JP5768745B2 - Adhesive comprising photosensitive resin composition - Google Patents

Description

  The present invention relates to an adhesive comprising a photosensitive resin composition and a hollow package structure using the same.

  Conventionally, a liquid UV curable photosensitive resin composition applied by a printing method may be used for adhesion of each member when producing a hollow package structure for various sensors. For example, when a CCD / CMOS image sensor package is manufactured, a UV curable photosensitive resin composition is formed on a ceramic or epoxy resin rib on the chip in order to protect the sensor portion of the image sensor chip from moisture and dust. An object is applied, and a protective glass is placed thereon to adhere.

  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. Further, along with the recent price competition, there is a demand for a film type photosensitive resin composition (photosensitive element) capable of reducing the cost by shortening the number of processes and performing batch molding.

  Photosensitive elements are widely developed for circuit formation of printed wiring boards and solder resists. For example, Patent Document 1 discloses a photosensitive resin composition having excellent adhesion and resolution and suppressing generation of scum, and further a photosensitive element useful for increasing the density of printed wiring boards.

JP 2002-351070 A

  When a photosensitive element is used for producing a hollow package for an image sensor, a high temperature treatment such as reflow is performed. However, when a conventional photosensitive resin composition excellent in developability such as that described in Patent Document 1 is adopted for the photosensitive element, components derived from the composition are volatilized by the high-temperature treatment and outgas is generated. . This outgas adheres to the sensor portion and the protective glass in the package and deteriorates the sensor characteristics.

  The present invention has been made in view of the above circumstances, and provides a photosensitive resin composition having good developability and sufficiently reducing outgas after curing, and a photosensitive element using the same. Objective.

  In order to achieve the above object, the present invention provides (A) a binder polymer having a carboxyl group, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E And a photosensitive resin composition containing a compound having a heterocycle.

  In the photosensitive resin composition of this invention, by providing the said structure, while having favorable developability, it is possible to fully reduce the outgas after hardening. Here, the reason why the above effect is obtained is not necessarily clear, but the present inventors consider the following factors. However, the factor is not limited to this.

  It is preferable that the photosensitive resin composition contains a binder polymer having a carboxyl group from the viewpoint of improving alkali developability. However, since the carboxyl group is unstable due to heat treatment at high temperature, it is easily decomposed, and the component derived from the carboxyl group is considered to be outgassed and adhere to the sensor portion, the protective glass, or the like. In particular, in a binder polymer having a carboxyl group derived from an acid anhydride, the carboxyl group is easily decomposed, and outgassing becomes remarkable. Then, this invention contains the binder polymer which has a carboxyl group, and the compound which has a heterocyclic ring. Thus, it is presumed that the carboxyl group and the compound having a heterocycle are cross-linked, and the decomposition is suppressed by converting the carboxyl group into a stable structure, thereby sufficiently reducing the outgas.

The component (A) preferably includes a polymer having a group represented by the following general formula (2). In the general formula (2), L ³ represents an acid anhydride residue. Since the photosensitive resin composition containing such a polymer tends to generate outgas, the effect of the present invention by containing the component (E) can be more effectively expressed.

Moreover, it is preferable that the said (A) component contains the polymer which has a repeating unit represented by following General formula (1).


Here, L ¹ represents a divalent organic group that is a diglycidyl ether type epoxy compound residue, L ² represents a divalent organic group that is a dibasic acid residue, and ^one of R ¹ and R ² One represents a group represented by the general formula (2), and the other represents a hydrogen atom or a group represented by the general formula (2).

  Such a photosensitive resin composition not only can sufficiently satisfy both alkali developability and low outgassing properties, but also has a reduced water absorption rate and good adhesive strength.

  Furthermore, in the photosensitive resin composition of the present invention, the component (E) preferably contains a compound having an oxazoline skeleton and / or an epoxy skeleton. Thereby, the effect of the present invention that outgas can be reduced can be achieved more effectively and reliably.

  The present invention provides a photosensitive element comprising a support film and a photosensitive resin composition layer made of the photosensitive resin composition formed on the support film.

  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 has good developability and sufficiently reduces outgas. Can do.

