JP2008297540A - Photosensitive adhesive resin composition, adhesive film and light-receiving device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive adhesive resin composition having excellent developability and is used for a spacer which is arranged between a transparent substrate and a substrate on which a semiconductor element is mounted, and to provide an adhesive film using the same and a light-receiving device. <P>SOLUTION: The photosensitive adhesive resin composition comprises a compound (A) having a hydroxy group or carboxy group and a (meth)acryloyl group, a compound (B) thermosettingly reactive with the compound (A) having the hydroxy group or carboxy group and the (meth)acryloyl group, a compound (C) having a (meth)acryloyl group but not having a hydroxy group and a carboxy group, a phenol resin or phenols (D), and a sensitizer (E). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive adhesive resin composition, an adhesive film, and a light receiving device.

  In recent years, there has been a demand for a photosensitive film that can be bonded to a transparent substrate such as glass after a photosensitive film is bonded to a semiconductor wafer or the like and a pattern is formed by exposure and development (see, for example, Patent Document 1). When such a photosensitive film is used, the patterned photosensitive film has a function of a spacer between the semiconductor wafer and the transparent substrate.

This spacer resin composition is required to be capable of being patterned by a photolithography method and capable of retaining a shape as a spacer.
Further, as described above, the resin composition for spacers is also required to have excellent developability because it undergoes exposure and development processes.

JP 2006-323089 A, [Claim 1] to [Claim 20]

An object of the present invention is to provide a photosensitive adhesive resin composition excellent in developability used for manufacturing a spacer between a transparent substrate and a substrate on which a semiconductor element is mounted, and an adhesive film using the same. It is in.
Another object of the present invention is to provide a light receiving device in which a transparent substrate and a substrate on which a semiconductor element is mounted are bonded via a spacer formed of a cured product of the photosensitive adhesive resin composition. It is in.

で表される（メタ）アクリロイル変性ビスフェノールＡ、又は下記一般式（２）：

（式中、ｎは２〜１５の整数を示す。）
で表されるノボラック型ビスフェノールＡ樹脂の水酸基の一部が、下記式（３）：

で表される基で置換された（メタ）アクリロイル変性ノボラック型ビスフェノールＡ樹脂である、（１）に記載の感光性接着剤樹脂組成物。
（４）前記感光性接着剤樹脂組成物中の前記フェノール樹脂又はフェノール類（Ｄ）の含有量が、０．１〜２０質量％である、（１）ないし（３）のいずれかに記載の感光性接着剤樹脂組成物。
（５）前記フェノール樹脂又はフェノール類（Ｄ）が、ノボラック型フェノール樹脂又はフェノールモノマーである、（１）ないし（４）のいずれかに記載の感光性接着剤樹脂組成物。
（６）さらに、充填材（Ｆ）を含む、（１）ないし（５）のいずれかに記載の感光性接着剤樹脂組成物。
（７）前記感光性接着剤樹脂組成物中の前記充填材（Ｆ）の含有量が、３〜５０質量％である、（６）に記載の感光性接着剤樹脂組成物。
（８）前記充填材（Ｆ）の平均粒径が、０．０３〜０．４μｍである、（６）または（７）に記載の感光性接着剤樹脂組成物。
（９）前記充填材（Ｆ）が、シリカフィラーである、（６）ないし（８）の何れかに記載
の感光性接着剤樹脂組成物。
（１０）前記水酸基又はカルボキシル基と（メタ）アクリロイル基とを有する化合物（Ａ）と熱硬化反応する樹脂（Ｂ）が、２５℃で固形のエポキシ樹脂と、２５℃で液状のシリコーン変性エポキシ樹脂との組合せである、（１）ないし（９）のいずれかに記載の感光性接着剤樹脂組成物。
（１１）基材フィルムと、前記基材フィルムの表面に形成される接着層と、からなり、前記接着層が、（１）ないし（１０）のいずれかに記載の感光性接着剤樹脂組成物であることを特徴とする、接着フィルム。
（１２）半導体素子が搭載される基板と、前記半導体素子が搭載される基板と対向する透明基板と、前記透明基板と前記半導体素子が搭載される基板との間に設けられたスペーサーと、を備え、前記スペーサーが、（１）ないし（１１）のいずれかに記載の感光性接着剤樹脂組成物の硬化物であることを特徴とする受光装置。 Such an object can be achieved by the techniques described in the following (1) to (12). (1) A compound (A) having a hydroxyl group or a carboxyl group and a (meth) acryloyl group, and a resin (B) which undergoes a thermosetting reaction with the compound (A) having a hydroxyl group or a carboxyl group and a (meth) acryloyl group. , A compound (C) having a (meth) acryloyl group and not having a hydroxyl group or a carboxyl group, a phenol resin or phenols (D), and a photosensitizer (E). Adhesive resin composition.
(2) The photosensitive adhesive resin composition according to (1), wherein the compound (A) having the hydroxyl group or carboxyl group and the (meth) acryloyl group is a (meth) acryloyl-modified novolac type phenol resin.
(3) The compound (A) having the hydroxyl group or carboxyl group and the (meth) acryloyl group has the following chemical formula (1):

(Meth) acryloyl-modified bisphenol A represented by the following general formula (2):

(In the formula, n represents an integer of 2 to 15.)
A part of the hydroxyl groups of the novolac bisphenol A resin represented by the following formula (3):

The photosensitive adhesive resin composition according to (1), which is a (meth) acryloyl-modified novolac-type bisphenol A resin substituted with a group represented by:
(4) The content of the phenol resin or phenols (D) in the photosensitive adhesive resin composition is 0.1 to 20% by mass, according to any one of (1) to (3). Photosensitive adhesive resin composition.
(5) The photosensitive adhesive resin composition according to any one of (1) to (4), wherein the phenol resin or the phenol (D) is a novolak type phenol resin or a phenol monomer.
(6) The photosensitive adhesive resin composition according to any one of (1) to (5), further including a filler (F).
(7) The photosensitive adhesive resin composition according to (6), wherein the content of the filler (F) in the photosensitive adhesive resin composition is 3 to 50% by mass.
(8) The photosensitive adhesive resin composition as described in (6) or (7) whose average particle diameter of the said filler (F) is 0.03-0.4 micrometer.
(9) The photosensitive adhesive resin composition according to any one of (6) to (8), wherein the filler (F) is a silica filler.
(10) The resin (B) that undergoes a thermosetting reaction with the compound (A) having the hydroxyl group or carboxyl group and (meth) acryloyl group is a solid epoxy resin at 25 ° C. and a silicone-modified epoxy resin that is liquid at 25 ° C. The photosensitive adhesive resin composition according to any one of (1) to (9), which is a combination thereof.
(11) The photosensitive adhesive resin composition according to any one of (1) to (10), comprising a base film and an adhesive layer formed on a surface of the base film. An adhesive film, characterized in that
(12) A substrate on which a semiconductor element is mounted, a transparent substrate facing the substrate on which the semiconductor element is mounted, and a spacer provided between the transparent substrate and the substrate on which the semiconductor element is mounted. And the spacer is a cured product of the photosensitive adhesive resin composition according to any one of (1) to (11).

