JPWO2007119699A1 - Photosensitive resin composition and photosensitive element using the same - Google Patents

Abstract

(A) a base polymer having a repeating unit represented by the following general formula (1), (B) an acrylic polymer having a photopolymerizable unsaturated group, (C) an inorganic filler, and (D) photopolymerizability. A photosensitive element provided with the photosensitive resin composition containing a monomer and (E) photoreaction initiator, and the photosensitive resin composition layer formed using this. [In formula (1), R1 represents a divalent organic group that is a diglycidyl ether type epoxy compound residue, R2 represents a divalent organic group that is a dibasic acid residue, and R3 and R4 are each independently Represents a hydrogen atom or a group represented by the following general formula (2); (in the formula (2), R5 represents an acid anhydride residue). ]

Description

  The present invention relates to a photosensitive resin composition and a photosensitive element using the same.

  Conventionally, a photosensitive resin composition and a photosensitive element using the same are used for forming a circuit of a printed wiring board or a solder resist. In such applications, Patent Document 1 below discloses a photosensitive resin composition having excellent adhesion and resolution and suppressing the occurrence of scum and a photosensitive element useful for increasing the density of a printed wiring board.

  In addition, in the field of manufacturing a hollow package structure for various sensors, for example, in the field of CCD / CMOS image sensors, for bonding an image sensor chip and a glass that protects it, a liquid UV curing type applied by a printing method is used. Photosensitive resin compositions are widely used.

As such photosensitive resin compositions for image sensors, those satisfying characteristics such as high adhesive strength, hermetic sealing properties, developability, low water absorption, low ionic impurities, and high reliability are required. In addition, with the recent miniaturization of camera modules, development of photosensitive resin compositions that can satisfy the demands for miniaturization and improved positional accuracy has been demanded. Furthermore, with recent price competition, a film-type photosensitive resin composition (photosensitive element) capable of batch molding is required for cost reduction by shortening the number of processes.
JP 2002-351070 A

  However, it has been difficult for the above-described conventional photosensitive resin composition and photosensitive element to sufficiently satisfy all the characteristics of adhesive strength, developability, and low water absorption.

  The present invention has been made in view of the above-described problems of the prior art, and provides a photosensitive resin composition that has sufficiently high adhesive strength and has both good developability and sufficiently low water absorption. It aims at providing the photosensitive element using this.

［式（１）中、Ｒ^１はジグリシジルエーテル型エポキシ化合物残基である二価の有機基を示し、Ｒ^２は二塩基酸残基である二価の有機基を示し、Ｒ^３及びＲ^４は各々独立に水素原子又は下記一般式（２）；

（式（２）中、Ｒ^５は酸無水物残基を示す。）で表される基を示す。］In order to achieve the above object, the present invention comprises (A) a base polymer having a repeating unit represented by the following general formula (1), (B) an acrylic polymer having a photopolymerizable unsaturated group, A photosensitive resin composition comprising C) an inorganic filler, (D) a photopolymerizable monomer, and (E) a photoreaction initiator is provided.

[In the formula (1), R ¹ represents a divalent organic group which is a diglycidyl ether type epoxy compound residue, R ² represents a divalent organic group which is a dibasic acid residue, R ³ and R ⁴ each independently represents a hydrogen atom or the following general formula (2);

(In formula (2), R ⁵ represents an acid anhydride residue.). ]

  According to such a photosensitive resin composition, by having the above-described configuration, it is possible to obtain a sufficiently high adhesive strength and to achieve both good developability and a sufficiently low water absorption.

  The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer made of the above-described photosensitive resin composition of the present invention formed on the support.

  In such a photosensitive element, since the photosensitive resin composition layer is a layer formed by using the photosensitive resin composition of the present invention, it is possible to obtain a sufficiently high adhesive strength and good developability. It is possible to achieve both a sufficiently low water absorption rate.

  According to the present invention, a sufficiently high adhesive strength can be obtained, and a photosensitive resin composition having both good developability and a sufficiently low water absorption rate and a photosensitive element using the same can be provided.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 20 ... Photosensitive resin composition layer, 30 ... Protective film.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding to it, (meth) acrylate means acrylate and corresponding methacrylate, and (meth) acryloyl corresponds to acryloyl and it. And (meth) acryloxy means acryloxy and the corresponding methacryloxy.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention includes a base polymer having a repeating unit represented by the general formula (1) as the component (A), and an acrylic polymer having a photopolymerizable unsaturated group as the component (B). , (C) an inorganic filler, (D) a photopolymerizable monomer as a component, and (E) a photoreaction initiator as a component. Hereinafter, each component will be described in detail.

