JP5471966B2 - Photosensitive adhesive composition, laminate or solid-state image sensor manufacturing method using the composition, and solid-state image sensor - Google Patents

Description

  The present invention relates to a photosensitive adhesive composition that is suitably used when three-dimensionally mounting a semiconductor element, a substrate, and the like, a method for manufacturing a laminate or a solid-state image sensor using the composition, and a solid-state image sensor.

  In manufacturing a semiconductor device having a stacked structure, semiconductor elements, substrates, and the like are stacked on various substrates. For example, when bonding a semiconductor element and a board | substrate, the adhesive agent for die bonding is generally used. The adhesive is required to have various properties such as reflow resistance. In addition, since a patterned adhesive layer is often used for stacking semiconductor elements and substrates, the adhesive is required to have photosensitivity.

  In particular, in the field of solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal Oxide Semiconductor) image sensors, a photosensitive adhesive composition is used for bonding an image sensor chip and a glass for protecting the image sensor chip. Is often used.

  As such a composition used for adhesion between a substrate having a semiconductor element and a transparent substrate, and a composition used for adhesion between a semiconductor element and a substrate on which the semiconductor element is mounted, various photosensitive adhesives are used. Compositions are known.

  The composition includes a (meth) acryloyl-modified novolak type phenol resin, an epoxy resin, a compound having a (meth) acryloyl group, having no hydroxyl group and no carboxyl group, a phenol resin, and a photosensitizer. Photosensitive adhesive resin composition (Patent Document 1), an alkali-soluble polymer, a radiation polymerizable compound, and a photosensitive adhesive composition containing a photopolymerization initiator (Patent Document 2), polyamic acid, and ethylenic A photosensitive adhesive composition containing a photopolymerizable compound having an unsaturated group and a photopolymerization initiator (Patent Document 3), the minimum melt viscosity at 20 to 200 ° C. after pattern formation is 30000 Pa · s or less, Photosensitive adhesive composition containing alkali-soluble resin, thermosetting resin, radiation polymerizable compound and photoinitiator (Patent Document 4), glass transition point of 1 0 ℃ or more UV curable adhesive, or a glass transition point of 120 ° C. or more heat curable adhesive (Patent Document 5) are disclosed.

JP 2008-297540 A JP 2009-141008 A JP 2008-239802 A International Publication No. 2010/024087 Pamphlet JP 2007-188909 A

  Heat resistance is particularly required for an adhesive used when a solid-state imaging device or the like is produced by three-dimensional mounting. This is because solder reflow is necessary when forming bumps (solder balls) or the like, and a high temperature (eg, 250 ° C. or higher) thermal history is applied to the adhesive during reflow.

  However, according to the study by the present inventors, in the photosensitive adhesive composition described in the above-mentioned patent document, the carboxylic acid component contained in the alkali-soluble resin or the like is decomposed during solder reflow, and the carboxylic acid component is transparent. It was found that it adhered to the substrate and caused whitening.

  An object of the present invention is to provide a photosensitive adhesive composition capable of suppressing such whitening, a laminate or a solid-state imaging device manufacturing method using the composition, and a solid-state imaging device.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by a photosensitive adhesive composition having the following constitution, and the present invention has been completed. That is, the configuration of the present invention is as follows, for example.

[1] (A) Compound having carboxyl group, (B) Photopolymerizable compound, (C) Photopolymerization initiator, (D) Compound represented by formula (D1)

［式（Ｄ１）中、ｎは２以上の整数を示す。Ｒ¹はｎ価の脂肪族基または水酸基を有するｎ価の脂肪族基を示す。］、および（Ｅ）溶剤を含有し、受光部を有する基板と透明基板との接着に用いられる感光性接着剤組成物。

[In the formula (D1), n represents an integer of 2 or more. R ¹ represents an n-valent aliphatic group or an n-valent aliphatic group having a hydroxyl group. And (E) a photosensitive adhesive composition used for bonding a substrate having a light receiving part and a transparent substrate, containing a solvent.

[2] The photosensitive adhesive composition according to [1], wherein the compound (D) is contained in an amount of more than 0 part by mass and not more than 60 parts by mass with respect to 100 parts by mass of the compound (A). .

[3] The photosensitive adhesive composition according to [1] or [2], wherein the compound (A) is a polymer having a carboxyl group.

[4] The photosensitive adhesive composition according to any one of [1] to [3], wherein the compound (A) has an ethylenically unsaturated double bond.

[5] The above-mentioned [4], wherein the compound (A) is at least one selected from resins obtained by modifying an epoxy group-containing (meth) acrylate-modified novolac phenol resin with an acid anhydride. Photosensitive adhesive composition.

[6] Lamination having a step of bonding a substrate having a light receiving portion and a transparent substrate with a patterned coating film obtained from the photosensitive adhesive composition according to any one of [1] to [5]. Body manufacturing method.

[7] A solid having a step of bonding a substrate having a light receiving portion and a transparent substrate with a patterned coating film obtained from the photosensitive adhesive composition according to any one of [1] to [5]. Manufacturing method of imaging device.

[8] A substrate having a light receiving portion, a patterned coating film formed on the substrate and obtained from the photosensitive adhesive composition according to any one of [1] to [5], A solid-state imaging device having a transparent substrate bonded to the substrate by a patterned coating film.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive adhesive composition which can suppress whitening of a transparent substrate etc. also in the environment where the high temperature heat history by solder reflow etc. is applied, the laminated body using the said composition, or a solid-state image sensor And a solid-state imaging device.

FIG. 1 is a cross-sectional view showing an embodiment of the solid-state imaging device of the present invention. FIG. 2 is a perspective view for explaining the patterned coating film obtained in the example.