According to the present invention, a photosensitive adhesive resin composition excellent in developability used for manufacturing a spacer between a transparent substrate and a substrate on which a semiconductor element is mounted, an adhesive film manufactured using the same, and A light receiving device can be provided.
Another object of the present invention is to provide a light receiving device in which a transparent substrate and a substrate on which a semiconductor element is mounted are bonded via a spacer formed of a cured product of the photosensitive adhesive resin composition. It is in.

Hereinafter, preferred embodiments of the photosensitive adhesive resin composition, the adhesive film, and the light receiving device of the present invention will be described in detail.
1. Photosensitive adhesive resin composition The photosensitive adhesive resin composition of the present invention comprises a resin (A) having a hydroxyl group or a carboxyl group and a (meth) acryloyl group (hereinafter also referred to as compound (A)). A resin (B) that undergoes a thermosetting reaction with the compound (A) having the hydroxyl group or carboxyl group and a (meth) acryloyl group (hereinafter also referred to as compound (B));
A compound (C) having a (meth) acryloyl group and not having a hydroxyl group or a carboxyl group (hereinafter also referred to as compound (C));
Phenol resin or phenols (D) (hereinafter also referred to as compound (D));
Photosensitizer (E),
It is characterized by including. In particular, by containing a phenol resin or phenols (D), the solubility in an alkaline developer is improved after the photosensitive adhesive resin composition is exposed to light, so that the developability is improved.

であり、メタクリロイル基は

である。 In the present invention, the (meth) acryloyl group refers to an acryloyl group or a methacryloyl group. The acryloyl group is

And the methacryloyl group is

It is.

  In the photosensitive adhesive resin composition of the present invention, the compound (A) is a (meth) acryloyl-modified novolak type phenol resin, so that the amount of phenolic hydroxyl groups in the photosensitive adhesive resin composition is increased. Therefore, the solubility in an alkali developer is improved, and the developability is further improved.

  The compound (A) according to the present invention is a compound having a hydroxyl group or a carboxyl group and having a (meth) acryloyl group. The compound (A) is soluble in an alkali developer, has a hydroxyl group or a carboxyl group that reacts with the compound (B), and has a (meth) acryloyl group that reacts with both light and heat. If it has, it will not be restrict | limited in particular.

The weight average molecular weight of the compound (A) is 200 to 7000, preferably 300 to 500.
0. When the weight average molecular weight of the compound (A) is within the above range,
Since the solubility of the compound (A) is increased, the developability is improved. In the present invention, the weight level
The average molecular weight is measured by GPC (gel permeation chromatograph) and expressed in terms of polystyrene.
It is obtained.

  The number of hydroxyl groups or carboxyl groups in one molecule of the compound (A) is preferably 1 to 25, particularly preferably 2 to 20. When the number of hydroxyl groups or carboxyl groups in one molecule of the compound (A) is within the above range, developability is improved.

  The value of the weight average molecular weight of the compound (A) / the number of hydroxyl groups or carboxyl groups of the compound (A) is preferably 200 to 3500, particularly preferably 300 to 2000. When the value of the weight average molecular weight of the compound (A) / the number of hydroxyl groups or carboxyl groups of the compound (A) is within the above range, the solubility of the compound (A) in the developer is increased, so that developability is improved. Get better.

  The number of (meth) acryloyl groups in one molecule of the compound (A) is 1 to 40, preferably 2 to 30. When the number of (meth) acryloyl groups in one molecule of the compound (A) is within the above range, the heat resistance of the cured product is increased.

Specifically, as the compound (A), the molecular chain of the (meth) acryloyl-modified epoxy resin is included in the molecular chain of the (meth) acryloyl-modified epoxy resin in which (meth) acryloyl groups are introduced at both ends of the epoxy resin. A compound in which the dibasic acid is introduced by bonding an hydroxyl group therein and one carboxyl group in the dibasic acid by an ester bond (one or more repeating units of the epoxy resin in the compound, molecular chain The number of dibasic acids introduced therein is 1 or more), and the compound includes, for example, an epoxy group at both ends of an epoxy resin obtained by polymerizing epichlorohydrin and a polyhydric alcohol; By reacting with (meth) acrylic acid, a (meth) acryloyl-modified epoxy resin having (meth) acryloyl groups introduced at both ends of the epoxy resin is obtained. Next, it is obtained by forming an ester bond with one carboxyl group of the dibasic acid by reacting a hydroxyl group in the molecular chain of the obtained (meth) acryloyl-modified epoxy resin with an anhydride of the dibasic acid. It is done.
Further, examples of the compound (A) include (meth) acryloyl-modified bisphenols obtained by reacting one hydroxyl group of a bisphenol with an epoxy group of a compound having an epoxy group and a (meth) acryloyl group. .
Moreover, as a compound (A), the (meth) acrylic acid polymer (The repeating unit of (meth) acrylic acid is 2 or more) which has a carboxyl group and a (meth) acryloyl group is mentioned.
Among these, (meth) acryloyl-modified bisphenols, (meth) acryloyl-modified novolak-type phenol resins, carboxyl groups and (meth) acrylates are excellent in the balance between developability and heat resistance after curing of the photosensitive adhesive resin composition. ) A (meth) acrylic acid polymer having an acryloyl group is preferable, and (meth) acryloyl-modified bisphenols and (meth) acryloyl-modified novolak type phenol resins are particularly preferable.

（式中、Ｒ₁は水素原子又はメチル基であり、ｎは２〜１０の整数である。）
で表される（メタ）アクリル酸重合体中の酸基（−ＣＯＯＨ）の一部が、下記式（５）：

（式中、Ｒ₃はベンゼン環又はシクロヘキサン環であり、ｍは１又は２であり、ｎは０〜
２である。）
で表される基で置換されている化合物である。なお、該カルボキシル基および（メタ）アクリロイル基を有する（メタ）アクリル酸重合体は、酸基の一部がアルキルエステル又はヒドロアルキルエステルに変換されていてもよい。
上記、カルボキシル基および（メタ）アクリロイル基を有する（メタ）アクリル酸重合体は、一例示であり、特に制限されるものではない。 In the present invention, the acrylic acid copolymer having a carboxyl group and a (meth) acryloyl group is represented by the following formula (4):

(In the formula, R ₁ is a hydrogen atom or a methyl group, and n is an integer of 2 to 10.)
A part of the acid group (—COOH) in the (meth) acrylic acid polymer represented by the following formula (5):

(In the formula, R ₃ is a benzene ring or a cyclohexane ring, m is 1 or 2, and n is 0 to 0.
2. )
The compound substituted by group represented by these. In addition, as for the (meth) acrylic acid polymer which has this carboxyl group and (meth) acryloyl group, a part of acid group may be converted into the alkyl ester or the hydroalkyl ester.
The (meth) acrylic acid polymer having a carboxyl group and a (meth) acryloyl group is merely an example, and is not particularly limited.

