JP6003053B2 - Photosensitive resin composition for protective film of printed wiring board for semiconductor package and semiconductor package - Google Patents

Description

  The present invention relates to a photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package and a semiconductor package using the same.

  In the field of printed wiring boards, conventionally, a permanent mask resist (protective film) is formed on a printed wiring board. This permanent mask resist has a role of preventing the solder from adhering to unnecessary portions of the conductor layer of the printed wiring board in the process of flip chip mounting the semiconductor element on the printed wiring board via solder. Further, the permanent mask resist has a role of preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers when the printed wiring board is used.

  Conventionally, the permanent mask resist in printed wiring board manufacture is produced by a method of screen printing a thermosetting or photosensitive resin composition.

  For example, in a flexible wiring board using mounting methods such as FC, TAB, and COF, a thermosetting resin paste is screen printed except for a rigid wiring board, an IC chip, an electronic component, or an LCD panel and a connection wiring pattern portion, A permanent mask resist is formed by thermosetting (see, for example, Patent Document 1).

  Further, in a semiconductor package substrate such as BGA (ball grid array) and CSP (chip size package) mounted on a personal computer, (1) a semiconductor element is flip-chip mounted on the semiconductor package substrate via solder. (2) In order to wire-bond the semiconductor element and the semiconductor package substrate, (3) In order to solder-bond the semiconductor package substrate to the mother board, it is necessary to remove the permanent mask resist at the bonding portion. Such a photosensitive resin composition that can be easily removed is used as a permanent mask resist (see, for example, Patent Document 2).

  On the other hand, as a light-shielding material for forming a black matrix for a plasma display, a light-shielding film-forming photosensitive resin composition made of a specific metal oxide has been studied (for example, see Patent Document 3).

  When forming a thick resist layer using a colored photosensitive resin composition, increasing the amount of exposure to ultraviolet radiation to improve the bottom curability of the resist layer increases the halation accordingly, and the resist pattern cross section There is a problem that the line width of the intermediate portion and the deepest portion becomes larger than the line width of the surface portion of the surface portion, and the resolution is lowered.

  Therefore, in order to obtain a pattern with excellent resolution, the coloring includes a phosphine oxide and a hydrogen abstraction type polymerization initiator in a ratio of 5 to 40% by mass of the hydrogen abstraction type polymerization initiator with respect to the phosphine oxide. A photosensitive resin composition has been studied (Patent Document 4).

JP 2003-198105 A Japanese Patent Laid-Open No. 11-240930 JP-A-9-160243 JP 2006-276221 A

  However, when forming a via hole using the colored photosensitive resin composition as described above, if it is attempted to cure to the bottom of the resist, the developability of the bottom of the unexposed portion is reduced, and the bottom is skirted. The resulting via opening diameter tends to be smaller than the design dimension.

  The present invention has been made in view of the above-described problems of the prior art, and is a protective film for a printed wiring board for a semiconductor package that can form a resist film that has excellent bottom curability and has a sufficiently reduced bottom foot. An object of the present invention is to provide a photosensitive resin composition.

  When the bottom surface curability of the exposed portion in the photosensitive layer formed from the photosensitive resin composition is insufficient, an undercut may occur in the resist pattern after development. On the other hand, if it is attempted to cure to the bottom of the exposed part, the developability of the bottom part in the unexposed part is deteriorated, resulting in the development residue, and the trailing edge tends to occur from the bottom part of the exposed part to the unexposed part side. On the other hand, the present inventors combined a specific photopolymerization initiator and a sensitizer within a predetermined range, and combined with a specific epoxy resin, thereby improving the bottom curability of the exposed portion and reducing the bottom skirt. It has been found that a sufficiently reduced resist film can be formed.

  The present invention includes (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) an acyl sulfonate oxide polymerization initiator, and (D) an increase in which the maximum absorption wavelength is in the range of 350 to 420 nm. A photosensitive resin composition containing a sensitizer and (E) inorganic fine particles, wherein (C) an acyl phosphine oxide polymerization initiator and (D) a sensitizer having a maximum absorption wavelength in the range of 350 to 420 nm. The content is 0.2 to 15% by mass based on the total solid content of the photosensitive resin composition, and (D) the maximum absorption wavelength with respect to the (C) acylphosphine oxide polymerization initiator is 350 to 420 nm. Provided is a photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package, wherein the content of the sensitizer within the range is 0.5 to 4% by mass.

  According to such a photosensitive resin composition, by having the above configuration, it is possible to form a resist film that is excellent in bottom curability and has a sufficiently reduced bottom foot. Therefore, it is possible to form a via having a via diameter and a pitch between vias close to the design dimension and having excellent resolution. Therefore, the photosensitive resin composition of the present invention is very useful as a photosensitive resin composition for a protective film of a printed wiring board for semiconductor packages.

  In the photosensitive resin composition of the present invention, the (A) acid-modified vinyl group-containing epoxy resin is represented by the following general formula (4) from the viewpoint of being capable of alkali development and being excellent in resolution and adhesiveness. Novolak type epoxy resin, bisphenol type epoxy resin represented by the following general formula (5), salicylaldehyde type epoxy resin represented by the following general formula (6), and the following general formula (7) or (8) A resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of bisphenol-type novolak resins having a repeating unit represented by: and a vinyl group-containing monocarboxylic acid (b), A resin obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride (c) is preferred.