<(A) component>
The base polymer as the component (A) has a repeating unit represented by the general formula (1).

  The weight average molecular weight (Mw) of the (A) base polymer can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene). The conditions for GPC are as follows.

(GPC conditions)
Pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Detector: Hitachi L-4000 UV [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-S300MDT-5 (two in total) [manufactured by Hitachi Chemical Co., Ltd., trade name]
Column size: 8mmφ × 300mm
Eluent: DMF / THF = 1/1 + 0.06M phosphoric acid + 0.06M lithium bromide
Sample concentration: 5 mg / 1 mL
Injection volume: 5 μL
Pressure: 343 Pa (35 kgf / cm ² )
Flow rate: 1.0 mL / min

  The weight average molecular weight (Mw) of the (A) base polymer determined by this measurement method is preferably 10,000 to 70,000 from the viewpoint of coating properties (difficulty in stickiness) and developability with a dilute aqueous alkali solution. 20,000 to 60000 is more preferable, and 30000 to 50000 is particularly preferable.

(A) The acid value of the base polymer can be measured by the following method. First, (A) about 1 g of the base polymer solution is precisely weighed, and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And from the titration result, the following formula (I);
A = (10 × Vf × 56.1) / (Wp × I) (I)
Is used to calculate the acid value. In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of phenolphthalein, Wp represents (A) the base polymer solution mass (g), and I represents (A ) The ratio (% by mass) of non-volatile content in the base polymer solution.

  The acid value of the base polymer (A) obtained by this measurement method is preferably 60 to 200 mgKOH / g, more preferably 75 to 100 mgKOH / g, from the viewpoint of developability with a dilute alkaline aqueous solution.

  (A) The base polymer can be synthesized by the following method.

  (A) A base polymer synthesis method includes a first step of obtaining an intermediate product by a polymerization reaction of a diglycidyl ether type epoxy compound having two glycidyl groups in one molecule and a dibasic acid, and an intermediate product containing an acid. And (A) a second step of obtaining a base polymer as described above by adding an anhydride.

In addition, the diglycidyl ether type epoxy compound residue represented by R ¹ in the general formula (1) is a portion excluding the glycidyl group in the structure of the diglycidyl ether type epoxy compound. Further, the dibasic acid residue represented by R ² in the general formula (1) is a portion excluding the dibasic acid functional group in the structure of the dibasic acid.

(First step)
As the diglycidyl ether type epoxy compound used as a raw material in the first step, a compound represented by the following general formula (3) can be exemplified. Here, R ⁶ represents a divalent organic group.

  Examples of the diglycidyl ether type epoxy compound include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, and bisphenol S type epoxy resins such as bisphenol S diglycidyl ether, Biphenol type epoxy resins such as biphenol diglycidyl ether, bixylenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, and their dibasic acid-modified diglycidyl Examples include ether type epoxy resins. These can be used alone or in combination of two or more.

  Among these, as the diglycidyl ether type epoxy compound, a bisphenol A type epoxy resin is preferable from the viewpoints of heat resistance, chemical resistance, and less shrinkage in curing.

  A commercially available thing can be used as a diglycidyl ether type epoxy compound mentioned above. Examples of the bisphenol A diglycidyl ether include Epicoat 828, Epicoat 1001 and Epicoat 1002 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Examples of bisphenol F diglycidyl ether include Epicoat 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Examples of bisphenol S diglycidyl ether include EBPS-200 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and Epicron EXA-. 1514 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.). Examples of biphenol diglycidyl ether include YL-6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of bixylenol diglycidyl ether include YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Can be mentioned. Furthermore, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (manufactured by Tohto Kasei Co., Ltd., trade name), and the dibasic acid-modified diglycidyl ether type epoxy resin described above is ST. -5100 and ST-5080 (above, manufactured by Tohto Kasei Co., Ltd., trade name).

  The epoxy equivalent of these diglycidyl ether type epoxy compounds (gram weight of the compound containing 1 equivalent of an epoxy group) can be measured according to JIS K 7236 “How to determine the epoxy equivalent of an epoxy resin”. From this measurement method, the epoxy equivalent of the diglycidyl ether type epoxy compound is preferably 150 to 1000, and more preferably 180 to 330, from the viewpoint of developability with a dilute aqueous alkali solution.