  ADVANTAGE OF THE INVENTION According to this invention, while having favorable developability, the photosensitive resin composition which fully reduced the outgas after hardening, and the photosensitive element using the same can be provided.

It is a schematic cross section which shows suitable embodiment of the photosensitive element of this invention. 2 is a photomicrograph obtained by observing outgassing of the photosensitive resin composition layer of Example 1. FIG. 2 is a photomicrograph of the outgassing of the photosensitive resin composition layer of Comparative Example 1.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In addition, “(meth) acrylate” in the present specification means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” and corresponding “methacryloyl”.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) a binder polymer having a carboxyl group (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable compound (hereinafter sometimes referred to as “(B)”. (Component)), (C) a photopolymerization initiator (hereinafter sometimes referred to as “(C) component”), (D) an inorganic filler (hereinafter sometimes referred to as “(D) component”), and (E ) A compound having a heterocycle (hereinafter, sometimes referred to as “component (E)”).

  Hereinafter, each component contained in the photosensitive resin composition of the present invention will be described in detail.

<(A) component>
The binder polymer having a carboxyl group as the component (A) is not particularly limited as long as it is a polymer modified with a carboxyl group. Examples of the polymer modified with a carboxyl group include acrylic resins, epoxy acrylate resins, polyester resins, amide resins, amide imide resins, imide resins, and epoxy resins. Among these, acrylic resins and / or epoxy resins are preferable from the viewpoints of excellent alkali developability, high adhesion, low water absorption, and high adhesion.

  As the epoxy resin modified with a carboxyl group (hereinafter referred to as “carboxyl-modified epoxy resin”), a polymer having a group represented by the above general formula (2) is preferable, and a repeat represented by the above general formula (1) is preferable. More preferred are polymers having units.

  This polymer synthesis method includes a first step of obtaining an intermediate product by polymerization reaction of a diglycidyl ether type epoxy compound having two glycidyl groups in one molecule and a dibasic acid, and an acid anhydride is added to the intermediate product. And a second step of obtaining a polymer having a carboxyl group as described above by addition.

The above general formula (1) diglycidyl ether type epoxy compound residues represented by L ¹ in the structure of the diglycidyl ether-type epoxy compound, a portion excluding a glycidyl group. In addition, the dibasic acid residue represented by L 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, L ⁴ represents a divalent organic group, is preferably a divalent organic group having an aromatic ring or an alicyclic ring, and more preferably has a bisphenol skeleton.

  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.

  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. For example, as bisphenol A diglycidyl ether, Epicoat 828, Epicoat 1001 and Epicoat 1002 (above, product name manufactured by Japan Epoxy Resin Co., Ltd.) can be exemplified. Examples of bisphenol F diglycidyl ether include Epicoat 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of bisphenol S diglycidyl ether include EBPS-200 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and Epicron EXA-1514. (Dainippon Ink Chemical Co., Ltd., trade name). Examples of the biphenol diglycidyl ether include YL-6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), and examples of the bixylenol diglycidyl ether include YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). be able to. Furthermore, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (trade name, manufactured by Tohto Kasei Co., Ltd.). As the above-mentioned dibasic acid-modified diglycidyl ether type epoxy resin, ST- 5100 and ST-5080 (above, manufactured by Tohto Kasei Co., Ltd., trade name).

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

  The epoxy equivalent of the diglycidyl ether type epoxy compound (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 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.) and 1,4-cyclohexanedicarboxylic acid (manufactured by Aldrich). These dibasic acids can be used individually by 1 type or in combination of 2 or more types.

  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 compounding ratio of the diglycidyl ether type epoxy compound and the dibasic acid is determined from the viewpoint of the molecular weight of the carboxyl-modified epoxy resin, the developability with a dilute alkali aqueous solution, and the storage stability (functional group equivalent ratio (carboxyl group / epoxy group, mole). 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 carboxyl-modified epoxy resin is synthesized by reacting the intermediate product synthesized in the first step with an acid anhydride.

In addition, the acid anhydride residue represented by L ³ 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 synthesis method of the carboxyl-modified epoxy resin, 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 Petroleum solvents such as hydrogenated petroleum naphtha or solvent naphtha. These can be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the carboxyl-modified epoxy resin is preferably 10,000 to 70,000, and preferably 30,000 to 50,000 from the viewpoint of coating properties (difficulty in stickiness) and developability with a dilute aqueous alkali solution. Is more preferable.