［式（４）中、Ｒ^１１は水素原子又はメチル基を示し、Ｙ^１は水素原子又はグリシジル基を示し、ｎ１は１以上の整数を示す。なお、複数存在するＲ^１１及びＹ^１はそれぞれ同一でも異なっていてもよい。但し、少なくとも一つのＹ^１はグリシジル基を示す。］

[In Formula (4), R ¹¹ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a glycidyl group, and n 1 represents an integer of 1 or more. A plurality of R ¹¹ and Y ¹ may be the same or different. However, at least one Y ¹ represents a glycidyl group. ]

［式（５）中、Ｒ^１２は水素原子又はメチル基を示し、Ｙ^２は水素原子又はグリシジル基を示し、ｎ２は１以上の整数を示す。なお、複数存在するＲ^１２は同一でも異なっていてもよい。また、ｎ２が２以上の場合、複数存在するＹ^２は同一でも異なっていてもよい。］

[In the formula (5), R ¹² represents a hydrogen atom or a methyl group, Y ² represents a hydrogen atom or a glycidyl group, and n2 represents an integer of 1 or more. A plurality of R ¹² may be the same or different. Also, in the case of n2 is 2 or more, Y ² existing in plural numbers may be the same or different. ]

［式（６）中、Ｙ^３は水素原子又はグリシジル基を示し、ｎ３は１以上の整数を示す。なお、複数存在するＹ^３は同一でも異なっていてもよい。但し、少なくとも一つのＹ^３はグリシジル基を示す。］

Wherein (6), ^{Y 3} represents a hydrogen atom or a glycidyl group, n3 is an integer of 1 or more. A plurality of Y ³ may be the same or different. However, at least one Y ³ represents a glycidyl group. ]

［式（７）中、Ｒ^１３は水素原子又はメチル基を示し、Ｙ^４及びＹ^５はそれぞれ独立に水素原子又はグリシジル基を示す。なお、２つのＲ^１３は同一でも異なっていてもよい。但し、Ｙ^４及びＹ^５の少なくとも一方はグリシジル基を示す。］

[In Formula (7), R ¹³ represents a hydrogen atom or a methyl group, and Y ⁴ and Y ⁵ each independently represent a hydrogen atom or a glycidyl group. Two R ¹³ may be the same or different. However, at least one of Y ⁴ and Y ⁵ represents a glycidyl group. ]

［式（８）中、Ｒ^１４は水素原子又はメチル基を示し、Ｙ^６及びＹ^７はそれぞれ独立に水素原子又はグリシジル基を示す。なお、２つのＲ^１４は同一でも異なっていてもよい。但し、Ｙ^６及びＹ^７の少なくとも一方はグリシジル基を示す。］

Wherein ^{(8), R 14} represents hydrogen atom or a methyl group, respectively ^{Y 6} and ^{Y 7} are independently a hydrogen atom or glycidyl group. Two R ¹⁴ may be the same or different. However, at least one of Y ⁶ and Y ⁷ represents a glycidyl group. ]

  In the photosensitive resin composition of the present invention, the sensitizer preferably contains at least one compound selected from the group consisting of a dialkylaminobenzophenone compound and a xanthone compound.

  The present invention also provides a semiconductor package having a permanent resist layer made of a cured product of the photosensitive resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition for protective films of the printed wiring board for semiconductor packages which can be excellent in bottom part curability and can form the resist film which fully reduced the bottom | bottom (foot) of the bottom part can be provided.

It is a figure which shows typically the cross section of a semiconductor package. It is a figure which shows typically the cross section of a via opening part. It is a figure which shows typically the via diameter of a negative film, and the pitch between vias.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. In the present invention, (meth) acryl means acryl and methacryl corresponding thereto, and (meth) acrylate means acrylate and methacrylate corresponding thereto.

[Photosensitive resin composition]
The photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package according to the present invention comprises (A) an acid-modified vinyl group-containing epoxy resin (hereinafter sometimes referred to as “component (A)”) and (B) photopolymerization. Compound (hereinafter referred to as “component (B)” in some cases), (C) acylphosphine oxide polymerization initiator (hereinafter referred to as “component (C)” in some cases), and (D) a maximum absorption wavelength of 350 A sensitizer (hereinafter sometimes referred to as “component (D)”) in the range of −420 nm and (E) inorganic fine particles (hereinafter sometimes referred to as “component (E)”), The content of the component (C) and the component (D) is 0.2 to 15% by mass based on the total solid content of the photosensitive resin composition, and the content ratio of the component (D) to the component (C) is It is characterized by being 0.5 to 4% by mass. Hereinafter, each component will be described in detail.

<(A) Acid-modified vinyl group-containing epoxy resin>
(A) As an acid-modified vinyl group-containing epoxy resin, for example, a resin obtained by modifying an epoxy resin with a vinyl group-containing monocarboxylic acid can be used. In particular, a novolac type epoxy represented by the following general formula (4) Resin, bisphenol type epoxy resin represented by the following general formula (5), salicylaldehyde type epoxy resin represented by the following general formula (6), and repetition represented by the following general formula (7) or (8) Use of a resin (A ′) obtained by reacting at least one epoxy resin (a) selected from the group consisting of bisphenol-type novolak resins having units with a vinyl group-containing monocarboxylic acid (b) Is preferred.