  The above-mentioned diglycidyl ether type epoxy compounds can be used alone or in combination of two or more.

  The dibasic acid used as a raw material in the first step is preferably a dicarboxylic acid. Specifically, for example, maleic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, 4 , 4'-dicarboxydiphenyl ether, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl sulfone, 4,4'-dicarboxybenzophenone, 1,3-adamantane dicarboxylic acid, 9,9-dimethyl santhene -3,6-dicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,4-cyclohexanedicarboxylic acid (manufactured by Aldrich) and the like. These dibasic acids can be used alone or in combination of two or more.

  Among these, tetrahydrophthalic acid is preferable as the dibasic acid used in the first step.

  The polymerization reaction in the first step can be performed by a conventional method. The blending ratio of the diglycidyl ether type epoxy compound and the dibasic acid is such that the functional group equivalent ratio (carboxyl group / epoxy group, carboxyl group / epoxy group, from the viewpoint of (A) molecular weight of base polymer, developability with dilute aqueous alkali solution, and storage stability. The molar ratio is preferably 1.03-1.30.

  Examples of the catalyst used for the polymerization reaction in the first step include phosphines, alkali metal compounds, and amines. Specifically, for example, phosphines such as tributylphosphine and triphenylphosphine, alkali metal compounds such as sodium hydroxide, lithium hydroxide and potassium hydroxide, dimethylparatoluidine, triethanolamine, N, N′-dimethylpiperazine , Amines such as triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine and tetramethylammonium bromide. These can be used alone or in combination of two or more.

  Among these, as a catalyst used for the polymerization reaction in the first step, dimethylparatoluidine is preferable from the viewpoint of efficiently synthesizing the resin having the structure represented by the general formula (1).

  From the viewpoint of the polymerization reaction rate, the amount of the catalyst used is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the diglycidyl ether type epoxy compound and the dibasic acid.

  The reaction temperature in the first step is preferably 100 to 150 ° C. from the viewpoint of the polymerization reaction rate and the prevention of the side reaction.

(Second step)
In the second step, (A) the base polymer is synthesized by reacting the intermediate product synthesized in the first step with an acid anhydride.

In addition, the acid anhydride residue represented by R ⁵ in the general formula (2) is a portion excluding the acid anhydride functional group in the structure of the acid anhydride.

  Examples of the acid anhydride used in the second step include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, etc. Aromatic polycarboxylic anhydrides and other polyvalent carboxylic acids such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride associated therewith And acid anhydride derivatives. These can be used alone or in combination of two or more.

  Of these, tetrahydrophthalic anhydride is preferred as the acid anhydride used in the second step.

  The amount of acid anhydride added is the functional group equivalent ratio (acid anhydride group in the acid anhydride to be added / hydroxyl group of the intermediate product produced in the first step, molar ratio, from the viewpoint of improving developability and reducing water absorption. ), It is preferably 0.6 to 1.3.

  The reaction temperature in the second step is preferably 80 to 130 ° C. from the viewpoint of reaction rate and the prevention of side reactions.

  In the method for synthesizing the base polymer (A), an appropriate amount of solvent is usually used. Specifically, for example, ketone compounds such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or methylcyclohexanone, aromatic hydrocarbon compounds such as toluene, xylene or tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol , Glycol ether compounds such as butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether or triethylene glycol monoethyl ether, ester compounds such as acetate compounds of the above glycol ether compounds, ethylene glycol or Alcohol compounds such as propylene glycol, petroleum ether, petroleum naphtha And petroleum solvents such as hydrogenated petroleum naphtha or solvent naphtha. These can be used alone or in combination of two or more.

<(B) component>
The acrylic polymer having a photopolymerizable unsaturated group as component (B) is not particularly limited in its composition or synthesis method, and a radical polymerizable copolymer having an ethylenically unsaturated group in the side chain is used. be able to. Such a radical polymerizable copolymer includes, for example, a vinyl copolymer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, an oxirane ring, an acid anhydride, and at least one ethylenically unsaturated group. It can be obtained by addition reaction of a compound having one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group and a carboxyl group.

  Examples of the vinyl monomer used in the production of the vinyl copolymer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Acid, itaconic acid, cinnamic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, ethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic anhydride, etc. carboxyl group, hydroxyl group, amino acid And vinyl monomers having a functional group such as a group, an oxirane ring, and an acid anhydride. These can be used alone or in combination of two or more.