  Hereinafter, the photosensitive adhesive composition of the present invention, a laminate or a solid-state imaging device manufacturing method using the composition, and a solid-state imaging device will be described in detail. Hereinafter, the “photosensitive adhesive composition of the present invention” is also simply referred to as “the composition of the present invention”.

[Photosensitive adhesive composition]
The photosensitive adhesive composition of the present invention comprises a carboxyl group-containing compound (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a compound (D) represented by the formula (D1) described later. And a solvent (E), and is used for bonding a substrate having a light receiving portion and a transparent substrate. The composition may further contain an additive (F). Hereinafter, the compound (A) having a carboxyl group is also referred to as a component (A).

  The composition of the present invention contains a compound (A) having a carboxyl group and a compound (D) having an epoxy group having good reactivity with the carboxyl group. For this reason, the transparent substrate in which the carboxyl group of the compound (A) is deactivated by the epoxy group of the compound (D) by heating at the time of pre-baking or reflow after forming the adhesive layer, and the carboxyl group is considered as the cause at the time of reflow. Can prevent whitening.

<Compound (A) having carboxyl group>
The compound (A) having a carboxyl group contributes to developability.
Examples of the compound (A) having a carboxyl group include low molecular compounds such as oxalic acid and malonic acid, and polymers having a carboxyl group. Among the compounds having a carboxyl group (A), a polymer having a carboxyl group is preferable from the viewpoint of alkali developability and heat resistance, and a polymer having a carboxyl group and an ethylenically unsaturated double bond is particularly preferable.

  Examples of the polymer having a carboxyl group include structural units having a carboxyl group (eg, structural units derived from unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; maleic acid, fumaric acid, citraconic acid). , Structural units derived from unsaturated dicarboxylic acids such as mesaconic acid and itaconic acid; carboxyl groups such as 2-malenoyloxyethyl methacrylate, 2-succinoloyloxyethyl methacrylate and 2-hexahydrophthaloylethyl methacrylate A resin containing a (meth) acrylic acid derivative) and a polyamic acid.

  Examples of the polymer having a carboxyl group and an ethylenically unsaturated double bond include a resin obtained by modifying a phenol resin with an epoxy group-containing (meth) acrylate (hereinafter referred to as “epoxy group-containing (meth) acrylate-modified phenol resin”). And a resin obtained by further modification with an acid anhydride (hereinafter also referred to as “an acid anhydride-modified phenol resin”).

In these, an acid anhydride modified phenol resin is preferable.
<< Epoxy group-containing (meth) acrylate-modified phenolic resin >>
The epoxy group-containing (meth) acrylate-modified phenol resin is a resin obtained by modifying a phenol resin with an epoxy group-containing (meth) acrylate. By the modification, the hydroxyl group of the phenol resin reacts with the epoxy group of the epoxy group-containing (meth) acrylate to form a hydroxyl group. In the present invention, the “phenol resin” includes resins produced using phenols such as cresol in addition to phenol.

  Examples of the phenol resin include novolak type phenol resins, hydroxystyrene homo- or copolymers, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, phenol-dicyclopentadiene condensation resins, and the like. Type phenolic resin is preferred.

The novolac type phenol resin can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst (eg, oxalic acid).
Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3 -Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, bisphenol A, bisphenol F, and the like.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.
Preferable specific examples of the novolak type phenol resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and bisphenol A / formaldehyde condensed novolak resin.

  Examples of the epoxy group-containing (meth) acrylate include compounds having at least one epoxy group and at least one (meth) acryloyl group, such as glycidyl (meth) acrylate and 3,4-epoxybutyl (meth). Examples include acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether. Among these, glycidyl (meth) acrylate is preferable. Epoxy group containing (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.

  For example, when the phenol / formaldehyde condensed novolak resin and glycidyl methacrylate are used, the modification reaction proceeds as shown in the following reaction formula.

《酸無水物変性フェノール樹脂》
酸無水物変性フェノール樹脂とは、エポキシ基含有（メタ）アクリレート変性フェノール樹脂をさらに酸無水物で変性して得られる樹脂である。この酸変性により、エポキシ基含有（メタ）アクリレート変性フェノール樹脂の水酸基と酸無水物とが反応して、エステル構造およびカルボキシル基が形成される。

<Acid anhydride modified phenolic resin>
An acid anhydride-modified phenol resin is a resin obtained by further modifying an epoxy group-containing (meth) acrylate-modified phenol resin with an acid anhydride. By this acid modification, the hydroxyl group and acid anhydride of the epoxy group-containing (meth) acrylate-modified phenol resin react to form an ester structure and a carboxyl group.

  Examples of the acid anhydride include maleic anhydride, itaconic anhydride, succinic anhydride, naphthalic anhydride, citraconic anhydride, phthalic anhydride, methylphthalic anhydride, tetrahydrophthalic anhydride (4 -Cyclohexene-1,2-dicarboxylic anhydride), methyltetrahydrophthalic anhydride, butenyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, chlorendic anhydride, etc. An anhydride of a basic acid; an anhydride of a tribasic acid or more such as trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride. An acid anhydride may be used individually by 1 type, and may use 2 or more types together.

  In the case of using, for example, an epoxy group-containing (meth) acrylate-modified phenol resin obtained by using a phenol / formaldehyde condensed novolak resin and glycidyl methacrylate, and 4-cyclohexene-1,2-dicarboxylic acid anhydride The reaction proceeds as shown in the following reaction formula.