［式（４）中、Ｒ^１１は水素原子又はメチル基を示し、Ｙ^１は水素原子又はグリシジル基を示し、ｎ１は１以上の整数を示す。なお、複数存在するＲ^１１及びＹ^１はそれぞれ同一でも異なっていてもよい。但し、少なくとも一つのＹ^１はグリシジル基を示す。］

[In Formula (4), R ¹¹ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a glycidyl group, and n 1 represents an integer of 1 or more. A plurality of R ¹¹ and Y ¹ may be the same or different. However, at least one Y ¹ represents a glycidyl group. ]

［式（５）中、Ｒ^１２は水素原子又はメチル基を示し、Ｙ^２は水素原子又はグリシジル基を示し、ｎ２は１以上の整数を示す。なお、複数存在するＲ^１２は同一でも異なっていてもよい。また、ｎ２が２以上の場合、複数存在するＹ^２は同一でも異なっていてもよい。］

[In the formula (5), R ¹² represents a hydrogen atom or a methyl group, Y ² represents a hydrogen atom or a glycidyl group, and n2 represents an integer of 1 or more. A plurality of R ¹² may be the same or different. Also, in the case of n2 is 2 or more, Y ² existing in plural numbers may be the same or different. ]

［式（６）中、Ｙ^３は水素原子又はグリシジル基を示し、ｎ３は１以上の整数を示す。なお、複数存在するＹ^３は同一でも異なっていてもよい。但し、少なくとも一つのＹ^３はグリシジル基を示す。］

Wherein (6), ^{Y 3} represents a hydrogen atom or a glycidyl group, n3 is an integer of 1 or more. A plurality of Y ³ may be the same or different. However, at least one Y ³ represents a glycidyl group. ]

［式（７）中、Ｒ^１３は水素原子又はメチル基を示し、Ｙ^４及びＹ^５はそれぞれ独立に水素原子又はグリシジル基を示す。なお、２つのＲ^１３は同一でも異なっていてもよい。但し、Ｙ^４及びＹ^５の少なくとも一方はグリシジル基を示す。］

[In Formula (7), R ¹³ represents a hydrogen atom or a methyl group, and Y ⁴ and Y ⁵ each independently represent a hydrogen atom or a glycidyl group. Two R ¹³ may be the same or different. However, at least one of Y ⁴ and Y ⁵ represents a glycidyl group. ]

［式（８）中、Ｒ^１４は水素原子又はメチル基を示し、Ｙ^６及びＹ^７はそれぞれ独立に水素原子又はグリシジル基を示す。なお、２つのＲ^１４は同一でも異なっていてもよい。但し、Ｙ^６及びＹ^７の少なくとも一方はグリシジル基を示す。］

Wherein ^{(8), R 14} represents a hydrogen atom or a methyl group, respectively ^{Y 6} and ^{Y 7} are independently a hydrogen atom or a glycidyl group. Two R ¹⁴ may be the same or different. However, at least one of Y ⁶ and Y ⁷ represents a glycidyl group. ]

  The resin (A ′) is presumed to have a hydroxyl group formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b).

  Examples of the novolak type epoxy resin represented by the general formula (4) include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting a phenol novolak resin, a cresol novolak resin and epichlorohydrin by a known method.

  As the epoxy resin (a), a novolac type epoxy resin represented by the general formula (4) is preferable from the viewpoint of excellent process tolerance and improved solvent resistance.

  Examples of the phenol novolak type epoxy resin or cresol novolak type epoxy resin represented by the general formula (4) include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, and YDPN- 602 (above, Toto Kasei Co., Ltd., trade name), DEN-431, DEN-439 (above, Dow Chemical Co., Ltd., trade name), EOCN-120, EOCN-102S, EOCN-103S, EOCN- 104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (above, Nippon Kayaku Co., Ltd., trade name), EPN-1138, EPN-1235, EPN-1299 (above, Ciba Specialty Chemicals ( Co., Ltd., trade name), N-730, N-770, N- 65, N-665, N-673, VH-4150, VH-4240 (or more, Dainippon Ink & Chemicals Co., Ltd., trade name) and the like are commercially available.

Further, it indicated by general formula (5), ^{Y 2} is a glycidyl group;

であるビスフェノールＡ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、下記一般式（９）で示されるビスフェノールＡ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とを反応させることにより得ることができる。

The bisphenol A type epoxy resin and the bisphenol F type epoxy resin can be obtained, for example, by reacting the hydroxyl group of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the following general formula (9) with epichlorohydrin. it can.

［式中、Ｒ^１２は水素原子又はメチル基を示し、ｎ２は１以上の整数を示す。］

[Wherein, R ¹² represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more. ]

  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, 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 tend to occur.

  Examples of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (5) include, for example, Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (above, Japan Epoxy Resin) (Trade name), DER-330, DER-301, DER-361 (above, product name, manufactured by Dow Chemical Co., Ltd.), YD-8125, YDF-170, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (above, manufactured by Toto Kasei Co., Ltd., trade name) and the like are commercially available.

  As the salicylaldehyde type epoxy resin represented by the general formula (6), for example, FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) and the like are commercially available. It is.

  The epoxy resin (a) is a repeating unit represented by the general formula (7) and / or the general formula (8) from the viewpoint of further reducing the warpage of the thin film substrate and further improving the thermal shock resistance. It is preferable to use an epoxy resin having

In the above general formula (8), R ¹⁴ is a hydrogen atom and Y ⁶ and Y ⁷ are glycidyl groups as EXA-7376 series (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) and R ¹⁴ In which Y ⁶ and Y ⁷ are glycidyl groups are commercially available as EPON SU8 series (trade name, manufactured by Japan Epoxy Resin Co., Ltd.).

