Preferably it is 0.1-10 weight part with respect to a total of 100 weight part of an epoxy resin (a) and a vinyl group containing monocarboxylic acid (b).

Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction.
Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the amount used is 100 parts by weight of the total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount is preferably 0.01 to 1 part by weight. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  Use a vinyl group-containing monocarboxylic acid (b) with polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride as necessary. Can do.

  In the present invention, as the acid-modified vinyl group-containing epoxy resin (A), a resin obtained by reacting the reaction product (A ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c) is also used. It is done.

  Examples of the saturated or unsaturated group-containing polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydro anhydride Examples include phthalic acid, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the reaction product (A ′) with the saturated or unsaturated group-containing polybasic acid anhydride (c), the saturated or unsaturated group-containing polyhydric acid is added to 1 equivalent of the hydroxyl group in the reaction product (A ′). By reacting 0.1 to 1.0 equivalent of the basic acid anhydride (c), the acid value of the acid-modified vinyl group-containing epoxy resin (A) can be adjusted. The acid value of the acid-modified vinyl group-containing epoxy resin (A) is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the photocurable resin composition in a dilute alkali solution is lowered, and when it exceeds 150 mgKOH / g, the electric properties of the cured film tend to be lowered. The reaction temperature between the reaction product (A ′) and the saturated or unsaturated group-containing polybasic acid anhydride (c) is preferably 60 to 120 ° C.

  If necessary, as the epoxy resin (a), for example, a hydrogenated bisphenol-type epoxy resin, and further as an acid-modified vinyl group-containing epoxy resin (A), hydroxyethyl acrylate of a styrene-maleic anhydride copolymer Styrene-maleic acid-based resins such as modified products or hydroxyethyl acrylate modified products of styrene-maleic anhydride copolymers may be used in combination.

  Examples of the elastomer (B) used in the present invention include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These elastomers (B) are The hard segment component and the soft segment component are generally used. The former generally contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

  Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer. In addition to styrene, which is a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used. Specifically, Tufprene, Solprene T, Asaprene T, Tuftec (manufactured by Asahi Kasei Kogyo Co., Ltd.), Elastomer Α R (manufactured by Aron Kasei), Kraton G, Super Reflex (manufactured by Shell Japan), JSR-TR , TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.) ), Lavalon (Mitsubishi Chemical Co., Ltd.), Septon, Hibler (above, Kuraray Co., Ltd.), Sumiflex (Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (above, Riken Vinyl Industries).

  The olefin elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, for example, an ethylene-propylene copolymer (EPR). ), Ethylene-propylene-diene copolymer (EPDM), etc., and also having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene and the like. Non-conjugated dienes and α-olefin copolymers. Moreover, the carboxy modified NBR which copolymerized methacrylic acid to the butadiene-acrylonitrile copolymer is mentioned. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, etc. Can be mentioned. More specifically, Miralastoma (manufactured by Mitsui Petrochemical), EXΑCT (manufactured by Exxon Chemical), ENGΑGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (manufactured by Nippon Synthetic Rubber Co., Ltd.), butadiene -Acrylonitrile copolymer "NBR series" (manufactured by Nippon Synthetic Rubber Co., Ltd.), or "XER series" of carboxyl group-modified butadiene-acrylonitrile copolymers having cross-linking points (manufactured by Nippon Synthetic Rubber Co., Ltd.), etc. Is mentioned.

  Urethane elastomers consist of structural units of hard segments composed of low-molecular glycols and diisocyanates and soft segments composed of polymer (long-chain) diols and diisocyanates. Polypropylene glycol and polytetramethylene oxide as polymer (long-chain) diols. , Poly (1,4-butylene adipate), poly (ethylene 1,4-butylene adipate), polycaprolactone, poly (1,6-hexylene carbonate), poly (1,6-hexylene neopentylene adipate) Etc. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. In addition to ethylene glycol, short chain diols such as propylene glycol, 1,4-butanediol and bisphenol candy can be used, and the number average molecular weight of the short chain diol is preferably 48 to 500. Specific examples of the urethane elastomer include PΑNDEX T-2185, T-2983N (manufactured by Dainippon Ink), and sylactolan E790.

  Examples of the polyester elastomer include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, and the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more. Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And a dihydric phenol represented by the following general formula (V).