カルボキシル基を有する重合体は、耐熱性の観点から、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算の質量平均分子量（Ｍｗ）が１０００以上であることが好ましく、２０００〜１０００００であることがより好ましい。

From the viewpoint of heat resistance, the polymer having a carboxyl group preferably has a polystyrene-reduced mass average molecular weight (Mw) of 1000 or more by gel permeation chromatography (GPC), more preferably 2000 to 100,000. .

A compound (A) may be used individually by 1 type, and may use 2 or more types together.
In the composition of the present invention, the content of the component (A) is preferably 40 to 90% by mass, more preferably 40 to 85% by mass, and particularly preferably 50 to 80% by mass based on the solid content. When content of a component (A) is less than the said range, there exists a tendency for heat resistance to fall. If the content of the component (A) exceeds the above range, voids tend to occur.

<Photopolymerizable compound (B)>
Examples of the photopolymerizable compound (B) include at least one selected from a photopolymerizable compound having a polyalkylene glycol structure and a photopolymerizable compound having no polyalkylene glycol structure. When a photopolymerizable compound having a polyalkylene glycol structure is used, flexibility is imparted to the adhesive layer, and generation of voids on the surface of the adhesive layer and the like can be suppressed.

  The polyalkylene glycol structure refers to, for example, a structure represented by the formula (B1).

式（Ｂ１）中、Ｒは炭素数１〜２０、好ましくは１〜１０、特に好ましくは１〜５のアルキレン基を示し、ｎは２〜２０の整数、好ましくは２〜１０の整数、特に好ましくは２〜５の整数を示す。

In the formula (B1), R represents an alkylene group having 1 to 20, preferably 1 to 10, particularly preferably 1 to 5 carbon atoms, and n is an integer of 2 to 20, preferably 2 to 10, particularly preferably. Represents an integer of 2 to 5.

Examples of the photopolymerizable compound having a polyalkylene glycol structure include a (meth) acrylate compound having a polyalkylene glycol structure, specifically,
Dialkylene glycol monomethyl ether (meth) acrylate,
Dialkylene glycol monoethyl ether (meth) acrylate,
Dialkylene glycol monopropyl ether (meth) acrylate,
Dialkylene glycol monobutyl ether (meth) acrylate,
Dialkylene glycol mono (2-ethylhexyl) ether (meth) acrylate,
Dialkylene glycol monophenyl ether (meth) acrylate,
Trialkylene glycol monomethyl ether (meth) acrylate,
Trialkylene glycol monoethyl ether (meth) acrylate,
Trialkylene glycol monopropyl ether (meth) acrylate,
Trialkylene glycol monobutyl ether (meth) acrylate,
Trialkylene glycol mono (2-ethylhexyl) ether (meth) acrylate,
Trialkylene glycol monophenyl ether (meth) acrylate,
Dialkylene glycol di (meth) acrylate,
Trialkylene glycol di (meth) acrylate,
Tetraalkylene glycol di (meth) acrylate,
Pentaalkylene glycol di (meth) acrylate,
Hexaalkylene glycol di (meth) acrylate,
Alkylene glycol (400) di (meth) acrylate,
Alkylene glycol (600) di (meth) acrylate,
Polyalkylene glycol-modified trimethylolpropane tri (meth) acrylate,
Polyalkylene glycol-modified pentaerythritol tri (meth) acrylate,
Polyalkylene glycol-modified pentaerythritol tetra (meth) acrylate,
Polyalkylene glycol-modified dipentaerythritol penta (meth) acrylate,
Examples include polyalkylene glycol-modified dipentaerythritol hexa (meth) acrylate (in the example, alkylene has the same meaning as the alkylene group in formula (B1)).

  Examples of the photopolymerizable compound having no polypropylene glycol structure include monofunctional ethylenically unsaturated compounds such as monofunctional (meth) acrylate compounds and polyfunctional ethylenically unsaturated compounds such as polyfunctional (meth) acrylate compounds. It is done. However, a polymer having a carboxyl group and an ethylenically unsaturated double bond classified as component (A) is excluded from the photopolymerizable compound having no polypropylene glycol structure.

  Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) i Cyanurate tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, epoxy (meth) acrylate obtained by adding (meth) acrylic acid to diglycidyl ether of bisphenol A, bisphenol A di (meth) acrylate, bisphenol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether, bisphenol A di (meth) acryloyloxymethyloxyethyl ether, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Examples include acrylate and pentaerythritol poly (meth) acrylate.

  As the polyfunctional (meth) acrylate compound, a commercially available compound can be used as it is. Specific examples of commercially available compounds include Aronix M-210, M-240, M-245, M-309, M-310, M-6100, M-6200, and M-6250. M-6300, M-6400, M-6500, M-7500, M-7100, M-8030, M-8060, M-8100, M-9050 (above, manufactured by Toagosei Co., Ltd.) KAYARADR-551, R-712, TMPTA, HDDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-604 (above, Nippon Kayaku Co., Ltd.) Biscort # 260, 295, 300, 312, 335HP, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Co., Ltd.).

A photopolymerizable compound (B) may be used individually by 1 type, and may use 2 or more types together.
Content of the component (B) in the composition of this invention is 10-60 mass parts normally with respect to 100 mass parts of components (A), Preferably it is 15-50 mass parts, Most preferably, it is 20-50 mass parts. is there. When content of a component (B) is less than the said range, there exists a tendency for heat resistance to fall. When content of a component (B) exceeds the said range, there exists a tendency for alkali developability to fall.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C), for example,
Α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether;
Benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone;
Acetophenone, p-dimethylaminoacetophenone, α, α-dimethoxy-α-acetoxybenzophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1- [2-methyl-4-methylthiophenyl] -2- Morpholinopropan-1-one, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- ( Acetophenones such as dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone;
Quinones such as anthraquinone and 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, and tris (trichloromethyl) -s-triazine;
[1,2′-bisimidazole] -3,3 ′, 4,4′-tetraphenyl, [1,2′-bisimidazole] -1,2′-dichlorophenyl-3,3 ′, 4,4′- Bisimidazoles such as tetraphenyl, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole;
Peroxides such as di-tert-butyl peroxide; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Is mentioned.