  Examples of the vinyl group-containing monocarboxylic acid (b) include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α- Acrylic acid derivatives such as cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides The half-ester compound which is a reaction product of is mentioned.

  The half ester compound is obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids (b) can be used singly 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.

  As a dibasic acid anhydride used for the synthesis | combination of the said half ester compound, what contains a saturated group and what contains an unsaturated group can be used. Specific examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Examples include acid, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b), the vinyl group-containing monocarboxylic acid (b) is 0.6 to 1 with respect to 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, and it is more preferable to make it react by the ratio used as 0.8-1.0 equivalent.

  The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be reacted by dissolving in an organic solvent. 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.

  Furthermore, it is preferable to use a catalyst to promote the reaction. As the catalyst, for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like can be used. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the 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 like. The amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). Moreover, reaction temperature becomes like this. Preferably it is 60-150 degreeC, More preferably, it is 80-120 degreeC.

  Further, if necessary, a vinyl group-containing monocarboxylic acid (b) and a phenolic compound such as p-hydroxyphenethyl alcohol, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic acid A polybasic acid anhydride such as an anhydride can be used in combination.

  In this embodiment, as the acid-modified vinyl group-containing epoxy resin (A), a resin (A ″) obtained by reacting the above-mentioned resin (A ′) with a polybasic acid anhydride (c) is used. You can also

  In the resin (A ″), the hydroxyl group in the resin (A ′) (including the original hydroxyl group in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) are half-esterified. It is presumed that

  As the polybasic acid anhydride (c), one containing a saturated group or one containing an unsaturated group can be used. Specific examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like can be mentioned.

  In the reaction of the resin (A ′) and the polybasic acid anhydride (c), the polybasic acid anhydride (c) is 0.1 to 1.0 equivalent per 1 equivalent of the hydroxyl group in the resin (A ′). By reacting, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted.

  (A) The acid value of the acid-modified vinyl group-containing epoxy resin is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g. If the acid value is less than 30 mg KOH / g, the solubility of the photosensitive resin composition in a dilute alkaline solution tends to be reduced, and if it exceeds 150 mg KOH / g, the electric properties of the cured film tend to be reduced.

  The reaction temperature between the resin (A ′) and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.

  Moreover, as needed, as a epoxy resin (a), hydrogenated bisphenol A type epoxy resin can also be used together partially, for example. Further, (A) acid-modified vinyl group-containing epoxy resin, styrene-maleic acid series such as hydroxyethyl acrylate modified product of styrene-maleic anhydride copolymer or hydroxyethyl acrylate modified product of styrene-maleic anhydride copolymer A part of the resin may be used in combination.

  In the photosensitive resin composition, the content of the component (A) is preferably 5 to 60% by mass and more preferably 10 to 50% by mass based on the total solid content of the photosensitive resin composition. Preferably, it is 15-40 mass%, and it is especially preferable. When the content of the component (A) is within the above range, a coating film that is superior in heat resistance, electrical characteristics, and chemical resistance can be obtained.

<(B) Photopolymerizable compound>
Although it does not specifically limit as a photopolymerizable compound which is (B) component, The compound which has at least 1 ethylenically unsaturated group in a molecule | numerator can be used, and the compound whose molecular weight is 1000 or less is preferable. As the component (B), for example, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and monoglycols such as ethylene glycol, methoxytetraethylene glycol and polyethylene glycol Or (meth) acrylamides such as di (meth) acrylates, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, and aminoalkyls such as N, N-dimethylaminoethyl (meth) acrylate (meta) ) Polyhydric alcohols such as acrylates, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like. Polyhydric (meth) acrylates of oxides or propylene oxide adducts, phenoxyethyl (meth) acrylates, ethylene oxides of phenols such as polyethoxydi (meth) acrylate of bisphenol A, or (meth) acrylates of propylene oxide adducts, (Meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and melamine (meth) acrylate, acrylamide, acrylonitrile, diacetone acrylamide, styrene, vinyltoluene, etc. . These (B) photopolymerizable compounds are used singly or in combination of two or more.

  In the photosensitive resin composition, the content of the component (B) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the total solid content of the photosensitive resin composition. It is preferably 3 to 10% by mass. If the content of the component (B) is less than 1% by mass, the photosensitivity tends to be low and the exposed area tends to be eluted during development, and if it exceeds 30% by mass, the heat resistance tends to decrease.

<(C) Acylphosphine-based polymerization initiator>
Examples of (C) acylphosphine-based polymerization initiators include 2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6, trimethylbenzoyl) -phenylphosphine oxide, Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoyldiphenylphosphinate, and the like. These (C) acylphosphine-based polymerization initiators can be used singly or in combination of two or more.

<(D) Sensitizer having a maximum absorption wavelength in the range of 350 to 420 nm>
(D) As a sensitizer having a maximum absorption wavelength in the range of 350 to 420 nm, one or more compounds selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds and xanthone compounds, and / Or their derivatives can be used. The component (D) preferably contains at least one compound selected from the group consisting of dialkylaminobenzophenone compounds and xanthone compounds. The component (D) is more preferably a compound having a maximum absorption wavelength within a wavelength range of 370 nm to 450 nm. Specific examples of the component (D) include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthioxanthone, 2-chlorothioxanthone, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 7-amino-4-methylcoumarin, 7- Examples thereof include dimethylamino-4-methylcoumarin and 7-diethylamino-4-methylcoumarin. These may be used alone or in combination of two or more.