で表される基で置換されているノボラック型フェノール樹脂である。また、本発明では、
２以上のフェノール化合物がメチレン基で結合して重合しているものに対し、ノボラック型フェノール樹脂とのように、「樹脂」の文言を使用し、重合していないモノマーに対しフェノール類との文言を使用する。また、本発明で、ノボラック型フェノール樹脂は、分子鎖を構成するフェノールが、フェノール、クレゾール等のようにフェノール性の水酸基を１つ有するフェノール類である場合、ビスフェノールＡ、ビスフェノールＦ、カテコール、レゾルシノール、等のようにフェノール性の水酸基を２つ有するフェノール類である場合、ピロガロール等のようにフェノール性水酸基を３つ以上有するフェノール類である場合、あるいは、それらの併用である場合のいずれをも含む総称である。なお、ノボラック型フェノール樹脂のうち、フェノール（Ｃ₆Ｈ₅ＯＨ）の重合物のみを指す場合は、ノボラック型フェノール樹脂（フェノールの重合物）と記載する。 The (meth) acryloyl-modified novolak type phenolic resin according to the present invention is a part of the hydroxyl group of the novolak type phenolic resin represented by the following formula (3):

It is a novolak type phenol resin substituted by the group represented by these. In the present invention,
Where two or more phenolic compounds are bonded via a methylene group and are polymerized, the term “resin” is used as in the case of novolak-type phenolic resins, and the term “phenols” is used for monomers that are not polymerized. Is used. Further, in the present invention, the novolac type phenol resin is a bisphenol A, bisphenol F, catechol, or resorcinol when the phenol constituting the molecular chain is a phenol having one phenolic hydroxyl group such as phenol or cresol. In the case of phenols having two phenolic hydroxyl groups such as, etc., in the case of phenols having three or more phenolic hydroxyl groups such as pyrogallol, or in combination thereof It is a generic name including. Among the novolak type phenolic resin, when only point to a polymer of phenol (C ₆ H ₅ OH), referred to as novolak type phenolic resin (polymer of phenol).

  The phenols forming the molecular chain of the (meth) acryloyl-modified novolak type phenol resin related to the compound (A) include phenol, cresol, naphthol, hydroquinone, bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol AF, bisphenol. S, tetramethyl bisphenol F, tetramethyl bisphenol A, biphenol, diallyl bisphenol A, fluorenone bisphenol, pyrogallol, among these, phenol, cresol, bisphenol F, bisphenol A are preferred, and photosensitive adhesive resin after curing Phenol and bisphenol A are preferred because they are excellent in the balance between the heat resistance of the composition and the reliability of the semiconductor device.

  The (meth) acryloyl-modified novolak type phenolic resin related to the compound (A) is not particularly limited, but has a hydroxyl group of a novolac type phenolic resin obtained by reacting a phenolic compound with formaldehyde and an epoxy group (meta ) Resins obtained by ester reaction of acrylates with epoxy groups.

で表される（メタ）アクリロイル変性ビスフェノールＡ、又は下記一般式（２）：

（式中、ｎは２〜１５の整数を示す。）
で表されるノボラック型ビスフェノールＡ樹脂の水酸基の一部が、下記（３）式

で表される基で置換されている（メタ）アクリロイル変性ノボラック型ビスフェノールＡ樹脂であることが特に好ましい。 The compound (A) has the following chemical formula (1) in that it has an excellent balance between developability and high reactivity to heat and light.

(Meth) acryloyl-modified bisphenol A represented by the following general formula (2):

(In the formula, n represents an integer of 2 to 15.)
A part of the hydroxyl groups of the novolac bisphenol A resin represented by the formula:

(Meth) acryloyl-modified novolak bisphenol A resin substituted with a group represented by

  Compound (A) may be a single type or a combination of two or more types.

  When the compound (A) is a (meth) acryloyl-modified novolak type phenol resin, the number of phenols constituting the resin skeleton is 2 to 15, preferably 3 to 12, and the phenol constituting the resin skeleton When the number of classes is within the above range, developability is improved.

  The content of the compound (A) is preferably from 10 to 60% by mass, particularly preferably from 20 to 50% by mass, based on the entire photosensitive adhesive resin composition. When content of a compound (A) exists in the said range, high heat developability and the heat resistance of the photosensitive adhesive resin composition after hardening can be made compatible. In addition, when the photosensitive adhesive resin composition of this invention is a varnish shape which dissolved or disperse | distributed the structural component with the solvent, content of a compound (A) is the part except a solvent, ie, a compound (A ) To (E) and the percentage of the total amount of filler (F) and other additives added as necessary.

  The compound (B) according to the present invention is a resin that undergoes a thermosetting reaction with the compound (A), and the compound (B) is not particularly limited, but includes bisphenol A epoxy resin, bisphenol F epoxy resin, and the like. Bisphenol type epoxy resin, novolak epoxy resin, novolak type epoxy resin such as cresol novolak epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus Epoxy resins, epoxy resins such as dicyclopentadiene-modified phenolic epoxy resins, resins having a triazine ring such as urea (urea) resins, melamine resins, unsaturated polyester resins, bismaleimide resins, polyurethane resins, diallyl resins Rate resins, silicone resins, resins having a benzoxazine ring, cyanate ester resins, and the like. These may be used singly or in admixture. Among these, an epoxy resin is preferable because it is excellent in the balance between the heat resistance of the photosensitive adhesive resin composition and the adhesion to the adherend.

  The weight average molecular weight of the compound (B) is preferably 200 to 10,000, particularly preferably 300 to 5,000. When the weight average molecular weight of a compound (B) exists in the said range, high reactivity at the time of thermosetting and high adhesiveness with respect to a to-be-adhered member can be made compatible.

  The content of the compound (B) is preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass, based on the entire photosensitive adhesive resin composition. When the content of the compound (B) is within the above range, both the heat resistance and toughness of the cured photosensitive adhesive resin composition can be achieved. In addition, when the photosensitive adhesive resin composition of this invention is a varnish shape which dissolved or disperse | distributed the structural component with the solvent, content of a compound (B) is the part except a solvent, ie, a compound (A ) To (E) and the percentage of the total amount of the filler (F) and other additives added as necessary.

  Among the epoxy resins related to the compound (B), a bisphenol-type epoxy resin that is solid at 25 ° C. and a liquid at 25 ° C. in terms of excellent workability such as tack force of the photosensitive adhesive resin composition and toughness after curing. A combination with a silicone-modified epoxy resin is preferred. In the present invention, solid at 25 ° C. means that the softening point is 25 ° C. or more, and liquid at 25 ° C. means that the softening point is less than 25 ° C.

  In addition, when the compound (B) that is liquid at 25 ° C. is used as all or part of the compound (B), the content of the compound (B) that is liquid at 25 ° C. depends on the photosensitive adhesive resin composition. It is preferable that it is 20 mass% or less of the whole thing, and it is especially preferable that it is 15 mass% or less. When the content of the compound (B) that is liquid at 25 ° C. is within the above range, workability such as tack force of the photosensitive adhesive resin composition, toughness after curing, resolution during development, A photosensitive adhesive resin composition having an excellent balance of adhesiveness to the adherend can be obtained.

  Moreover, the compound (B) that is liquid at 25 ° C. is used as all or part of the compound (B), and the compound (C) that is liquid at 25 ° C. is used as all or part of the compound (C). In this case, the total content of the compound (B) that is liquid at 25 ° C. and the compound (C) that is liquid at 25 ° C. is preferably 20% by mass or less of the entire photosensitive adhesive resin composition. In particular, it is preferably 15% by mass or less. When the total content of the compound (B) which is liquid at 25 ° C. and the compound (C) which is liquid at 25 ° C. is within the above range, workability such as tackiness of the photosensitive adhesive resin composition, A photosensitive adhesive resin composition having an excellent balance of toughness after curing, resolution during development, and adhesion to an adherend can be obtained.