  For the production of a radical polymerizable copolymer having an ethylenically unsaturated group in the side chain, if necessary, other than vinyl monomers having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride The vinyl monomer can be copolymerized. Examples of these vinyl monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, and iso-propyl methacrylate. , N-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, Pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, Nonyl crylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, acrylic acid Eicosyl, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid Phenyl, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, acrylic acid Methylaminoethyl, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate 2-fluoroethyl methacrylate, styrene, α-methylstyrene, cyclohexylmaleimide, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, vinyl toluene, vinyl chloride, vinyl acetate, N-vinyl pyrrolidone, butadiene, isoprene, Examples include chloroprene. These can be used alone or in combination of two or more.

The concentration of the ethylenically unsaturated group of the radically polymerizable copolymer having an ethylenically unsaturated group in the side chain is preferably 1.0 × 10 ^{−4 to} 6.0 × 10 ⁻³ mol / g. It is more preferable to set it as 0.0 * 10 < ^-4 > -5.0 * 10 < ^-3 > mol / g, and it is still more preferable to set it as 3 * 10 < ^-4 > -4.0 * 10 < ^-3 > mol / g. When the ethylenically unsaturated group concentration exceeds 6.0 × 10 ⁻³ mol / g, gelation tends to occur when a radical polymerizable copolymer having an ethylenically unsaturated group in the side chain is produced. . On the other hand, when the ethylenically unsaturated group concentration is less than 1.0 × 10 ⁻⁴ mol / g, the photocurability tends to be insufficient.

  The weight average molecular weight (measured by gel permeation chromatography and converted to standard polystyrene) of the acrylic polymer having a photopolymerizable unsaturated group as component (B) is the heat resistance, coatability, photosensitive element and From the viewpoints of film properties (characteristics that maintain a film-like form), solubility in a solvent, solubility in a developing solution in the development step described later, and the like, it is preferably 1,000 to 300,000. 5,000 to 150,000, more preferably 10,000 to 70,000.

  In addition to the acrylic polymer that is the component (B), a so-called binder polymer that does not have a photopolymerizable unsaturated group can be used in combination as necessary.

  There is no restriction | limiting in particular as this binder polymer, For example, a vinyl copolymer can be used. The above-mentioned thing can be used as a vinyl monomer used for a vinyl copolymer. These can be used alone or in combination of two or more.

  It is preferable that the acrylic polymer as the component (B) and the above-described binder polymer have an acid value suitable for a developer used in the development step described later.

  When an alkaline aqueous solution such as sodium carbonate, potassium carbonate, tetramethylammonium hydroxide or triethanolamine is used as the developer, the acid value of the component (B) is preferably 50 to 260 mgKOH / g. If the acid value is less than 50 mgKOH / g, development tends to be difficult, and if it exceeds 260 mgKOH / g, the developer resistance (the portion that becomes a pattern without being removed by development is not affected by the developer). ) Tends to decrease.

  When an alkaline aqueous solution composed of water or an aqueous alkaline solution and one or more surfactants is used as the developer, the acid value of the component (B) is preferably 16 to 260 mgKOH / g. If the acid value is less than 16 mg KOH / g, development tends to be difficult, and if it exceeds 260 mg KOH / g, the developer resistance tends to be lowered.

  Content of (B) component in the photosensitive resin composition is 20-80 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of developability and adhesiveness. It is preferably 40 to 60 parts by mass.

<(C) component>
Examples of the inorganic filler (C) include alumina, cerium oxide, cobalt oxide, copper oxide, iron oxide, magnesium oxide, silicon dioxide, tin oxide, indium tin oxide, zinc oxide, yttrium oxide, holmium oxide, and oxide. Bismuth etc. are mentioned.

  The inorganic filler as the component (C) can be blended by dispersing in ethanol, isopropyl alcohol, xylene, toluene, butyl acetate or the like, if necessary.

  The content of the component (C) in the photosensitive resin composition is such that the components (A) and (B) are from the viewpoint of achieving all the properties of developability, adhesive strength and low water absorption at a higher level. The total amount is 100 parts by mass, preferably 60 to 140 parts by mass, more preferably 80 to 120 parts by mass, and particularly preferably 80 to 100 parts by mass. When the content is less than 60 parts by mass, the water absorption rate tends to increase, or the curing shrinkage caused by light or heat curing of the photosensitive resin composition tends to increase and the adhesive strength decreases, and 140 masses. When it exceeds the part, the developability and the coating property tend to be lowered.