In addition, the weight average molecular weight in this specification is calculated | required by measuring according to the following conditions by gel permeation chromatography (GPC) analysis, and converting using a standard polystyrene calibration curve.
(GPC conditions)
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name)
Detector: Hitachi L-4000 type UV (manufactured by Hitachi, Ltd., trade name)
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: 30 mg / 1 mL
Injection volume: 5 μL
Pressure: 274 Pa (28 kgf / cm ² )
Flow rate: 1.0 mL / min

  Moreover, it is preferable to use together a carboxyl modified epoxy resin and an acrylic resin from a viewpoint which can improve developability, resolution, and adhesiveness more. As said acrylic resin, what copolymerized (meth) acrylic acid and (meth) acrylic acid ester is preferable.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (meth) Dodecyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and dicyclo ring Or (meth) acrylic acid ester having a tricyclo ring .

Examples of the (meth) acrylic acid ester having a dicyclo ring or a tricyclo ring include dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and tricyclo [5.2.1.0 ^2.6. And (meth) acrylic acid ester having a decyl group. In particular, tricyclo [5.2.1.0 ^{2, 6]} decyl (meth) tricyclo [5.2.1.0 ^{2, 6]} having a decyl group (meth) acrylic acid esters such as acrylate is valid. These can be used individually by 1 type or in combination of 2 or more types.

  Furthermore, it is preferable that the said acrylic resin has an ethylenically unsaturated group from a viewpoint of improving adhesive force. The acrylic resin having an ethylenically unsaturated group is not particularly limited in its composition and synthesis method, and may have an ethylenically unsaturated group in the side chain. As an acrylic resin having an ethylenically unsaturated group in the side chain, for example, at least one acrylic resin having a functional group in the side chain such as a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, an oxirane ring, and an acid anhydride is included. The compound having an ethylenically unsaturated group and one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group and a carboxyl group can be obtained by addition reaction.

  The weight average molecular weight of the acrylic resin is as follows: heat resistance, coatability, film properties when used as a photosensitive element (characteristics that maintain a film-like form), solubility in a solvent, and dissolution in a developer in the development step described below. From the viewpoint of properties and the like, it is preferably 1000 to 300,000, more preferably 5000 to 150,000, and particularly preferably 10,000 to 100,000. If the weight average molecular weight of the acrylic resin is less than 1000, the alkali resistance tends to decrease, and if it exceeds 300,000, the viscosity of the photosensitive resin composition increases, and thus the applicability of the photosensitive resin composition tends to decrease. is there.

  The component (A) may be a radical polymerizable copolymer having an ethylenically unsaturated group in the side chain other than the acrylic resin. The radical polymerizable copolymer is, 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, and an acid anhydride in the side chain, and at least one ethylenically unsaturated copolymer. It can be obtained by addition reaction of a compound having a group and 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 carboxyl group, hydroxyl group, amino group, isocyanate group, oxirane ring, and acid anhydride include acrylic acid, methacrylic acid, and maleic acid. , Fumaric acid, itaconic acid, cinnamic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-isocyanate ethyl methacrylate, acrylamide, methacrylamide, ethyl isocyanate methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic anhydride Examples include acids. These can be used individually by 1 type or in combination of 2 or more types.

The ethylenically unsaturated group concentration in 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 2.0 * 10 < ^-4 > -5.0 * 10 < ^-3 > mol / g, and it is especially 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.

  (A) It is preferable that the binder polymer which has a carboxyl group has an acid value suitable for the developing solution used at the image development process mentioned later.

(A) The acid value of the binder polymer having a carboxyl group can be measured by the following method. First, (A) about 1 g of a binder polymer solution having a carboxyl group is precisely weighed, then 20 g of DMF is added to the binder polymer solution, and the binder polymer solution is uniformly dissolved. 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 binder polymer solution mass (g) having a carboxyl group, I shows the ratio (mass%) of the non volatile matter in the binder polymer solution which has (A) a carboxyl group.

  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 binder polymer having a carboxyl group (A) is preferably 50 to 260 mgKOH / g. 60 to 220 mgKOH / g, more preferably 70 to 200 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.