（但し、ＹはＣ₁〜Ｃ₁₀のアルキレン基、Ｃ₄〜Ｃ₈のシクロアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ₂−からなる群から選択され、又は直接ベンゼン環同志が結合しており、Ｒ¹及びＲ²はハロゲン又はＣ₁〜Ｃ₁₂のアルキル基であり、ｌ、ｍは０〜４の整数であり、ｐは０又は１である）
その具体例として、ビスフェノールΑ、ビス−（４−ヒドロキシフェニル）メタン、ビス−（４−ヒドロキシ−３−メチルフェニル）プロパン、レゾルシン等が挙げられる。これらの化合物は単独で又は２種以上用いることができる。また、芳香族ポリエステル（例えば、ポリブチレンテレフタレート）部分をハードセグメント成分に、脂肪族ポリエステル（例えば、ポリテトラメチレングリコール）部分をソフトセグメント成分にしたマルチブロック共重合体を用いることができる。ハードセグメントとソフトセグメントの種類、比率、分子量の違いによりさまざまなグレードのものがある。具体例として、ハイトレル（デュポン−東レ(株)製）、ペルプレン（東洋紡績(株)製）、エスペル（日立化成工業(株)製）等が挙げられる。

(Y is selected from the group consisting of a C _{1 to} C ₁₀ alkylene group, a C _{4 to} C ₈ cycloalkylene group, —O—, —S—, —SO ₂ —, or directly bonded to each other. R ¹ and R ² are halogen or a C _{1 to} C ₁₂ alkyl group, l and m are integers of 0 to 4, and p is 0 or 1)
Specific examples thereof include bisphenol soot, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, resorcin and the like. These compounds can be used alone or in combination of two or more. In addition, a multiblock copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used. There are various grades depending on the type, ratio, and molecular weight of the hard and soft segments. Specific examples include Hytrel (manufactured by DuPont-Toray Industries, Inc.), Perprene (manufactured by Toyobo Co., Ltd.), Espel (manufactured by Hitachi Chemical Co., Ltd.), and the like.

  Polyamide-based elastomers are roughly classified into two types, polyether block amide type and polyether ester block amide type, which use polyamide for the hard phase and polyether or polyester for the soft phase. 12 and the like, and as the polyether, polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used. Specifically, UBE polyamide elastomer (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls), PEBΑX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan), Nopamid ( Mitsubishi Chemical Co., Ltd.), Glais (Dainippon Ink Co., Ltd.) and the like.

  The acrylic elastomer is mainly composed of an acrylic ester, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, or the like is used, and glycidyl methacrylate, allyl glycidyl ether, or the like is used as a crosslinking point monomer. Furthermore, acrylonitrile and ethylene can be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

  Silicone elastomers are mainly composed of organopolysiloxane, and can be classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Some are modified with vinyl groups, alkoxy groups, and the like. Specific examples include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

  In addition to the above thermoplastic elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the above bisphenol F type epoxy resin, bisphenol エ ポ キ シ type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber or the like. Among these elastomers, in terms of shear adhesion, both end carboxyl group-modified butadiene-acrylonitrile copolymers and Espel (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), which are polyester elastomers having hydroxyl groups, are used. preferable.

  The blending amount of the elastomer (B) is preferably 2 to 30 parts by weight, more preferably 4 to 20 parts by weight with respect to 100 parts by weight of the acid-modified vinyl group-containing epoxy resin (A). If it is less than 2 parts by weight, the elastic modulus in the high temperature region of the cured film tends not to be low, and if it exceeds 50 parts by weight, the unexposed part tends not to be eluted with the developer.

  Examples of the photopolymerization initiator (C) used in the present invention include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, N, N-dimethylaminoacetophenone, etc. Acetophenones, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone and other anthraquinones, 2,4-dimethylthio Thioxanthones such as oxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, There are 4,4'-bis (diethylamino) benzophenone, Michler's ketone, benzophenones such as 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like, either alone or in combination of two or more Can be used in combination.

  Furthermore, photopolymerization initiation aids such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. An agent can be used individually or in combination of 2 or more types.

  The amount of the photopolymerization initiator (C) contained in the photocurable resin composition of the present invention is preferably 0.5 to 20 parts by weight, more preferably 2 to 2 parts by weight in 100 parts by weight of the photocurable resin composition. 15 parts by weight are used. If it is less than 0.5 part by weight, the exposed part tends to elute during development, and if it exceeds 20 part by weight, the heat resistance tends to decrease.

  As the diluent (D) used in the present invention, for example, an organic solvent and / or a photopolymerizable monomer can be used. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Examples of the photopolymerizable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol. Glycol mono- or di (meth) acrylates, N, N-dimethyl (meth) acrylamide, (meth) acrylamides such as N-methylol (meth) acrylamide, amino such as N, N-dimethylaminoethyl (meth) acrylate Polyhydric alcohols such as alkyl (meth) acrylates, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyethylene (meth) acrylates of these ethylene oxides or propylene oxide adducts, phenoxyethyl (meth) acrylates, (meth) acrylates of phenolic ethylene oxides or propylene oxide adducts such as polyethoxydi (meth) acrylates of bisphenolΑ And (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and melamine (meth) acrylate.