  Although the content rate of (D) component is 0.5-4 mass% with respect to (C) component, it is preferable that it is 0.6-3.8 mass%. When the content ratio of the component (D) is less than 0.5% by mass, the surface gloss of the cured film tends to decrease, and when it exceeds 4% by mass, the heat resistance tends to decrease.

  The content of the component (C) and the component (D) is preferably 0.2 to 15% by mass, and 0.2 to 9% by mass based on the total solid content of the photosensitive resin composition. Is more preferable, and it is especially preferable that it is 0.4-8 mass%. When the content of the component (C) and the component (D) is less than 0.2% by mass, the photosensitivity tends to be low and the exposed area tends to be eluted during development, and when it exceeds 15% by mass, an image cannot be obtained.

<(E) Inorganic fine particles>
Examples of the inorganic fine particles (E) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ ). N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT) , lead lanthanum zirconate titanate (PLZT), gallium oxide _{(Ga 2 O} 3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite (2MgO · _2Al 2 O ₃ / 5SiO _2), talc _{(3MgO · 4SiO 2 · H 2} O), aluminum titanate (TiO ₂ - l ₂ O _3), yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), barium sulfate (BaSO _4), sulfuric acid Calcium (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon (C) and the like can be used. These (E) inorganic fine particles can be used singly or in combination of two or more.

  In the photosensitive resin composition, the content of the component (E) is preferably 5 to 30% by mass, more preferably 5 to 20% by mass based on the total solid content of the photosensitive resin composition. 7 to 15% by mass is particularly preferable. When the content of the component (E) is within the above range, the film strength, heat resistance, insulation reliability, thermal shock resistance and resolution can be further improved.

  (E) The inorganic fine particles preferably have a maximum particle size of 0.1 to 20 μm, more preferably 0.1 to 10 μm, particularly preferably 0.1 to 5 μm, and 0.1 to 1 μm. Most preferred. When the maximum particle diameter exceeds 20 μm, the insulation reliability tends to be impaired.

  (E) Among inorganic fine particles, silica fine particles are preferably used from the viewpoint of improving heat resistance, solder heat resistance, HAST property (insulation reliability), crack resistance (heat shock resistance), and PCT resistance test. From the viewpoint of improving the adhesive strength between the later underfill material and the cured film, it is preferable to use barium sulfate fine particles. Moreover, it is preferable that the said barium sulfate microparticles | fine-particles are surface-treated with an alumina and / or an organosilane type compound from a viewpoint which can improve the aggregation prevention effect.

  When barium sulfate is used, the content is preferably 1 to 15% by mass, more preferably 3 to 10% by mass based on the total solid content of the photosensitive resin composition. When the content of the barium sulfate fine particles is within the above range, the solder heat resistance and the adhesive strength between the underfill material after the PCT resistance test and the cured film can be further improved.

  The photosensitive resin composition of the present embodiment further includes (F) a curable compound, (H) an epoxy resin curing agent, and / or (G) an elastomer in addition to the components (A) to (E) described above. You may go out. Hereinafter, each component will be described.

<(F) curable compound>
(F) As the curable compound, a compound that cures itself by heat, ultraviolet light, or the like, or (A) a compound that cures by reacting with a carboxyl group, a hydroxyl group, heat, ultraviolet light or the like of an acid-modified vinyl group-containing epoxy resin preferable. (F) By using a curable compound, the heat resistance, adhesiveness, chemical resistance, etc. of the cured film formed from the photosensitive resin composition can be improved. (F) By containing a curable compound, the via | veer shape of the cured film formed from the photosensitive resin composition can be maintained. The component (F) does not include the component (A).

  (F) As a curable compound, thermosetting compounds, such as an epoxy compound, a melamine compound, a urea compound, an oxazoline compound, block type isocyanate, are mentioned, for example. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. , Naphthalene type epoxy resin, dicyclo type epoxy resin, hydantoin type epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanurate, and bixylenol type epoxy resin. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. Examples of the urea compound include dimethylol urea.

  (F) It is preferable that a curable compound contains an epoxy compound (epoxy resin) and / or block-type isocyanate from a viewpoint which can improve the heat resistance of a cured film more, and an epoxy compound, block-type isocyanate, It is more preferable to use together.

  As the block type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. Polyisocyanate compounds, and adducts, burettes and isocyanurates of these.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  (F) A curable compound is used individually by 1 type or in combination of 2 or more types. (F) When using a sclerosing | hardenable compound, it is preferable that the content is 2-40 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, and it is more preferable that it is 3-30 mass%. 5 to 20% by mass is particularly preferable. (F) By making content of a sclerosing | hardenable compound in the range of 2-40 mass%, the heat resistance of the cured film formed can be improved more, maintaining favorable developability.

<(G) Elastomer>
(G) The elastomer can be suitably used when the photosensitive resin composition of the present invention is used for a semiconductor package substrate. By adding the (G) elastomer to the photosensitive resin composition of the present embodiment, the crosslinking reaction (curing reaction) proceeds by ultraviolet rays or heat, so that the (A) acid-modified vinyl group-containing epoxy resin is cured and contracted. Thus, it is possible to solve the problem that distortion (internal stress) is applied to the inside of the resin and flexibility and adhesiveness are lowered. (G) By containing an elastomer, the heat resistance of the via-shaped part of the cured film formed from the photosensitive resin composition can be improved.