  Moreover, when developing using the aqueous solution which consists of water or aqueous alkali solution and 1 or more types of surfactant as a developing solution, (A) Acid value of the binder polymer which has a carboxyl group is 16-260 mgKOH / g. It is preferable that 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.

<(B) component>
The photopolymerizable compound as component (B) preferably has at least one ethylenically unsaturated group in the molecule. Examples of such photopolymerizable compounds 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- Examples thereof include a urethane monomer or urethane oligomer such as a compound obtained by reacting an unsaturated carboxylic acid and a (meth) acrylate compound having a urethane bond. Other than these, nonylphenoxy polyoxyethylene 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, and EO-modified nonylphenyl (meth) acrylate. These can be used individually by 1 type or in combination of 2 or more types.

  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 and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane. It is done.

  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. 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 individually by 1 type or in combination of 2 or more types.

  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)) Acryloxyhexadecapropoxy) phenyl) propane. These can be used individually by 1 type or in combination of 2 or more types.

  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 individually by 1 type or in combination of 2 or more types.

  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 individually by 1 type or in combination of 2 or more types.

“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. Addition reactants, 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 alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B) in the photosensitive resin composition is preferably 40 to 120 parts by mass, and 60 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of resist formability. More preferably.

<(C) component>
Examples of the photopolymerization initiator that is the component (C) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). Aromatic ketones such as butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; quinones such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ethers; Benzoin compounds such as alkylbenzoin; benzyl derivatives such as benzyldimethyl ketal and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2,4,5-triarylimidazole dimer 9-phenylacridine, 1,7-bis (9,9′-acridinyl); Acridine derivatives such as heptane; N- phenylglycine, N- phenylglycine derivatives; coumarin compounds and the like. Among these, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) is particularly preferable from the viewpoint of low sublimation. These can be used individually by 1 type or in combination of 2 or more types.

  Content of (C) component in the photosensitive resin composition is 1-10 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 2 to 5 parts by mass. If the content of the component (C) exceeds 10 parts by mass, the cost tends to increase, and if it is less than 1 part by mass, it is difficult to obtain sufficient photosensitivity.

<(D) component>
The inorganic filler as component (D) functions as a component for reducing curing shrinkage and water absorption. The inorganic filler is preferably a metal oxide filler from the viewpoint of effectively exhibiting the above functions. Specific examples thereof include alumina, acid value cerium, acid value cobalt, copper oxide, acid value iron, acid value magnesium, silicon dioxide, acid value tin, acid value indium tin, acid value zinc, acid value yttrium, and acid value holmium. And acid value bismuth.

  The inorganic filler can be blended in ethanol, isopropyl alcohol, xylene, toluene, butyl acetate or the like, if necessary.

  The content of the component (D) in the photosensitive resin composition is 60% with respect to 100 parts by mass of the component (A) from the viewpoint of achieving all the properties of developability, adhesive strength and low water absorption at a higher level. It is preferable that it is -140 mass parts, It is more preferable that it is 80-120 mass parts, It is especially preferable that it is 80-100 mass parts. If this content is less than 60 parts by mass, the water absorption rate tends to increase, and if it exceeds 140 parts by mass, the developability and coating properties tend to decrease.

<(E) component>
The compound having a heterocyclic ring as component (E) is not particularly limited as long as it can be crosslinked by reacting with a carboxyl group in the binder polymer, and in particular, a compound having an oxazoline skeleton and / or a compound having an epoxy skeleton. Is preferred.

  Examples of the compound having an oxazoline skeleton include 2,2 ′-(1,3-phenylene) bis-2-oxazoline, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4, 4-dimethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-5,5-dihydro-4H-1,3-oxazine, 4,4,6-trimethyl-2-vinyl-5 Examples include vinyl oxazoline such as 6-dihydro-4H-1,3-oxazine, 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, but are particularly limited to these. It is not a thing. Among these compounds having an oxazoline skeleton, it does not react with the carboxyl group in the temperature range at the time of forming the photosensitive resin composition layer, but reacts well with the carboxyl group in the temperature range at the time of forming the bonded portion by thermocompression bonding. 2,2 ′-(1,3-phenylene) bis-2-oxazoline is preferred.