<(D) component>
The photopolymerizable monomer as component (D) has at least one ethylenically unsaturated group in the molecule. Examples of such photopolymerizable monomers include bisphenol A (meth) acrylate compounds, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, and glycidyl group-containing compounds with α, β-unsaturated compounds. Examples thereof include urethane monomers or urethane oligomers such as compounds obtained by reacting saturated carboxylic acids and (meth) acrylate compounds having urethane bonds. Besides these, nonylphenoxypolyoxyethylene acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl- Examples thereof include phthalic acid compounds such as o-phthalate, (meth) acrylic acid alkyl esters, EO-modified nonylphenyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Can be mentioned.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexa) Decaethoxy) phenyl) propane and the like. Of these, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). 4- (Methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These can be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Xinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane and 2,2-bis (4-((meth)) And acryloxyhexadecapropoxy) phenyl) propane. These can be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. These can be used alone or in combination of two or more.

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include those using (meth) acrylic acid or the like as the α, β-unsaturated carboxylic acid. Specifically, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, and 2 to 14 ethylene groups. Polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipenta Risuri penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. These can be used alone or in combination of two or more.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH (CH ₃ )). -O-) having a block structure.

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include those using (meth) acrylic acid or the like as the α, β-unsaturated carboxylic acid. Specific examples include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy) phenyl.

  Examples of urethane monomers include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Examples include addition reaction products, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO or PO-modified urethane di (meth) acrylate.

  Furthermore, examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester. It is done. These can be used alone or in combination of two or more.

  The content of the component (D) in the photosensitive resin composition is 40 to 120 parts by mass with respect to 100 parts by mass as a total of the components (A) and (B) from the viewpoint of resist formability. Preferably, it is 60-100 mass parts.

<(E) component>
Examples of the photoreaction initiator as component (E) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). -Butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin Benzoin compounds such as alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2,4,5-triarylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc. Acridine derivatives, N-phenylglycine, N-phenylglycine derivatives, Marine-based compounds, and the like. Among these, benzyl dimethyl ketal is particularly preferable. These can be used alone or in combination of two or more.

  Content of (E) component in the photosensitive resin composition is 1-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of economical efficiency and photosensitivity. It is preferably 5 to 8 parts by mass. When the component (E) exceeds 20 parts by mass, the cost tends to increase, and when it is less than 1 part by mass, sufficient photosensitivity tends to be not obtained.

  As mentioned above, although (A)-(E) component contained in the photosensitive resin composition of this invention was demonstrated in detail, components other than these, for example, a vinyl compound, a photoinitiator, a plasticizer, dye, as needed , Pigments, imaging agents, fillers, adhesion-imparting agents, and the like.

  For example, if a diallyl phthalate prepolymer having a repeating unit represented by the following formula (4) (Daiso Co., Ltd., trade name: DAP-K) is added to the photosensitive resin composition, the diallyl phthalate prepolymer becomes a hydrophilic group. By not having, water absorption can be further reduced.

  The weight average molecular weight of the diallyl phthalate prepolymer (measured by gel permeation chromatography and converted to standard polystyrene) is preferably in the range of 5000 to 50000, preferably in the range of 10,000 to 40000, from the viewpoint of developability and water absorption. Is more preferable.

  The addition amount of the diallyl phthalate prepolymer is preferably in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), from the viewpoint of water absorption and developability. The range of parts by mass is more preferable.

  Moreover, you may add a phenol resin to the photosensitive resin composition from a viewpoint of tackiness (adhesiveness of the surface of the photosensitive resin composition layer) reduction.

[Photosensitive element]
The photosensitive element of this invention is equipped with the support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition of this invention formed on this support body. The photosensitive resin composition layer can be formed by applying and drying the photosensitive resin composition of the present invention on a support. Moreover, the photosensitive element of this invention may further be equipped with the protective film laminated | stacked so that the surface on the opposite side to the support body of the photosensitive resin composition layer might be contact | connected.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. As shown in FIG. 1, the photosensitive element 1 includes a support 10, a photosensitive resin composition layer 20 provided on the support 10, and a protective film provided on the photosensitive resin composition layer 20. 30. Here, the photosensitive resin composition layer 20 is a layer formed using the photosensitive resin composition of the present invention.