  As a commercial item of a photoinitiator (C), for example, Irgacure 184, 500, 651, 107, CGI369, G24-61 (above, Ciba Specialty Chemicals Co., Ltd. product), Lucillin LR8728, TPO (above, manufactured by BASF Corp.), Darocur 1116, 1173 (above, made by Ciba Specialty Chemicals Co., Ltd.), Ubekrill P36 (produced by UCB Corp.).

  Among the photoinitiators (C), benzophenones such as 4,4′-bis (diethylamino) benzophenone; 1- [2-methyl-4-methylthiophenyl] -2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, α, α-dimethoxy-α-phenylacetophenone, 2- (dimethylamino) -2-[(4-methylphenyl) ) Acetophenones such as methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; phenacyl chloride, tribromomethylphenyl sulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1, 2'-bisimidazoles, 4,4'-bis (diethylamino) benzophenone and mercaptoben Combination with thiazole, Lucirin TPO, such as Irgacure 651 is preferred.

A photoinitiator (C) may be used individually by 1 type, and may use 2 or more types together.
The content of the component (C) in the composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, particularly preferably 100 parts by mass of the component (A). 1 to 10 parts by mass. When content of a component (C) is less than the said range, it will be easy to receive the influence (deterioration of a sensitivity) of the radical deactivation by oxygen. When content of a component (C) exceeds the said range, there exists a tendency for the compatibility with a component (C) and another component to worsen, and for the storage stability to fall.

<Compound (D)>
Compound (D) is represented by formula (D1).

式（Ｄ１）中、ｎは２以上の整数、好ましくは２〜２０の整数、より好ましくは２〜１０の整数を示す。Ｒ¹はｎ価の脂肪族基または水酸基を有するｎ価の脂肪族基を示す。脂肪族基の炭素数は、通常２〜２０、好ましくは２〜１０、特に好ましくは２〜６である。

In the formula (D1), n represents an integer of 2 or more, preferably an integer of 2 to 20, more preferably an integer of 2 to 10. R ¹ represents an n-valent aliphatic group or an n-valent aliphatic group having a hydroxyl group. Carbon number of an aliphatic group is 2-20 normally, Preferably it is 2-10, Most preferably, it is 2-6.

  Examples of the compound (D) include polyglycidyl ethers of aliphatic polyhydric alcohols. That is, a compound obtained by glycidyl etherification of n hydroxyl groups among aliphatic polyhydric alcohols having m hydroxyl groups (here, n is an integer of 2 or more and m or less). Specific examples of the compound (D) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether. And sorbitol polyglycidyl ether.

  The compound (D) has a function of deactivating the carboxyl group of the compound (A) by heating at the time of pre-baking or reflow after forming the adhesive layer. Thereby, whitening of the transparent substrate considered to be caused by the carboxyl group during reflow can be prevented. Moreover, since the basic skeleton of the compound (D) is an aliphatic group, the effect of improving the adhesiveness is achieved. On the other hand, when the basic skeleton is an aromatic group, the obtained adhesive layer becomes hard and the adhesiveness may be lowered.

A compound (D) may be used individually by 1 type, and may use 2 or more types together.
Content of the component (D) in the composition of this invention is more than 0 mass part with respect to 100 mass parts of components (A) normally, and is 60 mass parts or less, Preferably it is 1-60 mass parts, More preferably, it is 1 -30 mass parts, Especially preferably, it is 1-10 mass parts. When content of a component (D) is less than the said range, there exists a tendency for whitening to generate | occur | produce. When the content of the component (D) exceeds the above range, the resolution tends to decrease.

<Solvent (E)>
As the solvent (E), it is preferable to use a solvent that can uniformly dissolve other components and does not react with other components. Examples of such solvents include alcohols such as methanol, ethanol, ethylene glycol, diethylene glycol, and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene. Alkyl ethers of polyhydric alcohols such as glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; Alkyl ether acetates of polyhydric alcohols such as coal monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate; aromatic carbonization such as toluene and xylene Hydrogens; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol; ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy- Ethyl 2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoate Le, methyl 3-methoxypropionate, 3-methoxy propionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, esters such as butyl acetate.

  Others, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

  Among the solvents (E), alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether because of solubility, non-reactivity with other components, and ease of film formation; ethylene glycol mono Alkyl ether acetates of polyhydric alcohols such as ethyl ether acetate and propylene glycol monomethyl ether acetate; ketones such as diacetone alcohol; ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. Esters are preferred.

A solvent (E) may be used individually by 1 type, and may use 2 or more types together.
Content of the solvent (E) in the composition of this invention can be suitably determined according to the use of the said composition, a coating method, etc. For example, what is necessary is just to adjust content of a solvent (E) so that the solid content density | concentration of the said composition may be 30-80 mass% normally, Preferably it is 40-70 mass%. The “solid content concentration” refers to the total concentration of components other than the solvent (E) in the composition.

<Additive (F)>
The composition of the present invention may contain an additive (F) in addition to the components (A) to (E) described above. Examples of the additive (F) include a thermal polymerization inhibitor, a surfactant, an adhesion aid, an epoxy crosslinking agent other than the component (D), a filler, a colorant, a viscosity modifier, and a sensitizer. .