The compound (C) according to the present invention is a compound having a (meth) acryloyl group and not having a hydroxyl group or a carboxyl group. The compound (C) according to the present invention is not particularly limited as long as it has a (meth) acryloyl group. For example, a monofunctional (meth) acrylate having one (meth) acryloyl group, (Meth) acrylates such as bifunctional (meth) acrylates having two (meth) acryloyl groups and polyfunctional (meth) acrylates having three or more (meth) acryloyl groups, and more specifically, ethylene Bifunctional (meth) acrylates such as glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,10 decanediol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythri Ruhekisa (meth) polyfunctional (meth) acrylate acrylate. Moreover, polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate are also included in the compound according to compound (C). In addition, examples of the compound (C) include urethane (meth) acrylate and epoxy (meth) acrylate.
The urethane (meth) acrylate is a urethane compound formed by first reacting a hydroxyl group of a polyol with one isocyanate group in a compound having two or more isocyanate groups to form a urethane bond, In the obtained urethane compound, an isocyanate group that has not been used for the reaction with the polyol and a hydroxyl group of a compound having a hydroxyl group and a (meth) acryloyl group are reacted to form a urethane bond, is there.
Epoxy acrylate is a compound obtained by reacting an epoxy group of an epoxy resin with a carboxyl group of a compound having a carboxyl group and a (meth) acryloyl group to form an ester bond.
Examples of the urethane (meth) acrylate include a compound obtained by adding 2-hydroxyethyl (meth) acrylate to a urethane compound obtained by the reaction of polyalkylene glycol and diisocyanate. Moreover, as an epoxy (meth) acrylate, an epoxy bond at both ends of an epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is reacted with a carboxyl group of (meth) acrylic acid to form an ester bond. The compound obtained is mentioned.

  Among the compounds (C), triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and glycerin are excellent in the balance between photocuring reactivity and toughness of the photosensitive adhesive resin composition. Bifunctional (meth) acrylates such as di (meth) acrylate and 1,10-decanediol di (meth) acrylate are preferable, and among them, triethylene glycol di (meth) acrylate is particularly preferable.

  The weight average molecular weight of the compound (C) is 3000 or less, preferably 100 to 2500, particularly preferably 200 to 2000. When the weight average molecular weight of the compound (C) is within the above range, developability is improved.

  The compound (C) is not particularly limited, but is preferably liquid at 25 ° C. Thereby, photocuring reactivity can be improved. Furthermore, the mixing operation with the compound (B) can be facilitated.

  The content of the compound (C) is preferably from 3 to 30% by mass, particularly preferably from 5 to 20% by mass, based on the entire photosensitive adhesive resin composition. When the content of the compound (C) is in the above range, all of photocuring reactivity, heat resistance and toughness of the photosensitive adhesive resin composition can be increased. In addition, when the photosensitive adhesive resin composition of this invention is a varnish shape which melt | dissolved or disperse | distributed the structural component with the solvent, content of a compound (C) is the part except a solvent, ie, a compound (A ) To (E) and the percentage of the total amount of the filler (F) and other additives added as necessary.

  Moreover, when using the compound (C) which is liquid at 25 degreeC as all or one part of a compound (C), content of the compound (C) which is liquid state at 25 degreeC is the said photosensitive adhesive resin composition. It is preferable that it is 20 mass% or less of the whole thing, and it is especially preferable that it is 15 mass% or less. When the content of the compound (C) is within the above range, workability such as tack force of the photosensitive adhesive resin composition, photo-curing reactivity, resolution at the time of development, adhesion to the adherend member A photosensitive adhesive resin composition having an excellent balance can be obtained.

The compound (D) according to the present invention is a phenol resin or a phenol and is a compound having no (meth) acryloyl group. However, when the photosensitive adhesive resin composition is alkali-developed, the developability is improved. It has a function as an agent. The compound (A) contained in the photosensitive adhesive resin composition is also dissolved in the alkaline developer, but by adding the compound (D), the concentration of the phenolic hydroxyl group in the photosensitive adhesive resin composition is increased. , The solubility in an alkali developer is improved. The compound (D) has a function of reacting with the compound (B) during thermosetting after acting as a developability improver during alkali development. Therefore, since it is taken into the matrix of the cured product after curing, it is possible to suppress contamination of the transparent substrate, which is a member to be bonded, the substrate on which the semiconductor element is mounted, and the like, and it is also possible to suppress a decrease in heat resistance and moisture resistance. .

下記化学式（７）で表されるアラルキル基とフェノール類が結合したジシクロペンタジエンフェノール樹脂、

これらの中でも、現像性および感光性接着剤樹脂組成物の熱硬化後の耐熱性、靭性の全てを高くすることができる点で、ノボラック型フェノール樹脂が好ましい。また、化合物（Ｄ）に係るノボラック型フェノール樹脂の分子鎖を構成するフェノール類としては、化合物（Ａ）に係る（メタ）アクリロイル変性ノボラック型フェノール樹脂の分子鎖を構成するフェノール類の説明で列挙したフェノール類が挙げられる。 The phenol resin of the compound (D) according to the present invention is a resin having a phenolic hydroxyl group in the molecular chain. The phenol resin related to the compound (D) includes a novolac type phenol resin. The compound (D) is not particularly limited, and a novolak type phenol resin (a polymer of phenol), a novolac type orthocresol resin, a novolac type bisphenol A resin or the like,
Dicyclopentadiene phenol resin in which dicyclopentadiene represented by the following chemical formula (6) and phenols are bonded,

Dicyclopentadiene phenol resin in which an aralkyl group represented by the following chemical formula (7) and a phenol are bonded,

Among these, a novolak type phenol resin is preferable in that it can improve all of heat resistance and toughness after thermosetting of the developability and the photosensitive adhesive resin composition. Moreover, as phenols which comprise the molecular chain of the novolak-type phenol resin which concerns on a compound (D), it enumerates by description of the phenols which comprise the molecular chain of the (meth) acryloyl modified novolak-type phenol resin which concerns on a compound (A). Phenols.

  The phenols of the compound (D) according to the present invention are not particularly limited, and bisphenol A, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, bis (4-hydroxyphenyl) methane, bis (4- Hydroxyphenyl) propane, terpene diphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, bisphenol S, thiodiphenol, dihydroxydiphenyl ether, and dihydroxynaphthalene. Among these, bisphenol A, bisphenol F, biphenol, and bisphenol S are preferable, and bisphenol A and bisphenol F are particularly preferable in terms of excellent balance between developability, heat resistance after thermosetting of the photosensitive adhesive resin composition, and toughness. preferable.