  Although the thickness of the photosensitive resin composition layer 20 varies depending on the use, it is preferably 10 to 100 μm and more preferably 20 to 60 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. preferable. If the thickness is less than 10 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the above-described effects produced by the present invention tend to be reduced, and in particular, flexibility and resolution tend to decrease.

  Examples of the support 10 include polymer films having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

  The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. If the thickness is less than 5 μm, the support tends to be broken when the support is peeled off before development, and if it exceeds 100 μm, the resolution and flexibility tend to decrease.

  The photosensitive resin composition layer 20 is obtained by dissolving the photosensitive resin composition in a solvent or a mixed solvent to obtain a solution having a solid content of about 30 to 70% by mass, and then applying the solution on the support 10 to heat and It can be formed by removing the solvent by spraying hot air.

  The photosensitive element 1 can be produced by laminating a protective film 30 on the photosensitive resin composition layer 20 formed on the support 10.

  The photosensitive element consisting of two layers of the support and the photosensitive resin composition layer or the photosensitive element consisting of three layers of the support, the photosensitive resin composition layer and the protective film may be stored as they are, or It is also possible to wind up and store in a roll shape around a core after interposing a protective film.

[Method of forming resist pattern]
A method for forming a resist pattern using a photosensitive element includes a removing step of removing the protective film from the photosensitive element, and a laminating step of laminating the photosensitive element on the substrate in the order of the photosensitive resin composition layer and the support. , An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays to form a photocured portion on the photosensitive resin composition layer, and development for removing the photosensitive resin composition layer other than the photocured portion Process. In addition, in the case of the photosensitive element in which the protective film is not provided, the said removal process is not performed. Here, as the substrate, an insulating layer and a conductor layer formed on the insulating layer (copper, copper alloy, nickel, chromium, iron, stainless steel or other iron alloy, preferably copper, copper alloy, iron A silicon substrate, a glass substrate, and the like, and a silicon substrate and a glass substrate are preferable.

  In the laminating step, the photosensitive resin composition layer is laminated by being pressed onto the circuit forming substrate while heating. The atmosphere during the lamination is not particularly limited, but the lamination is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually the surface of the conductor layer of the circuit forming substrate, but may be a surface other than the conductor layer. The heating temperature of the photosensitive resin composition layer is preferably 70 to 130 ° C., the pressure bonding pressure is preferably about 0.1 to 1.0 MPa, and the ambient pressure is preferably 4000 Pa or less. These conditions are not particularly limited. If the photosensitive resin composition layer is heated to 70 to 130 ° C. when pressure-bonded to the circuit-forming substrate, it is not necessary to pre-heat the circuit-forming substrate in advance, but in order to further improve the laminating property, the substrate It is also possible to perform a pre-heat treatment.

  In the exposure step, the photosensitive resin composition layer is irradiated with actinic rays through a negative or positive mask pattern called artwork, and then developed with a developer to obtain a resist pattern. In this case, as the actinic ray used, one that effectively emits ultraviolet rays, such as a carbon arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, and a xenon lamp can be used.

  In the development process, a developer that is safe, stable, and has good operability is used. For example, a dilute solution of sodium carbonate at 20 to 50 ° C. or a tetramethylammonium hydroxide aqueous solution (both 1 to 5% by mass aqueous solution) is used. When it is necessary to reduce light elements such as for semiconductor use, an aqueous tetrahydroammonium hydroxide solution or the like can be used. Development methods include a dip method and a spray method, and the high pressure spray method is most suitable for improving the resolution.

  Through the above steps, the substrate on which the resist pattern is formed is thereafter mounted (for example, soldered) and mounted on an electronic device such as a camera.

  The resist pattern formed using the photosensitive resin composition of the present invention is suitably used as an adhesive between arbitrary substrates. For example, arbitrary base materials are bonded together by a thermocompression bonding process performed by heating and pressing for 10 to 30 seconds under conditions of a temperature of 140 to 160 ° C. and a pressure of 0.4 to 1.5 MPa. In order to improve adhesiveness etc., it is preferable to heat within the range of about 150-180 degreeC for about 30-90 minutes after a thermocompression bonding process.

  The photosensitive resin composition and photosensitive element of the present invention for bonding arbitrary substrates to each other can obtain sufficiently high adhesive strength and have good developability and a sufficiently low water absorption rate. For example, in the field of a CCD / CMOS image sensor, it can be suitably used for bonding an image sensor chip and a glass that protects the image sensor chip.