  The diluent (D) of the present invention is used alone or in combination of two or more, and the amount of the diluent (D) contained in the photocurable resin composition is in 100 parts by weight of the photocurable resin composition. The amount is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight. If it is less than 5 parts by weight, the photosensitivity tends to be low and the exposed part tends to elute during development, and if it exceeds 80 parts by weight, the heat resistance tends to decrease.

  The curing agent (E) used in the present invention is a compound that itself cures by heat, ultraviolet rays, or the like, or an acid-modified vinyl group-containing epoxy resin (A) that is a photocurable resin component in the composition of the present invention. The compound which hardens | cures with a carboxy group, a hydroxyl group and heat | fever, an ultraviolet-ray, etc. of this is preferable. By using a curing agent, the heat resistance, adhesion, chemical resistance, etc. of the final cured film can be improved.

  As a hardening | curing agent (E), an epoxy compound, a melamine compound, a urea compound, an oxazoline compound etc. can be mentioned as a thermosetting compound, for example. Examples of the epoxy compound include bisphenol Α type epoxy resin, bisphenol F type epoxide resin, hydrogenated bisphenol Α type epoxy resin, brominated bisphenol Α type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. Alternatively, heterocyclic epoxy resins such as triglycidyl isocyanurate, bixylenol type epoxy resins and the like can be mentioned. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. Examples of the urea compound include dimethylol urea.

  The curing agent (E) of the present invention is used alone or in combination of two or more, and the amount of the curing agent (E) contained in the photocurable resin composition is in 100 parts by weight of the photocurable resin composition. The amount is preferably 2 to 50 parts by weight, more preferably 10 to 40 parts by weight. If it is less than 2 parts by weight, the heat resistance of the final cured coating film tends to be low, and if it exceeds 50 parts by weight, the developability tends to decrease.

  The photocurable resin composition of the present invention can be used in combination with an epoxy resin curing agent for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the final cured film.

  Specific examples of such an epoxy resin curing agent include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl. Imidazole derivatives such as -5-hydroxymethylimidazole: guanamines such as acetoguanamine and benzoguanamine: diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide, etc. Polyamines: These organic acid salts and / or epoxy adducts: Amine complexes of boron trifluoride: ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl- S Triazine derivatives such as triazine: trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris ( Tertiary amines such as dimethylaminophenol), tetramethylguanidine and m-aminophenol: polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak: tributylphosphine, triphenylphosphine, tris-2-cyanoethyl Organic phosphines such as phosphine: phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosnium chloride : Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride: The above polybasic acid anhydrides: diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium Examples include hexafluorophosphate.

  The epoxy resin curing agent is used alone or in combination of two or more, and the amount of the epoxy resin curing agent contained in the photocurable resin composition is preferably 0.1% in 100 parts by weight of the photocurable resin composition. 01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight is used.

  In the photocurable resin composition of the present invention, for the purpose of further improving various properties such as adhesion and coating film hardness, if necessary, barium sulfate, barium titanate, silica, talc, calcined kaolin, Known inorganic fillers such as magnesium carbonate, aluminum oxide, aluminum hydroxide, and mica can be used alone or in combination of two or more. The amount used is preferably 2 to 80 parts by weight, more preferably 5 to 50 parts by weight, in 100 parts by weight of the photocurable resin composition.

  In the photocurable resin composition of the present invention, as required, known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, Polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, thickeners such as benton and montmorillonite, silicone-based, fluorine-based, vinyl resin-based antifoaming agents, silane coupling agents, etc. Various additives can be used. Further, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can be used.

  The photocurable resin composition of the present invention can be obtained by uniformly kneading and mixing the compounding components with a roll mill, a bead mill or the like.

The photocurable resin composition of the present invention forms an image as follows, for example, and is used for preparing a cured coating film. That is, it is applied to a copper-clad laminate with a film thickness of 10 to 200 μm by a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method or the like, and the coating film is then applied at 60 to 110 ° C. After drying, the negative film is directly contacted (or non-contacted through a transparent film) and irradiated with active light (eg, ultraviolet light), preferably 10 to 1,000 mJ / cm ² , and then unexposed. The portion is dissolved and removed (developed) with a dilute alkaline aqueous solution or an organic solvent. Next, the exposed portion is sufficiently cured by post-exposure (ultraviolet exposure) and / or post-heating to obtain a cured film. For example, the post-exposure is preferably 1 to 5 J / cm ² , and the post-heating is preferably 100 to 200 ° C. for 30 minutes to 12 hours.