  Examples of (G) elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These (G) elastomers are composed of a hard segment component and a soft segment component. In general, the former 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, styrene-ethylene-propylene-styrene block copolymer, and the like.

  The olefin-based elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. Specific examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, Examples thereof include non-conjugated dienes having 2 to 20 carbon atoms such as isoprene, α-olefin copolymers, and carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymers with methacrylic acid. More 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. Is mentioned. More specifically, Miralastoma (manufactured by Mitsui Chemicals), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (manufactured by JSR), butadiene -Partially epoxidized acrylonitrile copolymer "NBR series" (manufactured by JSR Corporation), or "XER series" of both-end carboxyl group-modified butadiene-acrylonitrile copolymers (manufactured by JSR Corporation), polybutadiene Epoxidized polybudadiene such as BF-1000 (manufactured by Nippon Soda), epolide PB-3600 (manufactured by Daicel Chemical Industries, Ltd.) and the like can be used.

  Examples of the urethane elastomer include those composed of structural units of a hard segment composed of a low molecular glycol and a diisocyanate and a soft segment composed of a polymer (long chain) diol and a diisocyanate.

  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.

  Polyamide elastomers are broadly classified into two types: polyether block amide type and polyether ester block amide type using polyamide for the hard segment and polyether or polyester for the soft segment.

  As the polyamide, polyamide-6, 11, 12 or the like is used. As the polyether, polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used. Specifically, UBE polyamide elastomer (manufactured by Ube Industries Co., Ltd.), Daiamide (manufactured by Daicel Huls Co., Ltd.), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan Co., Ltd.), Nopamid ( Mitsubishi Chemical Co., Ltd.), Glais (Dainippon Ink Co., Ltd.), etc. can be used.

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

  Silicone elastomers are mainly composed of organopolysiloxane, and are 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.

  (G) When using an elastomer, the content is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 10 to 10% by mass. (G) By making the content of the elastomer in the range of 1 to 20% by mass, the thermal shock resistance and the adhesive strength between the underfill material and the cured film can be further improved while maintaining good developability. it can. Moreover, when using for a thin film substrate, the curvature property of a thin film substrate can be reduced.

<(H) Epoxy resin curing agent>
In the photosensitive resin composition of the present embodiment, (H) an epoxy resin curing agent may be added for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the cured film to be formed. it can.

  Specific examples of such (H) epoxy resin curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Imidazole derivatives such as methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide 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 lyazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris ( Tertiary amines such as dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac; tributylphosphine, triphenylphosphine, tris-2-cyanoethyl Organic phosphines such as phosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosnium chloride Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; polybasic acid anhydrides as described above; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexa A fluorophosphate etc. are mentioned. These (H) epoxy resin curing agents are used singly or in combination of two or more.

  (H) When using an epoxy resin hardening | curing agent, it is preferable that the content is 0.01-20 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, and is 0.1-10 mass%. More preferably.

  In addition, (I) a thermoplastic resin can be added to the photosensitive resin composition of the present embodiment in order to further improve the flexibility of the cured film.

  (I) As a thermoplastic resin, an acrylic resin, a urethane resin, etc. are mentioned, for example. (I) When the thermoplastic resin is contained, the content is preferably 1 to 30% by mass and 5 to 20% by mass based on the total solid content of the photosensitive resin composition. More preferred.

  Furthermore, in the photosensitive resin composition of the present embodiment, if necessary, organic fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, Known colorants such as naphthalene black, polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, thickeners such as phenolic compounds, benton, montmorillonite, silicone-based, fluorine-based, vinyl resin-based Various commonly known additives such as foaming agents, silane coupling agents, diluents and the like can be added. Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorous compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can also be added.

  In particular, from the viewpoint of further improving the bottom curability of the resist film and further reducing the skirt, it is preferable to include a phenolic compound. Examples of the phenol compound include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis ( 3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 2,2 '-Methylenebis “6- (methylcyclohexyl) -p-cresol”, 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2,2′-butylidenebis (2-t-butyl-4) -Methylphenol), tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5 Di-t-butyl-4-hydroxybenzyl) benzene, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 4,4′-butylidenebis (3-methyl-6-t-) Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, and the like. Among these, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Phenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) is particularly preferred.

  As the diluent, for example, an organic solvent 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. A diluent is used individually by 1 type or in combination of 2 or more types. Content in the case of using a diluent can be suitably adjusted from a viewpoint of the applicability | paintability of the photosensitive resin composition.

  The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the above-described components with a roll mill, a bead mill or the like.

  For example, the photosensitive resin composition of the present embodiment forms an image as follows and can be used for the production of a cured film.

That is, the photosensitive resin composition of the embodiment is applied to a copper-clad laminate with a film thickness of 10 to 200 μm by a method such as a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, Next, after drying a coating film at 60-110 degreeC, a negative film is made to contact directly (or non-contact through a transparent film), and actinic light (for example, ultraviolet rays) becomes like this. Preferably it is 10-1000 mJ / cm < ² >. After that, the unexposed 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 performed at an exposure amount of 1 to ⁵ J / cm ² , and the post-heating is preferably performed at 100 to 200 ° C. for 30 minutes to 12 hours. The thickness of the coating film made of the photosensitive resin composition after drying is preferably 30 to 100 μm, more preferably 35 to 80 μm, and still more preferably 35 to 60 μm.