  Although content of the compound which has an oxazoline skeleton is not specifically limited, It is desirable that it is 25-75 mol% with respect to the carboxyl group equivalent in (A) component. If the amount is less than 25 mol%, the effect of oxazoline crosslinking is insufficient, and if it exceeds 75 mol%, the compound itself having an oxazoline skeleton tends to volatilize, and outgassing tends to occur.

  Examples of the compound having an epoxy skeleton used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy resin, and phenol novolac type epoxy resin. Cresol type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, and epoxidized polybutadiene resin. Among these, since a compound having an epoxy skeleton that is liquid at room temperature easily generates outgas, an epoxy resin that is solid at room temperature is preferable, and a cresol novolac type epoxy resin is preferable.

  Although content of the compound which has an epoxy skeleton is not specifically limited, It is desirable that it is 25-100 mol% of a carboxyl group equivalent. When the content of the compound having an epoxy skeleton is less than 25 mol%, the effect of epoxy crosslinking is insufficient, and when it exceeds 100 mol%, the effect of the present invention is not sufficiently achieved.

<Other ingredients>
As described above, the components (A) to (E) contained in the photosensitive resin composition of the present invention have been described in detail. However, the photosensitive resin composition of the present invention may include other components, for example, A vinyl compound, a plasticizer, a dye, a pigment, an imaging agent, a filler, an organic filler, and an adhesion promoter can be blended.

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

  The weight average molecular weight of the diallyl phthalate prepolymer is preferably 5,000 to 50,000, more preferably 10,000 to 40,000 from the viewpoints of developability and water absorption.

  The addition amount of the diallyl phthalate prepolymer is preferably 1 to 40 parts by mass, and 10 to 30 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of water absorption and developability. More preferred.

  The photosensitive resin composition of the present invention preferably contains a silane coupling agent as an adhesion-imparting agent from the viewpoint of further improving the adhesion. Examples of silane coupling agents include amino silane coupling agents, ureido silane coupling agents, vinyl silane coupling agents, methacrylic silane coupling agents, epoxy silane coupling agents, and mercapto silane couplings. And an isocyanate-based silane coupling agent. Specifically, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, ureidopropyltri Ethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane.

  Furthermore, the photosensitive resin composition of the present invention preferably contains a phenolic resin or the like from the viewpoint of suppressing bleeding (bleed out) of the photosensitive resin composition during substrate lamination.

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

  FIG. 1 is a diagram schematically showing a cross-sectional configuration of a photosensitive element according to a preferred embodiment. As shown in FIG. 1, the photosensitive element 1 includes a support film 10, a photosensitive resin composition layer 20 provided on the support film 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 above-described photosensitive resin composition of the present invention.

  Examples of the support film 10 include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate film, polypropylene film, polyethylene film, and polyester film. Among these, it is preferable to use a polyethylene terephthalate film from the viewpoint of transparency. In addition, since these polymer films must be removable from the photosensitive resin composition layer 20 later, they may be subjected to a surface treatment or a material that makes removal impossible. should not be done.

  Moreover, it is preferable that the thickness of the support film 10 is 5-100 micrometers, and it is more preferable that it is 10-50 micrometers. When the thickness of the support film is less than 5 μm, the support film tends to be easily broken when the support film is peeled off, while when it exceeds 100 μm, the resolution and flexibility tend to decrease.

  The photosensitive resin composition layer 20 can be formed, for example, by applying the photosensitive resin composition of the present invention on the support film 10 and then drying. The coating can be performed by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a slee coating method. Moreover, drying can be performed at 70-150 degreeC for about 5 to 30 minutes.

  When the photosensitive resin composition is applied on the support film 10, a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether is used as necessary. Or it is preferable to apply | coat the solution about 30-70 mass% of solid content which melt | dissolved the photosensitive resin composition in these mixed solvents.

  Although the thickness of the photosensitive resin composition layer 20 changes with uses, it is preferable that it is 10-100 micrometers by the thickness after drying, and it is more preferable that it is 20-60 micrometers. If the thickness is less than 10 μm, coating tends to be industrially difficult. If the thickness 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. .

  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.