The content of the compound (D) according to the present invention is 0.1 to 0.1% of the entire photosensitive adhesive resin composition.
It is preferable that it is 20 mass%, and 2-15 mass% is especially preferable. When content of a compound (D) exists in the said range, all the heat resistance of the developability and the photosensitive adhesive resin composition after hardening can be made high. In addition, when the photosensitive adhesive resin composition of this invention is a varnish shape which melt | dissolved or disperse | distributed the structural component with the solvent, content of a compound (D) is the part except a solvent, ie, a compound (A ) To (E) and the percentage of the total amount of the filler (F) and other additives added as necessary.

The weight average molecular weight of the compound (D) is 100 to 5000, preferably 200 to 300.
0. When the weight average molecular weight of the compound (D) is within the above range,
Since the solubility of the compound (D) is increased, the developability is improved.

  The photosensitizer (E) according to the present invention is not particularly limited, but benzophenone, acetophenone, benzoin, benzoin isobutyl ether, methyl benzoin benzoate, benzoin benzoic acid, benzoin methyl ether, benzyl phenyl sulfide, benzyl, dibenzyl , Diacetyl and the like.

  The content of the photosensitive agent (E) is preferably 0.5 to 5% by mass, and particularly preferably 0.8 to 2.5% by mass, based on the entire photosensitive adhesive resin composition. When the content of the photosensitive agent (E) is within the above range, the balance of photocurability, storage stability, and resolution can be maintained. In addition, when the photosensitive adhesive resin composition of this invention is a varnish shape which melt | dissolved or disperse | distributed the structural component with the solvent, content of a photosensitive agent (E) is the part except a solvent, ie, a compound ( It is a percentage with respect to the total amount of A) to (E) and the filler (F) and other additives added as necessary.

The photosensitive adhesive resin composition of the present invention may contain a filler (F) for the purpose of improving heat resistance, moisture resistance, and mechanical strength after curing.
The filler (F) according to the photosensitive adhesive resin composition of the present invention is not particularly limited, but examples thereof include fibrous fillers such as alumina fibers and glass fibers, potassium titanate, wollastonite, aluminum borate, Needle-like fillers such as acicular magnesium hydroxide and whiskers, talc, mica, sericite, glass flakes, flake graphite, plate-like fillers such as plate-like calcium carbonate, calcium carbonate, silica, fused silica, calcined clay, Examples thereof include spherical (granular) fillers such as unfired clay. Of these, spherical fillers are preferable because they have a good balance between developability and fluidity during thermocompression bonding. Further, the amount of contamination on the adherend is small and the cured photosensitive adhesive resin. Silica is particularly preferable because it is excellent in the balance of the mechanical strength of the composition.

  The content of the filler (F) is preferably 3 to 50% by mass, and particularly preferably 10 to 40% by mass, based on the entire photosensitive adhesive resin composition. When the content of the filler (F) is within the above range, the heat-resistant, moisture-resistant and photosensitive adhesive resin composition of the cured photosensitive adhesive resin composition is transferred to the transparent substrate and the semiconductor device. It is possible to obtain a photosensitive adhesive resin composition having an excellent balance between strength when placed between a substrate to be mounted and light transmittance upon exposure.

  The average particle diameter of the filler (F) is preferably 0.03 to 0.40 μm, and particularly preferably 0.10 to 0.30 μm. A photosensitive adhesive resin composition having an excellent balance between mechanical properties of the cured photosensitive adhesive resin composition and light transmission upon exposure when the average particle size of the filler (F) is within the above range. You can get things.

The measuring method of the average particle diameter of the filler (F) is as follows.
Using a laser diffraction particle size distribution analyzer SALD-7000, the filler was dispersed in water by ultrasonic treatment for 1 minute and measured. The D50 value (number integration) is taken as the average particle size.

  Further, the maximum particle size of the filler (F) is preferably 0.10 to 1.0 μm, particularly preferably 0.15 to 0.90 μm. A photosensitive adhesive resin composition having an excellent balance between mechanical properties of the cured photosensitive adhesive resin composition and light transmission upon exposure when the maximum particle size of the filler (F) is within the above range. You can get things.

The maximum particle size of the filler can be measured as follows.
Using a laser diffraction particle size distribution analyzer SALD-7000, the filler (F) is dispersed in water by ultrasonic treatment for 1 minute, and measurement is performed. The D100 value (number integration) is taken as the maximum particle size.

  The filler (F) may be subjected to a coupling treatment. By using such a filler, the adhesion between the resin component and the filler interface is increased, and the effect of increasing the strength of the photosensitive adhesive resin composition can be obtained.

  The photosensitive adhesive resin composition of this invention can contain additives, such as a plastic resin, a leveling agent, an antifoamer, a coupling agent, and an organic peroxide, in the range which does not impair the objective of this invention.

  The photosensitive adhesive resin composition of the present invention may be in the form of a varnish or may be formed into a film. Compounds constituting the photosensitive adhesive resin composition such as the compound (A), the compound (B), the compound (C), the compound (D), and the photosensitive agent (E) are removed from an organic solvent such as N-methyl- A varnish can be obtained by dissolving or dispersing in 2-pyrrolidone, anisole, methyl ethyl ketone, toluene, ethyl acetate or the like. By forming this varnish-like photosensitive adhesive resin composition into a layer, removing the solvent, and drying it, the photosensitive adhesive resin composition can be formed into a film.

  The adhesive film of the present invention is a photosensitive adhesive resin composition of the present invention comprising a base film and an adhesive layer formed on the surface of the base film, and the adhesive layer is formed into a film shape. .

  The base film is a film support base material that is excellent in film characteristics that can maintain the film state of the adhesive layer, for example, breaking strength, flexibility, etc., and is exposed and patterned by placing a mask pattern on the base film. When performing this, it is preferable that this base film has a light transmittance. Examples of such a base film include polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), etc., but polyethylene terephthalate (PET) is excellent in the balance between light transmittance and breaking strength. preferable.

  Moreover, you may provide the protective film for protecting the contact bonding layer on the surface in the adhesive film of this invention. The protective film may be any material as long as it is excellent in film characteristics that can maintain the film state of the adhesive layer, such as breaking strength and flexibility, and particularly excellent in peelability from the adhesive layer. For example, polyethylene terephthalate ( PET), polypropylene (PP), and polyethylene (PE). The protective film may be formed from an opaque material.