  Moreover, the photosensitive resin composition of this embodiment can also be laminated | stacked on a support body, and can also be set as a photosensitive element. The thickness of the layer made of the photosensitive resin composition is preferably 10 to 100 μm, more preferably 30 to 100 μm, still more preferably 35 to 80 μm, and particularly preferably 35 to 60 μm. . As the support, a film having a thickness of 5 to 100 μm such as polyethylene terephthalate is preferably used. The layer made of the photosensitive resin composition is preferably formed by applying and drying a solution of the photosensitive resin composition on a support film.

[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.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Synthesis Example 1: Production of acid-modified vinyl group-containing epoxy resin (A-1)]
Bisphenol F novolak type epoxy resin (EXA-7376, manufactured by Dainippon Ink & Chemicals, Inc.) 350 having a repeating unit represented by the above general formula (8) (R ¹⁴ = hydrogen atom, Y ⁶ and Y ⁷ = glycidyl group) Part by mass, 70 parts by mass of acrylic acid, 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged and reacted by heating to 90 ° C. and stirring to completely dissolve the mixture. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, cooled, and the solid content was 73 parts by mass. % Solution of THPAC-modified bisphenol F type novolac epoxy acrylate (hereinafter referred to as “acid-modified vinyl group-containing epoxy resin (A-1)”) as a component (A).

[Synthesis Example 2: Production Example of Acid-Modified Vinyl Group-Containing Epoxy Resin (A-2)]
382 parts by mass of cresol novolac epoxy resin (ESCN-195, manufactured by Sumitomo Chemical Co., Ltd.) represented by the general formula (4) (R ¹¹ = hydrogen atom, Y ¹ = glycidyl group), 90 parts by mass of acrylic acid, methyl hydroquinone 0.5 parts by mass and 120 parts by mass of carbitol acetate were charged and reacted by heating to 90 ° C. and stirring to completely dissolve the mixture. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. until the acid value of the solution became 1 mgKOH / g or less. To the solution after the reaction, 100 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate are added, heated to 80 ° C. and reacted for about 6 hours, and then cooled to obtain a solid content concentration of 75. %, A solution of THPAC-modified cresol novolac type epoxy acrylate (hereinafter referred to as “acid-modified vinyl group-containing epoxy resin (A-2)”) as component (A).

(Examples 1-6, Comparative Examples 1-4)
Each material shown in the following Table 1 was blended in the blending amount (unit: parts by mass) shown in the same table, then kneaded with a three-roll mill, and carbitol acetate was added so that the solid content concentration became 70% by mass. A photosensitive resin composition was obtained. In addition, the compounding quantity of each material in following Table 1 shows the compounding quantity of solid content.

The details of each material in Table 1 are as follows.
DPHA; dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name),
I819; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals Co., Ltd., trade name),
TPO; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name) manufactured by Ciba Specialty Chemicals,
I907; 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.
DETX-S; 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name, λ = 383 nm),
EAB; 4,4′-bis (diethylamino) benzophenone (manufactured by Hodogaya Chemical Co., Ltd., trade name, λ = 365 nm),
SiO ₂ ; silica fine particles (manufactured by Tatsumori Co., Ltd., trade name: CRS2101-41),
BaSO ₄ ; barium sulfate fine particles (manufactured by Sakai Chemical Co., Ltd., trade name: # 100),
Epicoat 828; Bisphenol A type epoxy resin (trade name, manufactured by Japan Epoxy Resin Co., Ltd.).

[Evaluation of skirting properties]
The photosensitive resin compositions of Examples and Comparative Examples were applied to a copper-clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) by screen printing so that the film thickness after drying was 40 μm. Then, it was dried using a hot air circulation dryer at 75 ° C. for 30 minutes. The obtained coating film was irradiated with ultraviolet rays having an integrated exposure amount of 600 mJ / cm ² through a negative film in which light-opaque portions with via diameters of φ80 μm and φ110 μm were scattered in an area of 1 × 1 cm square. Subsequently, spray development was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm ² , and the unexposed portion was dissolved and developed, and then heated at 150 ° C. for 30 minutes to form a via opening. Heat cured at 150 ° C. for 30 minutes. Thereafter, the cross section of the via opening was observed using a microscope (manufactured by HIROX, model number: KH-3000), the length of the hem was measured, and the skirting property was evaluated. FIG. 2 is a diagram schematically showing a cross section of the via opening of the resist film 1 formed on the copper-clad laminate 4. As shown in FIG. 2, when the length of the skirt is less than 2 μm, the cross section of the resist film is almost rectangular (FIG. 2A), and when the length of the skirt is 2 μm or more, the bottom of the resist film is formed. Bottoming occurs ((b) in FIG. 2). Both skirt lengths of φ80 μm and φ110 μm at the bottom of the via are less than 2 μm. The evaluation results are shown in Table 2.

[Evaluation of pitch between vias]
The photosensitive resin compositions of Examples and Comparative Examples were applied to a copper-clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) by screen printing so that the film thickness after drying was 20 μm. Then, it was dried using a hot air circulation dryer at 75 ° C. for 30 minutes. The obtained coating film was irradiated with ultraviolet rays having an integrated exposure amount of 600 mJ / cm ² through a negative film in which light non-transmitting portions having a via diameter of 100 μm and a pitch of 10 μm were scattered in an area of 1 × 1 cm square. Subsequently, spray development was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm ² , and the unexposed portion was dissolved and developed, and then heated at 150 ° C. for 30 minutes to form a via opening. Then, the cross section of the via opening was observed using a microscope (manufactured by HIROX, model number: KH-3000), and the pitch between vias was evaluated. The evaluation results are shown in Table 2. FIG. 3 is a diagram schematically showing the via diameter (100 μm) and the pitch between vias (10 μm) of the negative film. A pitch length of 7 μm or more is considered acceptable.