  As the protective film 30, for example, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, a polyethylene film, and a polyester film can be used. In the photosensitive element 1, a polymer film similar to the support film 10 described above may be used as the protective film 30.

  The adhesive force between the protective film 30 and the photosensitive resin composition layer 20 is such that the protective resin 30 is easily peeled off from the photosensitive resin composition layer 20, It is preferable that it is smaller than the adhesive force between.

  The thickness of the protective film 30 is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. When the thickness of the protective film is less than 1 μm, the protective film tends to be broken during lamination, and when it exceeds 100 μm, the price tends to increase.

  The photosensitive element 1 can be stored, for example, in the form of a flat plate as it is or in the form of a roll wound around a cylindrical core. In addition, it is preferable to wind up so that the support film 10 may become the outermost side in this case.

  Further, when the photosensitive element 1 has a two-layer configuration not having the protective film 30, the photosensitive element is in the form of a flat plate as it is or on the support film side of the photosensitive resin composition layer 20. A protective film can be further laminated on the opposite surface, wound around a cylindrical core, and stored in a roll form.

[Pattern formation method]
The pattern forming method using the photosensitive element of the present invention includes a removal step of removing the protective film from the photosensitive element, and the photosensitive element on the substrate or member in the order of the photosensitive resin composition layer and the support. Laminating step of laminating, 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 photosensitive resin composition other than the photocured portion And a developing step for removing the physical layer. In addition, in the case of the photosensitive element in which the protective film is not provided, the said removal process is not performed.

  In the laminating step, the photosensitive resin composition layer is laminated by being pressure-bonded to the substrate or member surface 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 heating temperature of the photosensitive resin composition layer is preferably 70 to 130 ° C., and the pressure is preferably about 0.1 to 1.0 MPa, but these conditions are not particularly limited. In addition, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the base material or member in advance, but in order to further improve the laminating property, The member can also be preheated.

  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 pattern. In this case, as the actinic ray used, those that effectively emit ultraviolet rays such as a carbon arc lamp, an ultrahigh 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. As the developer, for example, a dilute solution (1 to 5% by mass aqueous solution) of sodium carbonate at 20 to 50 ° C. is used. When it is necessary to reduce light metal elements such as for semiconductor use, for example, an aqueous tetramethylammonium hydroxide solution can be used. Development methods include a dip method and a spray method, and the high pressure spray method is most suitable for improving developability and resolution.

  The base material or member on which the pattern has been formed by the above steps is then subjected to component mounting (for example, soldering) and mounted on an electronic device such as a camera.

  The pattern formed using the photosensitive resin composition of the present invention is suitably used as an adhesive between arbitrary base materials or members. For example, it may be used as an adhesive for bonding a CCD / CMOS image sensor chip and its protective glass. In this case, the image sensor chip is provided with a rib, and a patterned photosensitive resin composition layer is formed on the rib, and a protective glass is further applied thereon to perform a predetermined treatment and adhere. Good. Alternatively, when the image sensor chip does not include a rib, a patterned photosensitive resin composition layer is formed on the peripheral edge of the image sensor chip, and further, a protective glass is placed thereon to perform a predetermined treatment and adhesion. May be. In this case, according to the photosensitive resin composition of the present invention, since the developability is excellent, the photosensitive resin composition layer can be formed in a desired pattern.

  For example, arbitrary base materials are bonded together by a thermocompression bonding process performed by heating and pressing for 1 to 60 seconds under conditions of a temperature of 130 to 180 ° C. and a pressure of 0.1 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 also have good developability and a sufficiently low water absorption rate. It is also effective for the production of a hollow package structure for various sensors other than the above.

  Further, the pattern obtained by the above-described forming method can also be used as a resist such as a permanent resist formed on the substrate. 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 And a silicon substrate, a glass substrate, and the like.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

Preparation of component (A) (Synthesis Example 1)
A carboxyl-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 inlet tube, a bisphenol A type liquid epoxy resin (trade name “EPOMIK R140Q”, epoxy equivalent 187 g / eq, manufactured by Mitsui Chemicals, Inc.) 67.9 mass Part, 15.0 parts by mass of cyclohexanone and 10.0 parts by mass of toluene were added, and the mixture was stirred while being heated to 140 ° C. while blowing nitrogen gas, thereby performing reflux dehydration of water contained in the epoxy resin.