Next, a method for using the adhesive film of the present invention and an embodiment of a light receiving device will be described with reference to FIGS. FIG. 1 is a schematic cross-sectional view showing an embodiment of a method for using the adhesive film of the present invention, and FIG. 2 is a schematic cross-sectional view of a light receiving device.
As shown in FIGS. 1A and 1B, a semiconductor element assembly 9 in which a large number of semiconductor elements 11 are regularly held in a plane direction is connected to a base substrate 12 by connecting the semiconductor elements 11 with a support 10. Then, an adhesive film 14 is attached to the base substrate 12 on which the semiconductor element assembly 9 is mounted so as to cover the base substrate 12. Here, the thickness of the adhesive layer 15 of the adhesive film 14 is 5 to 100 μm.
Next, the base film 16 is peeled off, and the base substrate 12 with the adhesive layer 15 attached is aligned with an exposure apparatus (not shown).
At this time, an alignment mark (not shown) is formed on the surface of the base substrate 12 to which the adhesive layer 15 is attached. With this alignment mark as a reference, alignment between the mask of the exposure apparatus and the base substrate 12 is performed. The alignment is performed in the visible light region (wavelength 400 to 750 nm).
When the alignment between the base substrate 12 and the exposure apparatus is completed, the exposure apparatus selectively irradiates the adhesive layer 15 with light (ultraviolet rays). Thereby, the portion irradiated with light in the adhesive layer 15 is photocured. When the exposed adhesive layer 15 is developed with a developing solution (for example, an alkaline aqueous solution, an organic solvent, etc.), the light irradiated portion remains without being dissolved in the developing solution. The adhesive layer 15 is left in a region other than the light receiving portions 17 on the base substrate 12 so as to surround the light receiving portions 17 (see FIG. 1C).
After that, the transparent substrate 13 is placed on the adhesive layer 15, and the base substrate 12 and the transparent substrate 13 are bonded by the adhesive layer 15 (see FIG. 1D). For example, the base substrate 12 and the transparent substrate 13 are heated and pressurized, and the thermosetting component of the adhesive layer 15 is cured, so that the base substrate 12 and the transparent substrate 13 are bonded via the adhesive layer 15. The temperature at the time of thermocompression bonding is 80 ° C to 180 ° C.
At this time, the transparent substrate 13 is set with reference to the alignment mark formed on the base substrate 12.
Thereafter, the bonded base substrate 12 and transparent substrate 13 are divided according to the light receiving unit (see FIG. 1E). Specifically, a cut 18 is made by a dicing saw from the base substrate 12 side, and the base substrate 12 and the transparent substrate 13 are divided according to the light receiving unit.
Through such a process, the light receiving device 1 shown in FIG. 2 can be obtained.

  Thus, the photosensitive adhesive resin composition of the present invention is a photosensitive adhesive resin for spacers between a substrate on which a semiconductor element is mounted and a transparent substrate facing the substrate on which the semiconductor element is mounted. It is a composition.

Next, the effect of the photosensitive adhesive resin composition of this invention is demonstrated.
The photosensitive adhesive resin composition of this invention contains the compound (D). By incorporating the compound (D) into the photosensitive adhesive resin composition of the present invention, after the photosensitive adhesive resin composition is exposed, the solubility in an alkali developer can be improved, and the developability is improved. It becomes good.

  Moreover, the photosensitive adhesive resin composition of this invention applies the amount of the phenolic hydroxyl group in a photosensitive adhesive resin composition by applying (meth) acryloyl modified novolak-type phenol resin as a compound (A). Since it can increase, the effect that the solubility with respect to an alkali developing solution improves further and developability becomes favorable further increases.

Further, the photosensitive adhesive resin composition of the present invention further improves the heat resistance and moisture resistance of the photosensitive adhesive resin composition by containing 3 to 50% by mass of a filler, and transmits light. The photosensitive adhesive resin composition of the present invention can be made into a photosensitive adhesive resin composition excellent in alignment and alignment properties. The photosensitive adhesive resin composition of the present invention is filled with an average particle size of 0.03 to 0.4 μm. By containing the material, it is possible to realize both high light transmittance of the photosensitive adhesive composition and reduction of residues during development. As a result, alignment between the base substrate 12 and the mask of the exposure apparatus can be easily performed, and alignment between the base substrate 12 and the transparent substrate 13 after curing the photosensitive adhesive resin composition is also easy. Can be done. Furthermore, since there is no residue on the transparent substrate or the semiconductor element, the image recognizability is good.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

Further, in the above embodiment, the base film 12 and the transparent substrate 13 are bonded to each other after the adhesive film 14 formed of the photosensitive adhesive resin composition in a film shape is attached to the base substrate 12. However, the adhesive film may be attached to the transparent substrate. In this case, the alignment mark formed on the transparent substrate and the mask are aligned.
Moreover, in the said embodiment, after bonding the adhesive film 14 to the base substrate 12, after bonding the transparent substrate 13 by the contact bonding layer 15, dicing was performed, it is not restricted to this, The adhesive film 14 is used as a base substrate. After being attached to 12, the base substrate 12 may be diced in units of semiconductor elements, and then the transparent substrate 13 may be attached.
Moreover, in the said embodiment, although the adhesive film obtained by forming the photosensitive adhesive resin composition on a base film was affixed on the base substrate 12, it is not restricted to this, The photosensitive adhesive resin composition The object may be varnished and applied to the base substrate 12.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.
<Example 1>
1. Compound A Synthesis of methacryloyl-modified novolak bisphenol A resin MPN001 500 g of a 60% solid content MEK (methyl ethyl ketone) solution of novolak bisphenol A resin (Phenolite LF-4871, manufactured by Dainippon Ink & Chemicals) in a 2 L flask Into this, 1.5 g of tributylamine as a catalyst and 0.15 g of hydroquinone as a polymerization inhibitor were added and heated to 100 ° C. The glycidyl methacrylate 180.9g was dripped in 30 minutes in it, and the methacryloyl modified novolak-type bisphenol A resin MPN001 (methacryloyl modification rate 50%) of solid content 74% was obtained by making it stir-react at 100 degreeC for 5 hours. .

2. Preparation of Photosensitive Adhesive Resin Composition Varnish 44.5% by mass of methacryloyl-modified novolac bisphenol A resin MPN001 as compound (A) and bisphenol A novolac epoxy resin (Dainippon Ink Chemical Co., Ltd.) as compound (B) Industrial Co., Ltd., trade name: N865) 30.0% by mass, silicone-modified epoxy resin (Toray Dow Corning Silicone Co., Ltd., trade name: BY16-115) 5.3% by mass, compound ( C) as triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester 3G), 14.7% by mass, and compound (D) as a phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd.) Name: PR53467) 3.5% by mass and 2,2 dimethoxy-1,2 diphef as photosensitive agent (E) Nilethane-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 651) is dissolved in MEK (methyl ethyl ketone, manufactured by Daishin Chemical Co., Ltd.) in a solid content concentration of 71%. A photosensitive adhesive resin composition varnish was obtained. The content of the methacryloyl-modified novolak bisphenol A resin MPN001 in the photosensitive adhesive resin composition varnish is a value in terms of solid content.

3. Production of Adhesive Film After that, the photosensitive adhesive resin composition varnish was applied on transparent PET (film thickness 25 μm) and dried at 80 ° C. for 15 minutes to form a 50 μm thick adhesive layer to obtain an adhesive film It was.

4). Production of light-receiving device The above-mentioned adhesive film was laminated on a semiconductor wafer, exposed and developed to form a resin spacer (gap), and a glass substrate was thermocompression bonded at 120 ° C. to the upper end of the resin spacer. Next, the semiconductor wafer was diced (divided into pieces) to obtain a light receiving device.

<Example 2>
The compound (D) is a phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name: PR53467) instead of 3.5% by mass, and the compound (D) is bisphenol A (Honshu Chemical Co., Ltd., trade name: BPA ) Was used in the same manner as in Example 1 except that 3.5% by mass was used.
Got.