《Thermal polymerization inhibitor》
Examples of the thermal polymerization inhibitor include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4. '-(1-methylethylidene) bis (2-methylphenol), 4,4'-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4- [1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4 ', 4 "-ethylidenetris (2-methylphenol), 4,4', 4" -ethylidenetrisphenol, 1,1 , 3-Tris (2,5-dimethyl-4-hydroxyphenyl)- - it includes phenyl propane.

  When a thermal polymerization inhibitor is used, the content of the thermal polymerization inhibitor in the composition of the present invention is more than 0 parts by mass and 5 parts by mass or less with respect to 100 parts by mass of the heat resistant polymer (A). Is preferred. A thermal polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.

<Surfactant>
In the present invention, a surfactant can be used for the purpose of improving the coating property, defoaming property, leveling property and the like of the composition. Examples of the surfactant include BM-1000, BM-1100 (above, manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (above, Dainippon Ink & Chemicals, Inc.), Fluorad FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S-141, S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), Footgent FTX -218 (manufactured by Neos Co., Ltd.) and other commercially available fluorine-based surfactants.

  When a surfactant is used, the content of the surfactant in the composition of the present invention is preferably more than 0 parts by mass and 5 parts by mass or less with respect to 100 parts by mass of the heat resistant polymer (A). . Surfactant may be used individually by 1 type and may use 2 or more types together.

<Adhesion aid>
In the present invention, an adhesion aid can be used for the purpose of improving the adhesion between the coating film formed from the composition and the substrate. As the adhesion assistant, a functional silane coupling agent is preferable. The functional silane coupling agent means a silane coupling agent having a reactive group such as a carboxyl group, a methacryloyl group, an isocyanate group, a vinyl group, and an epoxy group. For example, trimethoxysilylbenzoic acid, γ-methacryloxy Examples include propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. It is done. Some functional silane coupling agents have a carboxyl group or a methacryloyl group, but in the present invention, these are not included in component (A) and component (B).

  When using an adhesion assistant, the content of the adhesion assistant in the composition of the present invention is preferably more than 0 parts by mass and 20 parts by mass or less with respect to 100 parts by mass of the heat-resistant polymer (A). . Adhesion aids may be used alone or in combination of two or more.

<< Epoxy-based crosslinking agent >>
In this invention, epoxy-type crosslinking agents other than a compound (D) can be used. Examples of the epoxy crosslinking agent include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, trisphenol type epoxy resins, tetraphenol type epoxy resins, phenol-xylylene type epoxy resins, and naphthol-xylylene types. Epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aromatic epoxy resin, aliphatic epoxy resin other than compound (D), N, N, N ′, N ′ -Tetraglycidyl-m-xylylenediamine, N, N, N ', N'-pentaglycidyldiethylenetriamine, N, N, N', N'-tetraglycidylethylenediamine and the like.

  Examples of the aliphatic epoxy resin other than the compound (D) include polyglycidyl ether of an alkylene oxide adduct of an aliphatic polyhydric alcohol, and specific examples thereof include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Examples thereof include glycerol polyglycidyl ether and polyglycerol polyglycidyl ether.

《Filler, colorant, viscosity modifier》
In the present invention, a filler, a colorant, and a viscosity modifier can be used.
Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, and powdered glass. Examples of colorants include extender pigments such as alumina white, clay, barium carbonate, and barium sulfate; zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black, and the like. Inorganic pigments; organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green; basic dyes such as magenta and rhodamine; direct dyes such as direct scarlet and direct orange; Acid dyes such as metanil yellow are listed. Examples of the viscosity modifier include bentonite, silica gel, and aluminum powder. A filler, a coloring agent, and a viscosity modifier may be used individually by 1 type, and may use 2 or more types together.

  An additive (F) can be mix | blended in the range which does not impair the essential characteristic of this invention. The total content of the additive (F) is preferably 50% by mass or less based on the total amount of the composition of the present invention.

<Preparation of photosensitive adhesive composition>
The photosensitive adhesive composition of the present invention can be prepared by mixing and stirring the above-mentioned components by a usual method when no filler and pigment are added. When a filler and a pigment are added to the composition, the filler and the pigment and other components may be dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three roll mill. If necessary, the components before mixing or the obtained composition may be filtered using a mesh, a membrane filter, or the like.

<Use of photosensitive adhesive composition>
Since the photosensitive adhesive composition of this invention contains curable components, such as a photopolymerizable compound (B), an exposed part hardens | cures by exposing through a desired mask. For this reason, a desired pattern can be formed by development processing.

  The photosensitive adhesive composition of the present invention is less susceptible to whitening of a transparent substrate even under a high temperature environment such as solder reflow, and is excellent in adhesiveness and resolution. It can be particularly suitably used as an adhesive for bonding a substrate having a portion and a transparent substrate. The composition can also be used for bonding a semiconductor element or a substrate in the manufacture of a semiconductor device having a laminated structure. Specifically, an adhesive for mounting a semiconductor element such as an IC or LSI on a substrate, or an adhesive for laminating a substrate having a semiconductor element on another substrate (the obtained adhesive layer may be used as an interlayer insulating film) Etc.).

[Manufacturing method of laminate or solid-state imaging device]
The manufacturing method of the laminated body of this invention has the process of adhere | attaching the board | substrate which has a light-receiving part, and a transparent substrate with the patterned coating film obtained from the above-mentioned photosensitive adhesive composition. The manufacturing method of the solid-state image sensor of this invention has the process of adhere | attaching the board | substrate which has a light-receiving part, and a transparent substrate with the patterned coating film obtained from the above-mentioned photosensitive adhesive composition.