[Preparation of test piece]
The photosensitive resin compositions of Examples and Comparative Examples were dried on a copper-clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 0.6 mm so that the film thickness after drying was 25 μm. After coating by screen printing, it was dried at 80 ° C. for 20 minutes using a hot air circulation dryer. Next, a negative mask having a predetermined pattern was brought into close contact with the coating film, and exposed with an exposure amount of 600 mJ / cm ² using an ultraviolet exposure device. Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm ² , and the unexposed portion was dissolved and developed. Next, it exposed with the exposure amount of 1000 mJ / cm < ² > using the ultraviolet exposure apparatus, and heated at 150 degreeC for 1 hour, and produced the test piece.

[Solder heat resistance]
A water-soluble flux was applied to the test piece and immersed in a solder bath at 265 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the coating film was visually observed and evaluated according to the following criteria. The evaluation results are shown in Table 2.
A: No change in appearance.
B: Within 50 mm ² of the coating film, there are 1 to 2 lacquer or swelling of the coating film.
C: There are 3 to 5 lacquers or blisters in the coating film 50 mm ² .
D: There are 6 or more lacquers or blisters in the coating film 50 mm ² .

[Thermal shock resistance]
The test piece was subjected to thermal history with 1 cycle of −55 ° C./30 minutes and 125 ° C./30 minutes, and after 1,000 cycles, the test piece was visually and microscopically evaluated according to the following criteria. The evaluation results are shown in Table 2.
A: No crack occurred.
B: Cracks are generated.

[Warpage]
The photosensitive resin compositions of Examples and Comparative Examples were applied to a copper foil having a length of 5 cm, a width of 5 cm, and a thickness of 18 μm by screen printing so that the film thickness after drying was 25 μm, and then 30 ° C. at 30 ° C. It dried using the hot-air circulation type dryer for a minute, and exposed with the exposure amount of 600 mJ / cm < ² > using the ultraviolet-ray exposure apparatus. Thereafter, spraying was performed with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm ² . Next, it exposed with the exposure amount of 1000 mJ / cm < ² > using the ultraviolet exposure apparatus, and heated at 150 degreeC for 1 hour, and obtained the test piece for curvature evaluation. The obtained test piece was placed on a surface plate with the coating surface down, and the warp height was evaluated. The evaluation results are shown in Table 2.

  It has been confirmed that the photosensitive resin composition having the configuration of the present invention has an excellent bottom curability and can form a via shape with sufficiently reduced skirting.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition for protective films of the printed wiring board for semiconductor packages which can be excellent in bottom part curability and can form the resist film which fully reduced the bottom | bottom (foot) of the bottom part can be provided.

  DESCRIPTION OF SYMBOLS 1 ... Resist film, 4 ... Copper clad laminated substrate, 10 ... Semiconductor package, 50 ... Semiconductor chip mounting substrate, 90 ... Permanent resist layer, 110 ... Wire terminal for wire bonding, 111 ... Connection terminal for solder connection, 114 ... Solder Balls, 115... Gold wire, 116... Semiconductor sealing resin, 117. Adhesive, 120.

Claims (4)

(A) vinyl-group-containing Yuki fat, (B) a photopolymerizable compound, (C) acyl phosphine oxide-based polymerization initiator, a sensitizer in the range of (D) a maximum absorption wavelength 350 to 420 nm, and (E) a photosensitive resin composition containing inorganic fine particles,
Wherein the (A) vinyl-group-containing Yuki fat, the following general formula (7) or at least one epoxy resin selected from bisphenol type novolak resin having a repeating unit represented by (8) (a), A reaction product with a vinyl group-containing monocarboxylic acid (b),
The content of the (C) acylphosphine oxide polymerization initiator and the (D) sensitizer having a maximum absorption wavelength in the range of 350 to 420 nm is 0. 0 based on the total solid content of the photosensitive resin composition. The content ratio of the sensitizer is 2 to 15% by mass, and the (D) maximum absorption wavelength with respect to the (C) acylphosphine oxide polymerization initiator is in the range of 350 to 420 nm. The photosensitive resin composition for protective films of the printed wiring board for semiconductor packages which is mass%.

[In Formula (7), R ¹³ represents a hydrogen atom or a methyl group, and Y ⁴ and Y ⁵ each independently represent a hydrogen atom or a glycidyl group. Two R ¹³ may be the same or different. However, at least one of Y ⁴ and Y ⁵ represents a glycidyl group. ]

Wherein ^{(8), R 14} represents a hydrogen atom or a methyl group, respectively ^{Y 6} and ^{Y 7} are independently a hydrogen atom or a glycidyl group. Two R ¹⁴ may be the same or different. However, at least one of Y ⁶ and Y ⁷ represents a glycidyl group. ] (A) the vinyl-group-containing Yuki fat, and the reaction product is a reaction product of a saturated or unsaturated group-containing polybasic acid anhydride (c), the photosensitive resin composition according to claim 1 .   The photosensitive resin composition according to claim 1 or 2, wherein the sensitizer includes at least one compound selected from the group consisting of a dialkylaminobenzophenone compound and a xanthone compound. The semiconductor package which has a permanent resist layer which consists of a hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-3.

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