<Example 3>
The methacryloyl-modified novolak bisphenol A resin MPN001, which is the compound (A), is replaced with 44.5% by mass, and an acrylic acid polymer having a carboxyl group and a (meth) acryloyl group as a compound (A) (Daicel Chemical Industries, Ltd.) An adhesive film and a light receiving device were obtained in the same manner as in Example 1 except that 44.5% by mass of (trade name: Cyclomer P ACA200M) was used. The content of the acrylic acid polymer having a carboxyl group and a (meth) acryloyl group (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer P ACA200M) in the photosensitive adhesive resin composition varnish is solid. It is a value in terms of minutes.

<Example 4>
The compound (A) methacryloyl-modified novolak bisphenol A resin MPN001 was changed from 44.5% by mass to 40.5% by mass, and further, the compound (D) phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd.) An adhesive film and a light receiving device were obtained in the same manner as in Example 1 except that the trade name: PR53467) was changed from 3.5 mass% to 7.5 mass%.

<Example 5>
The compound (A) methacryloyl-modified novolak bisphenol A resin MPN001 was changed from 44.5% by mass to 33.0% by mass, and further, the compound (D) phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd.) An adhesive film and a light receiving device were obtained in the same manner as in Example 1 except that the trade name: PR53467) was changed from 3.5% by mass to 15.0% by mass.

<Example 6>
An adhesive film and a light receiving device were obtained in the same manner as in Example 1 except that the composition of the photosensitive adhesive resin composition varnish was as follows.
As compound (A), 29.5% by mass of methacryloyl-modified novolak bisphenol A resin MPN001, and as compound (B), bisphenol A novolak epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: N865) ) 19.9 mass%, silicone-modified epoxy resin (Toray Dow Corning Silicone Co., Ltd., trade name: BY16-115) 3.6 mass%, and compound (C) as triethylene glycol dimethacrylate ( Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester 3G) 9.8% by mass and, as compound (D), phenol novolac resin (Sumitomo Bakelite Co., Ltd., trade name: PR53467) 2.3% by mass Is dissolved in MEK (methyl ethyl ketone, manufactured by Daishin Chemical Co., Ltd.) so that the solid content concentration becomes 71%. To obtain a photosensitive adhesive resin composition varnish.
Next, using a bead mill (bead diameter: 400 μm, processing speed: 6 g / s, 5 passes), the filler (F) is silica (manufactured by Admatex, SO-E2, average particle size: 0.5 μm, maximum) 33.7% by mass) was dispersed.
Further, 1.2% by mass of 2,2dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals, Irgacure 651) was added as a photosensitizer (E), and a stirring blade (450 rpm) ) To obtain a photosensitive adhesive resin composition varnish by stirring for 1 hour.

<Example 6>
An adhesive film and a light receiving device were obtained in the same manner as in Example 1 except that the composition of the photosensitive adhesive resin composition varnish was as follows.
As compound (A), 29.5% by mass of methacryloyl-modified novolak bisphenol A resin MPN001, and as compound (B), bisphenol A novolak epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: N865) ) 19.9 mass%, silicone-modified epoxy resin (Toray Dow Corning Silicone Co., Ltd., trade name: BY16-115) 3.6 mass%, and compound (C) as triethylene glycol dimethacrylate ( Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester 3G) 9.8% by mass and, as compound (D), phenol novolac resin (Sumitomo Bakelite Co., Ltd., trade name: PR53467) 2.3% by mass Is dissolved in MEK (methyl ethyl ketone, manufactured by Daishin Chemical Co., Ltd.) so that the solid content concentration becomes 71%. To obtain a photosensitive adhesive resin composition varnish.
Next, using a bead mill (bead diameter 400 μm, treatment speed 6 g / s, 5 passes) as a filler (F), silica (manufactured by Nippon Shokubai Co., Ltd., trade name: KE-P30, average particle size: 0.00). 33.7% by mass) was dispersed (28 μm, maximum particle size: 0.9 μm).
Further, 1.2% by mass of 2,2dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals, Irgacure 651) was added as a photosensitizer (E), and a stirring blade (450 rpm) ) To obtain a photosensitive adhesive resin composition varnish by stirring for 1 hour.

<Example 7>
In place of 33.7% by mass of the filler (F), silica (manufactured by Admatechs Co., Ltd., SO-E2, average particle size: 0.5 μm, maximum particle size: 2.0 μm), the filler (F) Adhesive film as in Example 6 except that 33.7% by mass of silica (manufactured by Tokuyama Corporation, trade name: NSS-3N, average particle size: 0.125 μm, maximum particle size: 0.35 μm) A light receiving device was obtained.

<Example 8>
The filler (F) was replaced with 33.7% by mass of silica (manufactured by Admatex Co., Ltd., SO-E2, average particle size: 0.5 μm, maximum particle size: 2.0 μm) as the filler (F). Adhesive film as in Example 6 except that 33.7% by mass of silica (manufactured by Denka Co., Ltd., trade name: SFP-20M, average particle size: 0.33 μm, maximum particle size: 0.8 μm) is used. A light receiving device was obtained.

<Example 9>
In place of 33.7% by mass of the filler (F), silica (manufactured by Admatechs Co., Ltd., SO-E2, average particle size: 0.5 μm, maximum particle size: 2.0 μm), the filler (F) As in Example 6 except that the amount of silica was 33.7% by mass (made by Nippon Shokubai Co., Ltd., trade name: KE-S30, average particle size: 0.24 μm, maximum particle size: 0.9 μm). A film and a light receiving device were obtained.

<Example 10>
An adhesive film and a light receiving device were obtained in the same manner as in Example 6 except that the composition of the photosensitive adhesive resin composition varnish was as follows.
As compound (A), methacryloyl-modified novolak bisphenol A resin MPN001 is 42.0% by mass, and as compound (B), bisphenol A novolak epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: N865) ) 28.5% by mass, 5.1% by mass of silicone-modified epoxy resin (Toray Dow Corning Silicone Co., Ltd., trade name: BY16-115), and triethylene glycol dimethacrylate (C) as a compound (C) Shinnakamura Chemical Co., Ltd., trade name: NK Ester 3G) 13.9% by mass, and as compound (D), phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name: PR53467) 3.3% by mass Is dissolved in MEK (Methyl ethyl ketone, manufactured by Daishin Chemical Co., Ltd.), resulting in a solid content concentration of 71%. To obtain a photosensitive adhesive resin composition varnish.
Next, using a bead mill (bead diameter: 400 μm, processing speed: 6 g / s, 5 passes), the filler (F) is silica (manufactured by Admatex, SO-E2, average particle size: 0.5 μm, maximum) Particle size: 2.0 μm) 5.0% by mass was dispersed.
Further, 2.2% by mass of 2,2dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals, Irgacure 651) was added as a photosensitizer (E), and a stirring blade (450 rpm) ) To obtain a photosensitive adhesive resin composition varnish by stirring for 1 hour.