  The manufacturing method includes (1) a step of coating the photosensitive adhesive composition of the present invention on a substrate to form a coating film (coating film forming step), and (2) a step of prebaking the coating film (prebaking step). ), (3) a step of selectively exposing the coating film after pre-baking (exposure step), (4) a step of developing the coating film after exposure with alkali to form a pattern (developing step), (5) the substrate It is preferable to have the process (crimping process) of crimping | bonding an adherend to the pattern formation surface.

(1) Coating film formation process In a coating film formation process, the photosensitive adhesive composition of this invention is apply | coated on a board | substrate, and a coating film is formed. As the substrate, a resin substrate (for example, a resin substrate made of polyimide resin or epoxy resin), a copper foil with resin, a copper-clad laminate, a silicon wafer that may have a metal sputtered film, an alumina substrate, a transparent substrate (for example: Glass substrate). In the present invention, a transparent substrate (eg, a glass substrate) is usually used as the substrate. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method. The thickness of the coating film can be controlled by adjusting the solid content concentration and viscosity of the coating means and the composition solution, and is usually 10 to 100 μm, preferably 20 to 50 μm.

(2) Pre-baking step In the pre-baking step, the coating film is pre-baked. Pre-baking removes the solvent (D) in the composition of the present invention. The heating temperature in the pre-baking is usually 50 to 150 ° C., preferably 80 to 120 ° C., and the heating time is usually 0.5 to 60 minutes, preferably 1 to 30 minutes.

(3) Exposure process In an exposure process, the coating film after a prebaking is selectively exposed through the mask according to a desired pattern. In the present invention, exposure is performed through a mask so that an opening corresponding to the light receiving portion is formed at a predetermined position. Examples of the light source used for exposure include a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line stepper, an i-line stepper, a laser apparatus, and the like, and an electron beam irradiation apparatus. Exposure is selected such as by the thickness of the light source and the coating film to be used, for example, in the case of ultraviolet irradiation with a high-pressure mercury lamp, a 100~10000mJ / cm ² about the thickness 1 to 50 [mu] m.

(4) Development Step In the development step, a desired pattern is formed by developing (eg, alkali development) the exposed coating film and dissolving / removing non-exposed portions. Thereby, the coating film or adhesive layer which has a pattern, ie, a patterned coating film or adhesive layer, is obtained. Examples of the development method include shower development, spray development, immersion development, and paddle development. The development conditions are, for example, about 20 to 40 ° C. and about 1 to 10 minutes. As an alkaline developer, an alkaline aqueous solution obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide and choline in water so that the concentration is about 1 to 10% by mass. Etc. An appropriate amount of a water-soluble organic solvent (eg, methanol, ethanol) or a surfactant can be added to the alkaline aqueous solution. The coating film is developed with a developer (eg, alkaline developer), washed with water, and dried.

  Next, the substrate having the patterned coating film is appropriately heated. The heating temperature is usually 80 to 200 ° C, preferably 100 to 170 ° C, and the heating time is usually 1 to 60 minutes, preferably 5 to 30 minutes.

(5) Crimping step In the crimping step, the adherend is crimped to the surface of the substrate on which the patterned coating film is formed. The adherend may have a semiconductor element such as an IC or LSI, a resin substrate (eg, a resin substrate made of polyimide resin, epoxy resin, etc.), a copper foil with resin, a copper-clad laminate, or a metal sputtered film. A silicon wafer, an alumina substrate, a transparent substrate (example: glass substrate), etc. are mentioned. In the present invention, a substrate having a light receiving portion (for example, a substrate provided with a color filter and a microlens array) is usually used as an adherend, and for example, a substrate having a plurality of light receiving portions can also be used. In this case, the substrate and the transparent substrate are bonded so that the plurality of light receiving portions on the substrate are surrounded by the patterned adhesive layer. A press machine manufactured by Applied Power Japan (model number: ENERPACESE-924-00) or the like can be used for the pressure-bonding process. The treatment temperature in the crimping treatment is usually 50 to 250 ° C., the pressure is usually 0.1 to 10 MPa, and the treatment time is usually 0.5 seconds to 60 minutes.

(6) Other steps In the present invention, other steps may be provided in addition to the above steps. Examples of other processes include a dicing process, a wiring portion forming process, an infrared cut filter attaching process, and an optical lens connecting process. In the dicing process, the substrate and the adherend bonded together are diced using a dicing blade or the like for each desired section (eg, light receiving portion). Thereby, a plurality of semiconductor devices are obtained, and a plurality of solid-state imaging elements are obtained in the manufacture of a solid-state imaging element described later.

  As described above, according to the manufacturing method of the present invention, the substrate having the light receiving portion and the transparent substrate can be bonded to obtain a laminate. In the obtained laminate, the transparent substrate is less likely to be whitened, and the adhesive layer formed between the substrate having the light receiving portion and the transparent substrate is excellent in adhesion and resolution.

  The above manufacturing method is suitably used for manufacturing a solid-state imaging device. In this manufacturing method, a substrate having a plurality of light receiving portions and a transparent substrate having an adhesive layer formed corresponding to a position surrounding each light receiving portion are bonded via the adhesive layer, and the resulting laminate is obtained. A plurality of solid-state imaging devices can be manufactured collectively by dicing the body for each light receiving unit.

[Solid-state image sensor]
The solid-state imaging device of the present invention is a substrate having a light receiving portion, a patterned coating film formed from the above-described photosensitive adhesive composition formed on the substrate, and bonded to the substrate by the patterned coating film. And a transparent substrate. The patterned coating film is preferably formed on a substrate around the light receiving portion.