  Moreover, the resist pattern obtained by the above-mentioned formation method can also be used as a permanent resist formed on a base material.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1)
A modified epoxy resin as component (A) was prepared by the following method. First, in a flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, 67.9 parts by mass of a bisphenol A type liquid epoxy resin (manufactured by Mitsui Chemicals, trade name: EPOMIK R140Q, epoxy equivalent 187 g / eq). Then, 15.0 parts by mass of cyclohexanone and 10.0 parts by mass of toluene were charged, and the mixture was stirred while being heated to 140 ° C. while blowing nitrogen gas, whereby the water contained in the epoxy resin was refluxed and dehydrated.

  Subsequently, the temperature was lowered to 70 ° C., and 31.8 parts by mass of tetrahydrophthalic acid (manufactured by Nippon Nippon Chemical Co., Ltd.) and 1.4 parts by mass of dimethylparatoluidine (manufactured by Samsung Chemical Co., Ltd.) were added. Immediately after the addition, the temperature was raised to 85 ° C. and kept at 85 ° C. for 1 hour. Thereafter, similarly, the temperature increase and the heat retention were repeated in steps of 90 ° C. for 1 hour, 105 ° C. for 1 hour, 120 ° C. for 2 hours, and 140 ° C. for 10 hours.

  Next, 25.5 parts by mass of tetrahydrophthalic anhydride (manufactured by Nippon Nippon Chemical Co., Ltd.) and 6.7 parts by mass of cyclohexanone are added and kept at 120 ° C. for 2.5 hours, thereby modifying the modified epoxy as component (A). A resin was obtained. Thereafter, this modified epoxy resin was diluted with 50.0 parts by mass of methyl ethyl ketone. The resulting modified epoxy resin had a weight average molecular weight of 49000 and an acid value of 78 mgKOH / g. Further, the solid content of the diluted resin solution was 61.8% by mass.

  As the acrylic polymer having a photopolymerizable unsaturated group (B), methacrylic acid / dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-513M) / benzyl methacrylate / methacrylic acid An acid 2-hydroxyethyl / 2,2′-azobis (isobutyronitrile) copolymer (weight ratio 15 / 18.6 / 20 / 1.4 / 45, weight average molecular weight 26000) was used.

  20 parts by mass (solid content) of the above component (A), 30 parts by mass of the above component (B), 10 parts by mass of diallyl phthalate polymer (trade name: DAP-K, manufactured by Daiso), 4,4-bis (diethylamino) benzophenone (Hodogaya Chemical Co., Ltd., trade name: EAB) 0.2 parts by mass, bisphenol A type maleimide (Daiwa Kasei Co., Ltd., trade name: BMI-4000), 15 parts by mass, 2,5-dimethyl-2,5-di- [T-Butylperoxy] hexyne-3 (Nippon Yushi Co., Ltd., trade name: Perhexine B25) 2.1 parts by mass, and methacryloxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd., trade name: SZ-6030) 5 parts by mass was blended to prepare a mixed solution.

  Next, (C) component inorganic silica filler (Hitachi Chemical Industry Co., Ltd. prototype, average particle size: 0.54 μm) is dispersed in methyl ethyl ketone so that its concentration is 50.1% by mass. A dispersion was prepared. 100 parts by mass of this dispersion (50 parts by mass of solid content) was blended in a mixed solution containing the above component (A) and component (B).

  Next, as a photopolymerizable monomer as component (D), 20 parts by mass of urethane acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: TMCH-5), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product) Name: DPHA) 15 parts by mass and ethoxylated bisphenol A type dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: BPE-200) 10 parts by mass mixed solution containing the above components (A) to (C) Blended into

  Next, 8 parts by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals, Inc., trade name: Irgacure 651) is used as a photoreaction initiator as component (E). (A)-(D) It mix | blended with the mixed solution containing a component, and the solution of the negative photosensitive resin composition was obtained.

  This photosensitive resin composition solution is uniformly applied onto a 16 μm-thick polyethylene terephthalate film as a support, and dried with a hot air convection dryer at 100 ° C. for about 10 minutes to form a photosensitive resin composition layer. did. Thereby, a negative photosensitive element was obtained. The film thickness of the photosensitive resin composition layer after drying was 50 μm.