  Moreover, the layer of the photocurable resin composition of this invention can also be laminated | stacked on a support body, and it can also be set as a photosensitive element. The thickness of the layer of the photocurable resin composition is preferably 10 to 100 μm, and a film of 5 to 100 μm in thickness such as polyethylene terephthalate is preferably used as the support. The layer of the photocurable resin composition is preferably formed by applying and drying a solution of the photocurable resin composition on the support film.

  Hereinafter, although the synthesis example and Example of this invention demonstrate further more concretely, this invention is not limited to this. In addition, the part in an Example and the compounding quantity in a table | surface in a synthesis example show a weight part.

Synthesis example 1
YDCN704 (manufactured by Toto Kasei Co., Ltd., cresol novolac type epoxy resin, in general formula (I), X = glycidyl group, R = methyl group) 220 parts, acrylic acid 72 parts, hydroquinone 1.0 part, carbitol acetate 180 The reaction mixture was dissolved by heating and stirring to 90 ° C. Next, the mixture was cooled to 60 ° C., 1 part of benzyltrimethylammonium chloride was charged, heated to 100 ° C., and reacted until the solid content acid value reached 1 mg KOH / g. Next, 152 parts of tetrahydrophthalic anhydride and 100 parts of carbitol acetate are added, heated to 80 ° C., reacted and cooled for about 6 hours, and diluted with carbitol acetate to a solid content concentration of 60% by weight. A modified vinyl group-containing epoxy resin (I) was obtained.

Synthesis example 2
EPPN502H (manufactured by Nippon Kayaku Co., Ltd., salicylaldehyde type epoxy resin, in general formula (III), X = glycidyl group) 330 parts, acrylic acid 144 parts, hydroquinone 1.5 parts, carbitol acetate 250 parts The reaction mixture was dissolved by heating to 90 ° C. and stirring. Next, the mixture was cooled to 60 ° C., charged with 2 parts of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mg KOH / g. After cooling, it was diluted with carbitol acetate so that the solid content concentration was 60% by weight to obtain an acid-modified vinyl group-containing epoxy resin (II).

Synthesis example 3
EPPN502H (manufactured by Nippon Kayaku Co., Ltd., salicylaldehyde type epoxy resin, in general formula (III), X = glycidyl group) 330 parts, acrylic acid 144 parts, hydroquinone 1.5 parts, carbitol acetate 250 parts The reaction mixture was dissolved by heating to 90 ° C. and stirring. Next, the mixture was cooled to 60 ° C., charged with 2 parts of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mg KOH / g. Next, 230 parts of tetrahydrophthalic anhydride and 180 parts of carbitol acetate are charged, heated to 80 ° C., reacted for about 6 hours, cooled, and diluted with carbitol acetate to a solid content concentration of 60% by weight. A modified vinyl group-containing epoxy resin (III) was obtained.

Synthesis example 4
YDF2001 (manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin, in general formula (II), X = glycidyl group, R = H) 475 parts, acrylic acid 72 parts, hydroquinone 0.5 part, carbitol acetate 120 parts Was heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C., charged with 2 parts of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mg KOH / g. Next, 98 parts of maleic anhydride and 85 parts of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, cooled, diluted with carbitol acetate to a solid content concentration of 60% by weight, and acid-modified. A vinyl group-containing epoxy resin (IV) was obtained.

Examples 1 to 3 and Comparative Examples 1 to 4
Compositions were blended according to the blending compositions shown in Tables 1 and 2, and kneaded with a three-roll mill to prepare a photocurable resin composition. This is applied to the copper-clad laminate by screen printing using a 120 mesh Tetron screen to a thickness of about 30 μm (after drying), and dried at 80 ° C. for 30 minutes with a hot air circulation dryer. It was. Next, a negative mask having a predetermined pattern was brought into close contact with the coating film and exposed to 500 mJ / cm ² using an ultraviolet exposure device. Thereafter, spray development was performed with a 1% by weight sodium carbonate aqueous solution or chlorocene solvent at a pressure of 1.8 kgf / cm ² for 60 seconds, and the unexposed portion was dissolved and developed. The developability and photosensitivity were evaluated using the obtained image, and then heated at 150 ° C. for 1 hour to prepare a test plate.