An example of the configuration of the solid-state imaging device of the present invention will be described with reference to FIG. 1 as appropriate.
FIG. 1 is a cross-sectional view of an embodiment of the solid-state imaging device of the present invention. The solid-state imaging device 1 is formed on the substrate 10 by the substrate 10 having the light receiving unit 40, the patterned coating film 20 formed on the substrate 10 and obtained from the above-described photosensitive adhesive composition, and the patterned coating film 20. And a transparent substrate 30 bonded thereto.

  Examples of the substrate 10 include an image sensor chip having a light receiving unit 40 that performs photoelectric conversion. The image sensor chip is a rectangular silicon wafer made of a silicon single crystal. A wiring portion 50 and a bump electrode 51 are formed on the lower surface of the substrate 10, and the solid-state imaging device and the mounting substrate can be electrically connected by flip chip mounting. Wiring between the solid-state imaging device and the mounting substrate may be performed by wire bonding instead of flip-chip mounting. The light receiving unit 40 (not shown) has, for example, a CCD or a CMOS, and is provided in the image sensor chip by a known semiconductor process. Further, a color filter (RGB) 41 and a microlens array 42 provided on the color filter 41 are arranged corresponding to the light receiving unit 40.

  The patterned coating film 20 is a frame-shaped resin layer having an opening, and is formed on the substrate 10 so as to surround the light receiving unit 40. The patterned coating film 20 also functions as a spacer between the substrate 10 and the transparent substrate 30.

  Examples of the transparent substrate 30 include cover glass such as transparent glass (eg, low α-ray glass). The transparent substrate 30 is bonded to the upper surface of the coating film 20 so as to close the opening of the patterned coating film 20 and plays a role of sealing the light receiving unit 40. A gap is formed by the patterned coating film 20 between the transparent substrate 30 and the microlens array 42.

  On the transparent substrate 30, an infrared cut filter, an antireflection filter, or the like may be provided as an optical plate (not shown). For example, when an infrared cut filter is provided on a transparent substrate, infrared rays in a specific wavelength region are cut, and ghosts and the like due to infrared light are prevented.

  The embodiment of the present invention with reference to FIG. 1 is merely an example, and the scope of the present invention is not limited to the scope of these descriptions. The scope of the present invention is indicated by the description of the scope of claims, and further includes meanings equivalent to the description of the scope of claims and all modifications within the scope.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Here, “parts”, “%” and “mixing ratio” are based on mass unless otherwise specified.

[1] Preparation of photosensitive adhesive composition [Example 1]
100 parts of acid anhydride-modified phenolic resin (trade name “KAYARAD CCR-1308H”, manufactured by Nippon Kayaku Co., Ltd.) as component (A), 10 parts of propylene glycol-modified trimethylolpropane triacrylate (B) as component (A) Trade name "Aronix TO-1670", manufactured by Toa Gosei Co., Ltd.) and 20 parts of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (mixing ratio is 1: 1), component (C). As 5-part 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name “IRGACURE 379EG”, Ciba Specialty Chemicals) and 1 part of 4,4'-bis (diethylamino) ben Phenone, 70 parts propylene glycol monomethyl ether acetate as component (E), 5 parts trimethylolpropane polyglycidyl ether (trade name “Denacol EX-321L”, manufactured by Nagase ChemteX Corporation) as component (D), and As component (F), 2.5 parts of γ-glycidoxypropyltrimethoxysilane (trade name “A-187”, manufactured by Nippon Unicar Co., Ltd.) and 0.1 part of a fluorosurfactant (trade name “ FTX-218 ”(manufactured by Neos Co., Ltd.) was mixed to obtain a photosensitive composition of Example 1.

[Examples 2 to 8, Comparative Example 1]
Except having used the component shown in Table 1 in the quantity shown in Table 1, it carried out similarly to Example 1, and obtained the photosensitive adhesive composition of Examples 2-8 and the comparative example 1, respectively.

表１中に記載の各成分の詳細は以下のとおりである。
Ａ１：商品名「ＫＡＹＡＲＡＤ ＣＣＲ−１３０８Ｈ」、日本化薬（株）製
Ａ２：商品名「ＫＡＹＡＲＡＤ ＺＡＲ−１０３５」、日本化薬（株）製
Ｂ１：プロピレングリコール変性トリメチロールプロパントリアクリレート（商品名「アロニックスＴＯ−１６７０」、東亜合成（株）製、下記式で表される化合物）

The detail of each component described in Table 1 is as follows.
A1: Trade name “KAYARAD CCR-1308H”, Nippon Kayaku Co., Ltd. A2: Trade name “KAYARAD ZAR-1035”, Nippon Kayaku Co., Ltd. B1: Propylene glycol modified trimethylolpropane triacrylate (trade name “ Aronix TO-1670 ", manufactured by Toa Gosei Co., Ltd., a compound represented by the following formula)

Ｂ２：ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートとの混合物（混合比は１：１である。）
Ｂ３：トリメチロールプロパントリアクリレート
Ｃ１：２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルフォリニル）フェニル］−１−ブタノン
Ｃ２：４，４’−ビス（ジエチルアミノ）ベンゾフェノン
Ｄ１：トリメチロールプロパンポリグリシジルエーテル
Ｅ１：プロピレングリコールモノメチルエーテルアセテート
Ｆ１：γ−グリシドキシプロピルトリメトキシシラン
Ｆ２：フッ素系界面活性剤（商品名「ＦＴＸ−２１８」、（株）ネオス製）

B2: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (mixing ratio is 1: 1)
B3: Trimethylolpropane triacrylate C1: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone C2: 4,4 ′ -Bis (diethylamino) benzophenone D1: Trimethylolpropane polyglycidyl ether E1: Propylene glycol monomethyl ether acetate F1: γ-glycidoxypropyltrimethoxysilane F2: Fluorosurfactant (trade name “FTX-218”, (stock) ) Made by Neos)

[2] Evaluation The performance of the photosensitive adhesive compositions obtained in the above Examples and Comparative Examples was evaluated by the following method. The evaluation results are shown in Table 2.