(Examples 2 to 4 and Comparative Examples 1 to 3)
Photosensitive elements of Examples 2 to 4 and Comparative Examples 1 to 3 were produced in the same manner as in Example 1 except that the blending amounts of the components (A) to (E) were changed to the blending amounts shown in Table 1.

[Evaluation of developability]
The photosensitive resin composition layers of the photosensitive elements of Examples 1 to 4 and Comparative Examples 1 to 3 were each laminated on a silicon wafer while being heated to 80 ° C. to prepare a substrate. Using a negative film having a pattern with a line width / space width of 30 to 200/400 (unit: μm) as a negative for evaluation on the produced substrate, a 5 kW high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., trade name: HMW-201GX) was exposed with an energy amount of 317 mJ / cm ² . After the exposure, each substrate was evaluated as follows.

  After removing the polyethylene terephthalate film from the exposed substrate, a 3.3 mass% tetramethylammonium hydroxide aqueous solution was sprayed at 22 ° C for 60 seconds to remove unexposed portions. In this case, in a pattern having a line width of 150 μm, A is the pattern tailing (development residue) less than 5 μm, B is the case where the pattern is in the range of 5 to 15 μm, and C is the case exceeding 15 μm. It was evaluated. Here, the skirting is a phenomenon in which the width (150 μm) of the resist pattern in the bonded portion with the silicon wafer becomes large without being developed, and indicates that a resist pattern with a smaller skirting has better developability. Yes. The evaluation results are shown in Table 1.

[Evaluation of adhesive strength]
Substrate preparation, exposure and development in the same manner as in the above “evaluation of developability”, except that a negative film having a grid pattern with a line width / space width of 0.1 / 2.0 (unit: mm) was used. Went. After development, a substrate having a size of 6.2 mm × 6.2 mm (having two resists having a width of 0.1 mm in both length and width) is cut out, and the substrate and the soda glass substrate are heated at 150 ° C., 1.2 MPa for 30 seconds. Thermocompression bonding was performed under the conditions. Next, after thermosetting at 160 ° C. for 1 hour, shear strength measurement was performed at room temperature using sereis 4000 manufactured by dage, and adhesive strength was calculated. The results are shown in Table 1. In addition, as shown in the evaluation results of developability in Table 1, there was a sample in which an unexposed part remained, but the unexposed part does not contribute to the adhesive strength because it does not have adhesiveness.

[Evaluation of water absorption rate]
Based on JIS K7209, the water absorption rate measurement of the photosensitive resin composition layer after thermosetting was performed as follows. Laminate each photosensitive element (80 mm × 140 mm) of Examples 1 to 4 and Comparative Examples 1 to 3 with heating to 80 ° C. on a substrate that does not absorb water (SUS plate, size: 100 mm × 160 mm, mass; M1). A substrate was produced. Thereafter, in the same manner as in “Evaluation of Adhesive Strength”, exposure, development, thermocompression bonding, and thermosetting were performed to prepare each test piece (mass; M2). The test piece was immersed in water at room temperature for 24 hours, and the mass (M3) after the immersion was measured. From these results, the following formula (II):
Water absorption (%) = {(M3-M2) / (M2-M1)} × 100 (II)
The water absorption was calculated by The results are shown in Table 1.

  As is clear from the results shown in Table 1, according to the photosensitive resin composition and the photosensitive resin element (Examples 1 to 4) of the present invention, the photosensitive resin composition and the photosensitive property of Comparative Examples 1 to 3 were used. Compared with the resin element, it is possible to obtain a sufficiently high adhesive strength and to have both good developability and a sufficiently low water absorption (particularly, a sufficiently low water absorption of 1.0% or less). confirmed.

  As described above, according to the present invention, a sufficiently high adhesive strength can be obtained, and a photosensitive resin composition having a good developability and a sufficiently low water absorption rate, and a photosensitive element using the same. Can be provided.

Claims (2)

(A) a base polymer having a repeating unit represented by the following general formula (1), (B) an acrylic polymer having a photopolymerizable unsaturated group, (C) an inorganic filler, and (D) photopolymerizability. A photosensitive resin composition comprising a monomer and (E) a photoreaction initiator.

[In the formula (1), R ¹ represents a divalent organic group which is a diglycidyl ether type epoxy compound residue, R ² represents a divalent organic group which is a dibasic acid residue, R ³ and R ⁴ each independently represents a hydrogen atom or the following general formula (2);

(In formula (2), R ⁵ represents an acid anhydride residue.). ]   A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition of Claim 1 formed on this support body.

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