<Example 11>
An adhesive film and a light receiving device were obtained in the same manner as in Example 6 except that the composition of the photosensitive adhesive resin composition varnish was as follows.
As compound (A), 35.0% by mass of methacryloyl-modified novolak bisphenol A resin MPN001 and as compound (B), bisphenol A novolac epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: N865) ) 24.3 mass%, silicone-modified epoxy resin (Toray Dow Corning Silicone Co., Ltd., trade name: BY16-115) 4.3 mass%, and compound (C) as triethylene glycol dimethacrylate ( Shinnakamura Chemical Co., Ltd., trade name: NK Ester 3G) 11.8% by mass, and compound (D), phenol novolac resin (Sumitomo Bakelite Co., Ltd., trade name: PR53467) 2.8% by mass Is dissolved in MEK (Methyl ethyl ketone, manufactured by Daishin Chemical Co., Ltd.), resulting in a solid content concentration of 71%. To obtain a photosensitive adhesive resin composition varnish.
Next, using a bead mill (bead diameter: 400 μm, processing speed: 6 g / s, 5 passes), the filler (F) is silica (manufactured by Admatex, SO-E2, average particle size: 0.5 μm, maximum) 20.0% by mass) was dispersed.
Further, 1.8% by mass of 2,2dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals, Irgacure 651) was added as a photosensitive agent (E), and a stirring blade (450 rpm) ) To obtain a photosensitive adhesive resin composition varnish by stirring for 1 hour.

<Comparative Example 1>
An adhesive film and a light receiving device were obtained in the same manner as in Example 1 except that the composition of the photosensitive adhesive resin composition varnish was as follows.
As compound (A), 46.5% by mass of methacryloyl-modified novolak bisphenol A resin MPN001, and as compound (B), bisphenol A novolac epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: N865) ) 31.0% by mass, silicone-modified epoxy resin (Toray Dow Corning Silicone Co., Ltd., trade name: BY16-115) 5.4% by mass, and compound (C) as triethylene glycol dimethacrylate ( Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester 3G (14.8% by mass) and 2,2 dimethoxy-1,2-diphenylethane-1-one (Ciba Specialty Chemicals) as the photosensitizer (E) Made by Co., Ltd., trade name: Irgacure 651) 2.4% by mass, MEK (methyl ethyl ketone, Daishin) To obtain a photosensitive adhesive resin composition as dissolved in KK) a solid content concentration of 71%.

The following evaluation was performed about the adhesive film obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.
1. Developability Laminate an adhesive film on a semiconductor wafer (temperature 60 ° C., speed 0.3 m / min), and expose using a pattern mask so that resin spacers remain in a lattice shape (exposure amount: 700 mJ / cm ² ), Development using 3% TMAH (developer pressure: 0.2 MPa, development time: 150
Seconds). The obtained lattice pattern portion was observed with an electron microscope (x5,000 times), and the presence or absence of a residue was evaluated. Each code is as follows.
(Double-circle): A residue is not confirmed at all and there is no problem practically.
◯: Residue can be confirmed slightly, but at a level that does not cause any practical problems.
Δ: A relatively large amount of residue is observed, which is not a practical level.
X: Many residues are confirmed and it is not a practical use level.
The pattern mask was in a lattice shape with a resin width of 1.2 mm and an interval of 5 mm.

2. Photoreceptor Reliability 100 cycles of a temperature cycle test in which the photoreceptive devices obtained in each Example and Comparative Example were processed at -55 ° C for 1 hour and 125 ° C for 1 hour were repeated (n = 10), cracks and Observation of peeling was performed. Each code is as follows.
A: All sample cracks and peeling did not occur and there was no problem in practical use.
○: Slight cracks and peeling are confirmed in 2 or less samples, but there are practical problems
None.
(Triangle | delta): A crack and peeling are observed by three or more samples, and it is not a practical use level.

X: Cracks and peeling were observed in 8 or more samples, which is not a practical level.

3. Alignment For resin spacers, an adhesive film is laminated on a semiconductor wafer (temperature 60 ° C., speed 0.3 m / min) and the pattern on the semiconductor wafer surface is laminated using an exposure machine PLA-600FA (Canon). It was evaluated whether it was visible from the film. Each code is as follows.
(Double-circle): The pattern shape looks clear to the boundary part, and is a level which does not have any problem practically.
○: Although the pattern shape can be understood, the boundary portion looks somewhat blurred, but there is a problem in practical use.
None.
X: A pattern is not seen at all and is not a practical use level.

It is typical sectional drawing which shows one Embodiment of the usage method of the adhesive film of this invention. It is typical sectional drawing which shows a light-receiving device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light receiving device 9 Semiconductor element assembly 10 Support body 11 Semiconductor element 12 Base substrate 13 Transparent substrate 14 Adhesive film 15 Adhesive layer 16 Base film 17 Light-receiving part 18 Cutting

Claims (12)

A compound (A) having a hydroxyl group or a carboxyl group and a (meth) acryloyl group;
A resin (B) that undergoes a thermosetting reaction with the compound (A) having the hydroxyl group or carboxyl group and a (meth) acryloyl group;
A compound (C) having a (meth) acryloyl group and not having a hydroxyl group and a carboxyl group;
Phenol resin or phenols (D),
Photosensitizer (E),
A photosensitive adhesive resin composition comprising:   The photosensitive adhesive resin composition of Claim 1 whose compound (A) which has the said hydroxyl group or a carboxyl group, and a (meth) acryloyl group is a (meth) acryloyl modified novolak-type phenol resin. The compound (A) having the hydroxyl group or carboxyl group and the (meth) acryloyl group has the following chemical formula (1):

(Meth) acryloyl-modified bisphenol A represented by the following general formula (2):

(In the formula, n represents an integer of 2 to 15.)
A part of the hydroxyl groups of the novolac bisphenol A resin represented by the following formula (3):

The photosensitive adhesive resin composition of Claim 1 which is the (meth) acryloyl modified novolak-type bisphenol A resin substituted by group represented by these.   The photosensitive adhesive resin in any one of Claims 1 thru | or 3 whose content of the said phenol resin or phenols (D) in the said photosensitive adhesive resin composition is 0.1-20 mass%. Composition.   The photosensitive adhesive resin composition in any one of Claims 1 thru | or 4 in which the said phenol resin or phenols (D) is a novolak-type phenol resin or a phenol monomer.   Furthermore, the photosensitive adhesive resin composition in any one of Claims 1 thru | or 5 containing a filler (F).   The photosensitive adhesive resin composition of Claim 6 whose content of the said filler (F) in the said photosensitive adhesive resin composition is 3-50 mass%.   The photosensitive adhesive resin composition of Claim 6 or 7 whose average particle diameter of the said filler (F) is 0.03-0.4 micrometer.   The photosensitive adhesive resin composition according to any one of claims 6 to 8, wherein the filler (F) is a silica filler.   A resin (B) that undergoes a thermosetting reaction with the compound (A) having a hydroxyl group or a carboxyl group and a (meth) acryloyl group is a combination of an epoxy resin that is solid at 25 ° C. and a silicone-modified epoxy resin that is liquid at 25 ° C. The photosensitive adhesive resin composition according to any one of claims 1 to 9.   It consists of a base film and the contact bonding layer formed in the surface of the said base film, The said contact bonding layer is the photosensitive adhesive resin composition in any one of Claim 1 thru | or 10. An adhesive film. A substrate on which a semiconductor element is mounted;
A transparent substrate facing the substrate on which the semiconductor element is mounted;
A spacer provided between the transparent substrate and the substrate on which the semiconductor element is mounted;
With
A light receiving device, wherein the spacer is a cured product of the photosensitive adhesive resin composition according to any one of claims 1 to 11.

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