  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 Shin Nippon Rika Co., Ltd.) and 6.7 parts by mass of cyclohexanone are added and kept at 120 ° C. for 2.5 hours, and the carboxyl-modified epoxy resin as component (A) Got. Thereafter, the carboxyl-modified epoxy resin was diluted with 50.0 parts by mass of methyl ethyl ketone to prepare a solution of the carboxyl-modified epoxy resin. The resulting carboxyl-modified epoxy resin had a weight average molecular weight of 49000 and an acid value of 78 mgKOH / g. The solid content of the diluted carboxyl-modified epoxy resin solution was 64.0% by mass.

(Synthesis Example 2)
As the acrylic resin as component (A), methacrylic acid / dicyclopentanyl methacrylate (made by Hitachi Chemical Co., Ltd., trade name “FA-513M”) / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer (mass) An acrylic resin obtained by reacting 2-isocyanatoethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI”) with a ratio of 15/45/20/20) was synthesized by a conventional method. The weight average molecular weight of the obtained acrylic resin was 26000.

Preparation of component (B) As component (B), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA”) and ethoxylated bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “BPE”) -200 ").

Preparation of component (C) As component (C), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name “Irg-369” manufactured by Ciba Specialty Chemicals) And 4,4-bis (diethylamino) benzophenone (manufactured by Hodogaya Chemical Co., Ltd., trade name “EAB”).

Preparation of Component (D) As component (D), an inorganic silica filler (average particle size: 0.54 μm, diluted with 70 wt% methyl isobutyl ketone) was prepared.

(E) Preparation of Component As component (E), 2,2 ′-(1,3-phenylene) bis-2-oxazoline (trade name “1,3-PBO” manufactured by Mikuni Pharmaceutical Co., Ltd.) and cresol novolak type An epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name “EPICLON N-665-EXP”) was prepared.

  As other components, thermosetting agent “BMI-4000” (bisphenol A maleimide), thermal polymerization initiator “Perhexa HC” (1,1-di- [t-hexylperoxy] cyclohexane, manufactured by NOF Corporation , Product name), film property imparting polymer “MEH-7851M” (biphenyl-phenol resin, product name, manufactured by Meiwa Kasei Co., Ltd.), coupling agent “SZ-6030” (methacryloxypropyltrimethoxysilane, Toray Dow Corning Product name) and “SILQUEST A-187” (3-glycidoxypropyltrimethoxysilane, manufactured by GE Toshiba Silicone, product name) were prepared.

(Examples 1-2 and Comparative Example 1)
The above components were blended in the blending amounts (unit: parts by mass) shown in Table 1, and solutions of photosensitive resin compositions of Examples and Comparative Examples were prepared. In addition, the numerical value in a table | surface shows the compounding ratio of solid content of each component.

  This photosensitive resin composition solution is uniformly applied onto a 16 μm-thick polyethylene terephthalate film, which is a support film, and dried for about 10 minutes with a 100 ° C. hot air convection dryer 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.

[Evaluation of photosensitive properties]
A normal pressure laminator (manufactured by Taisei Laminator Co., Ltd.) was used on a silicon wafer while heating the photosensitive resin composition layers of the photosensitive elements obtained in Examples and Comparative Examples to 80 ° C., and 80 ° C., 0.4 MPa, 1 Lamination was performed under the condition of 0.0 m / min. Next, on the substrate thus obtained, Hitachi 41 step tablet scale (ST = x / 41) and Hitachi test pattern G2 negative film (resolution line width / space width (L / S) = 30 to 200/30). ˜200 μm, adhesion L / S = 30 to 200/400 μm, dropout resolution L / S = 400/30 to 200 μm), and 5 kW high-pressure mercury lamp (trade name “HMW-201GX” manufactured by Oak Manufacturing Co., Ltd.) Then, an exposure of 600 mJ / cm ² was performed. Next, after removing the polyethylene terephthalate film from the exposed substrate, spray with a 3.3% tetramethylammonium hydroxide aqueous solution (containing 0.3% surfactant) at 23 ° C. for 110 seconds to remove the unexposed portions. did.