  The test plate was tested for adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, and shear adhesion described later. Moreover, the dynamic viscoelasticity was measured about the coating film peeled from the board | substrate (copper clad laminated board). Tables 3 and 4 summarize the evaluation results. The test method and evaluation method are as follows. In FIG. 1, the measurement result of the viscoelasticity of the coating film produced in Example 1 and Comparative Example 1 is shown.

[Photosensitivity]: After drying at 80 ° C., 21 steps of Step tablet (manufactured by Stoffer) were brought into close contact with the coating film, and irradiated with ultraviolet rays with an integrated exposure amount of 500 mJ / cm ^2. Development was performed for 2 seconds, and then the number of steps of the coating film remaining without being developed was confirmed.

○: 8 steps or more Δ: 5 to 7 steps ×: 4 steps or less [Adhesion]: According to JIS K5400, 100 1-mm goblets were prepared on a test piece, and a peel test was performed using a cellophane tape. The state of peeling of the goblet was observed and evaluated according to the following criteria.

○: No peeling at 90/100 or more Δ: No peeling at 50/100 or more and less than 90/100 ×: No peeling at 0/100 to less than 50/100 [Solvent resistance]: Test specimen in isopropyl alcohol at room temperature After dipping for 30 minutes and confirming that there was no abnormality in the appearance, a peel test was performed with a cellophane tape.

○: No abnormality in the coating film appearance and no peeling ×: No abnormality in the coating film appearance or peeling off [acid resistance]: The test piece was immersed in a 10 wt% hydrochloric acid aqueous solution at room temperature for 30 minutes, After confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape.

○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the coating film appearance or peeling off [alkali resistance]: The test piece was immersed in a 5 wt% sodium hydroxide aqueous solution at room temperature for 30 minutes Then, after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape.

○: No abnormality in the coating film appearance and no peeling ×: No abnormality in the coating film appearance or peeling off [Solder heat resistance]: Apply rosin-based flux or water-soluble flux to the test piece, 260 It was immersed in a solder bath at 0 ° C. for 10 seconds. This was defined as one cycle, and after repeating 6 cycles, the appearance of the coating film was visually observed.

○: No abnormal appearance (peeling or blistering) in the coating film appearance and no solder peeling ×: Abnormality (peeling or blistering) in the coating film appearance or solder peeling [shear adhesiveness]: A sealing material (CEL9200 manufactured by Hitachi Chemical Co., Ltd.) was molded into a test piece having a conical shape with a diameter of 3.6 mm and a height of 4 mm, and the adhesion after moisture absorption was evaluated.
The equipment used is a bond tester (DΑGE), measuring temperature 245 ° C.

[Thermal shock resistance]: The test piece was subjected to thermal history with -55 ° C./30 minutes and 125 ° C./30 minutes as one cycle, and after 1,000 cycles, the test piece was visually observed and observed with a microscope.

◯: No crack was generated ×: Crack was generated [Dynamic viscoelasticity]: Dynamic viscoelasticity was measured using a solid analyzer RSA II (manufactured by Rheometrics) at a vibration frequency of 1 Hz (6.28 rad / sec). Sample size is 22.5 x width 3.0 x thickness 0.06mm, measurement temperature 40-250 ° C (temperature rise 5 ° C / min), strain 0.15%, mode static force tracking The dynamic force was set as 15.0 g of the initial static force, and the viscoelasticity at 220 ° C. was examined.

The graph which shows the measurement result of the viscoelasticity of the coating film produced in Example 1 and Comparative Example 1. FIG.

Claims (2)

Contains acid-modified vinyl group-containing epoxy resin (A), olefin elastomer and / or polyester elastomer (B), photopolymerization initiator (C), diluent (D), curing agent (E) and barium sulfate and silica. A photocurable resin composition containing an inorganic filler as an essential component,
Tetrahydrophthalic anhydride is obtained by reacting the acid-modified vinyl group-containing epoxy resin (A) with a resin obtained by reacting an epoxy resin containing a novolac type epoxy resin represented by the general formula (I) with a vinyl group-containing monocarboxylic acid. A resin obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride containing
The diluent (D) contains a polyvalent (meth) acrylate of dipentaerythritol,
A surface-mounting type photocurable resin composition for a semiconductor package, wherein the cured film of the photocurable resin composition has an elastic modulus of 1 to 100 MPa as measured by dynamic viscoelasticity in a 200 to 220 ° C. region.

(In the formula, X is a hydrogen atom or glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), R is a hydrogen atom or methyl group, and n is an integer of 1 or more. )   A photosensitive element formed by laminating a layer of the photo-curable resin composition for a surface-mounting type semiconductor package according to claim 1 on a support.

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