[2-1] Formation of patterned coating film A photosensitive adhesive composition is applied onto a silicon wafer by a spin coating method and heated on a hot plate at 110 ° C. for 5 minutes to form a coating film having a thickness of 30 μm. Formed. Next, the exposure amount at a wavelength of 350 nm from a high-pressure mercury lamp is 350 mJ / cm ² with an aligner (manufactured by Suss Microtec, model number “MA-200”) through a patterned mask having a square pattern. The coating film was exposed. Using the 2.38% tetramethylammonium hydroxide aqueous solution as a developer, the exposed coating film was developed at 23 ° C. for 1 minute. The substrate having the developed coating film was heated at 160 ° C. for 5 minutes using a hot plate. As a result, as shown in FIG. 2, a patterned coating film having a plurality of holes having a depth of 30 μm, a vertical width of 6 mm and a horizontal width of 6 mm and a pitch of 6 mm for each hole was obtained.

[2-2] Presence or absence of whitening After a glass substrate was placed on the patterned coating film obtained in [2-1] above, a load of 0.6 MPa was applied at 180 ° C. for 1 minute, and the silicon wafer and the glass substrate And thermocompression bonded. Next, after heating at 180 ° C. for 1 hour using a convection oven, the mixture was further heated at 280 ° C. for 3 minutes using a reflow apparatus. The following criteria evaluated the presence or absence of whitening between the patterned coating film after heating and the glass substrate.
-AA: No whitening-BB: Whitening

[2-3] Adhesiveness After placing the glass substrate on the patterned coating film obtained in [2-1] above, a load of 0.6 MPa was applied at 180 ° C. for 1 minute, and the silicon wafer and the glass substrate Was thermocompression bonded. Next, after heating at 180 ° C. for 1 hour using a convection oven, the mixture was further heated at 280 ° C. for 3 minutes using a reflow apparatus. The presence or absence of adhesion between the patterned coating film after heating and the glass substrate was defined as “adhesiveness” and evaluated according to the following criteria.
-AA: No peeling-BB: There is peeling.

[2-4] Resolution A photosensitive adhesive composition was applied on a silicon wafer by spin coating, and heated at 110 ° C. for 5 minutes on a hot plate to form a coating film having a thickness of 30 μm. Next, the exposure amount at a wavelength of 350 nm from a high-pressure mercury lamp is 350 mJ / cm ² with an aligner (manufactured by Suss Microtec, model number “MA-200”) through a patterned mask having a square pattern. The coating film was exposed. Using the 2.38% tetramethylammonium hydroxide aqueous solution as a developer, the exposed coating film was developed at 23 ° C. for 1 minute. The substrate having the developed coating film was heated at 160 ° C. for 5 minutes using a hot plate, and the minimum hole size (width) that could be resolved was measured.

DESCRIPTION OF SYMBOLS 1 ... Solid-state image sensor 10 ... Substrate 20 which has a light-receiving part ... Patterned coating film (adhesive layer)
DESCRIPTION OF SYMBOLS 30 ... Transparent substrate 40 ... Light-receiving part 41 not shown ... Color filter 42 ... Micro lens array 50 ... Wiring part 51 ... Electrode (bump)
DESCRIPTION OF SYMBOLS 100 ... Hole 101 ... Vertical width 102 ... Horizontal width 103 ... Depth 200 ... Patterned coating film 201 ... Pitch 300 ... Silicon wafer

Claims (8)

(A) a compound having a carboxyl group,
(B) a photopolymerizable compound,
(C) a photopolymerization initiator,
(D) Compound represented by formula (D1)

[In the formula (D1), n represents an integer of 2 or more. R ¹ represents an n-valent aliphatic group or an n-valent aliphatic group having a hydroxyl group. And (E) a photosensitive adhesive composition used for bonding a substrate having a light receiving part and a transparent substrate, containing a solvent.   The photosensitive adhesive composition of Claim 1 which contains the said compound (D) in 60 mass parts or less exceeding 0 mass part with respect to 100 mass parts of said compounds (A).   The photosensitive adhesive composition according to claim 1 or 2, wherein the compound (A) is a polymer having a carboxyl group.   The photosensitive adhesive composition as described in any one of Claims 1-3 in which the said compound (A) has an ethylenically unsaturated double bond.   The photosensitive adhesive according to claim 4, wherein the compound (A) is at least one selected from resins obtained by modifying an epoxy group-containing (meth) acrylate-modified novolak-type phenol resin with an acid anhydride. Composition.   The manufacturing method of the laminated body which has the process of adhere | attaching the board | substrate which has a light-receiving part, and a transparent substrate with the patterned coating film obtained from the photosensitive adhesive composition as described in any one of Claims 1-5.   The manufacturing method of the solid-state image sensor which has the process of adhere | attaching the board | substrate which has a light-receiving part, and a transparent substrate with the patterned coating film obtained from the photosensitive adhesive composition as described in any one of Claims 1-5. A substrate having a light receiving portion;
A patterned coating film obtained from the photosensitive adhesive composition according to any one of claims 1 to 5, formed on the substrate,
A solid-state imaging device having a transparent substrate bonded to the substrate by the patterned coating film.

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