  The final remaining number of steps on which a pattern after development was formed was read and used as sensitivity. Further, the minimum line width value of the test pattern in which the line is completely developed is defined as the resolution, and the minimum space width value is defined as the resolution. In addition, the minimum line width value of the test pattern that remained completely without expansion or lack of line width was defined as adhesion. The results are shown in Table 2.

[Evaluation of adhesive strength]
The evaluation substrate obtained by the above method was diced into 2 mm squares, and the substrate and a 10 mm square soda glass substrate were thermocompression bonded under the conditions of 150 ° C., 1.25 MPa, and 10 seconds. Next, after thermosetting at 160 ° C. for 1 hour, the shear strength was measured at room temperature using “sereis 4000” manufactured by dage, and the adhesive strength was calculated. The results are shown in Table 2.

[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 laminated 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) of the test piece after 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 2.

[Evaluation of outgas 1]
The photosensitive resin composition layers of the photosensitive elements obtained in Examples and Comparative Examples were laminated on a silicon substrate cut to an arbitrary size by the same method as described above, and exposed at 600 mJ / cm ² on the entire surface. And thermosetting at 160 ° C. for 1 hour to prepare an evaluation sample. The obtained evaluation sample was placed in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 24 hours, and then placed on a hot plate heated to 260 ° C. At this time, a glass substrate was placed on the evaluation sample at a certain distance. And the glass substrate after 20 second passed in the state which mounted the evaluation sample on the hotplate was observed with the microscope. The microscope picture which observed the outgas of the photosensitive resin composition layer of Example 1 is shown in FIG. 2, and the microscope picture which observed the outgas of the photosensitive resin composition layer of the comparative example 1 is shown in FIG. 3, respectively. The granular thing observed in FIG. 3 was a droplet.

[Outgas evaluation 2]
The entire surface of the photosensitive resin composition layer of the photosensitive element obtained in Examples and Comparative Examples was exposed to 600 mJ / cm ² and thermally cured at 160 ° C. for 1 hour to prepare an evaluation sample. The obtained evaluation sample was put into an 85 ° C., 85% constant temperature and humidity chamber for 24 hours, and 2000 μg of the photosensitive resin composition layer was collected and pyrolyzed GC / MS (manufactured by Agilent Technologies, trade name “5973MSD”). The peak area of the acid anhydride corresponding to the outgas detected at 200 ° C. for 10 minutes was measured. The results are shown in Table 2.

  As is apparent from the results of Table 2 and FIGS. 2 and 3, according to the photosensitive resin composition and photosensitive element of the present invention, compared to the photosensitive resin composition and photosensitive element of Comparative Example 1, It was confirmed that the properties were good, the water absorption was low, the adhesiveness was excellent, and the outgas after curing could be sufficiently reduced.

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

Claims (2)

Under the conditions of a temperature of 130 to 180 ° C. and a pressure of 0.1 to 1.5 MPa, it is an adhesive used for heating and pressurizing for 1 to 60 seconds to bond arbitrary base materials or members,
Photosensitive containing (A) a binder polymer having a carboxyl group, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a compound having a heterocycle. An adhesive resin composition,
The (A) binder polymer having a carboxyl group includes at least one selected from the group consisting of an acrylic resin, an epoxy acrylate resin, a polyester resin, an amide resin, and an epoxy resin,
(E) Adhesive agent in which the compound having a heterocycle includes a compound having an oxazoline skeleton and / or a compound having an epoxy skeleton (excluding the epoxy resin) . After heating and pressurizing for 1 to 60 seconds under conditions of a temperature of 130 to 180 ° C. and a pressure of 0.1 to 1.5 MPa, the substrate is further heated for 30 to 90 minutes in the range of 150 to 180 ° C. An adhesive used to bond members together,
Photosensitive containing (A) a binder polymer having a carboxyl group, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a compound having a heterocycle. An adhesive resin composition,
The (A) binder polymer having a carboxyl group includes at least one selected from the group consisting of an acrylic resin, an epoxy acrylate resin, a polyester resin, an amide resin, and an epoxy resin,
(E) Adhesive agent in which the compound having a heterocycle includes a compound having an oxazoline skeleton and / or a compound having an epoxy skeleton (excluding the epoxy resin) .