TW201425368A - Photosensitive resin composition, multi-layer body using the resin composition and cured product thereof - Google Patents

Abstract

The purpose of the present invention is to provide the following: a photosensitive epoxy resin composition that, via photolithography, can form a high-resolution, low-stress image that has vertical side walls and resists moisture and heat, and/or a resist laminate using said photosensitive epoxy resin composition; and an article or articles obtained by curing said photosensitive epoxy resin composition and/or resist laminate. The present invention is a photosensitive resin composition containing the following: an epoxy resin (A), a polyhydric phenol compound (B) having a specific structure, a cationic-polymerization photoinitiator (C), a silane compound (D) containing an epoxy group, and a reactive epoxy monomer (E) having a specific structure. The epoxy resin (A) contains the phenol derivative represented by formula (1), an epoxy resin (a) obtained via a reaction with epihalohydrin, and an epoxy resin (b) that can be represented by formula (2). The reactive epoxy monomer (E) is a polyoxyalkylene-glycol diglycidyl ether.

Description

Photosensitive resin composition, resist laminate, and cured products thereof

The present invention relates to a photosensitive resin composition which is excellent in the shape of a side wall and an excellent image, and which has a small internal stress after curing and which is excellent in substrate adhesion after a damp heat test. The cured product of the photosensitive resin composition of the present invention can be used for an insulating layer of an electronic component such as a MEMS (micro electro mechanical system) component, a μ-TAS (micro total analysis system) component, a microreactor component, a capacitor, or an inductor. , LIGA parts, micro-injection forming and scalding applications and embossing, micro-printing screens or stencils, MEMS and semiconductor package parts, BioMEMS and bio-optoelectronic devices, and the production of printed wiring boards.

In photosensitive resin compositions, photolithographic process processors are known as photoresists and are widely used in semiconductors or MEMS. Micromechanical applications, etc. In such applications, photolithographic processing is accomplished by patterning exposure on a substrate followed by development with a developer to selectively remove the exposed or non-exposed areas. The photoresist has positive and negative types, and the exposure part dissolves. The developer is positive, and the opposite is negative. In the electronic packaging application or MEMS application of the tip technology, not only the uniform spin coating film formation ability but also the high aspect ratio, the vertical sidewall shape in the thick film, and the high adhesion to the substrate are required. Here, the aspect ratio means an important characteristic which is calculated by the film thickness of the resist film/line width and represents the performance of the photolithography technique.

According to Patent Document 1 and Non-Patent Document 1, The bisphenol A type novolac epoxy resin is a composition of a main component, and can form a photosensitive image having a high resolution and a high aspect ratio, and a photosensitive resin cured product. However, the obtained cured resin has a tendency to be brittle due to its use, and tends to cause cleansing during development or when internal stress occurs. Therefore, the resin cured product is not only reduced in adhesion due to the type of the substrate using the resin composition, but may be peeled off between the substrate and the cured resin. All of these problems occur when the composition is hardened and shrunk, and are caused by stress accumulated in the cured resin. When the hardening shrinkage is large, the substrate is warped (warped).

Further, it is understood that the substrate forming the cured resin is resistant The wet heat test (80 ° C, 100%, 24 hours) of one of the long-term accelerated tests was carried out, and the cured resin was peeled off from the substrate. Therefore, when the cured resin is used for applications such as MEMS packaging, semiconductor packaging, and microreactor forming parts, durability is poor and it is not suitable.

In Patent Document 2, it is disclosed by an epoxy resin, a novolac tree A resin composition composed of a fat, a photocationic polymerization initiator, and a filler. It is described that by using the resin composition, the adhesion of the coating film is increased and the moisture permeability is lowered. However, it can be seen that there is no resolution as a photoresist according to the disclosed composition. Yes, high adhesion can not be achieved without filler. Therefore, the resin composition of Patent Document 2 is not suitable for use in MEMS packaging, semiconductor packaging, microreactors, and the like.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 4882245

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-24364

[Non-patent literature]

[Non-Patent Document 1] N. LaBianca and J.D. Gelorme, High Aspect Ratio Resist for Thick Film Applications, Proc. SPIE, vol. 2438, 846 (1995)

The present invention has been made in view of the above circumstances to provide a semiconductor or MEMS. In the field of micromechanical applications, an epoxy resin composition which is cured by cationic polymerization can form a photosensitive resin composition having a fine resolution, a low stress, and a moist heat resistance image, and/or a layer thereof, in a vertical side wall shape. For the purpose of combining, and their hardened materials.

As a result of intensive studies, the present inventors have found that the photosensitive resin composition of the present invention can solve the above problems.

Aspects of the invention are as follows.

A photosensitive resin composition comprising (A) an epoxy resin, (B) a polyhydric phenol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing decane compound, and (E) A photosensitive resin composition of a reactive epoxy monomer, the characteristics of which are

The (A) epoxy resin contains

The following formula (1) The epoxy resin (a) obtained by the reaction of the represented phenol derivative with an epihalohydrin, and the following formula (2) (wherein m is an average value, and represents a real number in the range of 2 to 30, and R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group, and X is independent. a hydrogen atom or a propylene oxide group, and at least one of X in the plural is an epoxy group (b) represented by a glycidyl group, and

The (B) polyphenol compound contains

The following formula (3) or even (6) (wherein p is an average value, and represents a real number in the range of 1 to 10, and R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) (where q is the average value, indicating a real number in the range of 1 to 10) (where z is the average value, indicating a real number in the range of 1 to 10)

(wherein, y is an average value, and a real number in the range of 1 to 10, and R ₈ and R ₉ are each independently, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) is selected from the group of phenol compounds. More than one, and

The (E) reactive epoxy monomer contains

The following formula (12) (In the formula, n is an average value, and is an epoxy compound represented by a real number in the range of 1 to 20 (except 1). R ₇ is a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms).

2. The photosensitive resin composition according to claim 1, wherein the (E) reactive epoxy monomer comprises poly n-propylene glycol diepoxypropyl ether, and/or polyisopropylene glycol diepoxypropyl ether, And/or polyethylene glycol diepoxypropyl ether.

3. The photosensitive resin composition according to claim 1, wherein the ratio of the ratio of the (E) reactive epoxy monomer to the total mass of the (A) epoxy resin and the (B) polyhydric phenol compound is 2 to 12 quality%.

4. The photosensitive resin composition according to claim 1, wherein the ratio of the (B) polyphenol compound to the (A) epoxy resin is from 1 to 40% by mass.

5. The photosensitive resin composition according to claim 1, wherein the ratio of the ratio of the (C) photocationic polymerization initiator to the total mass of the (A) epoxy resin and the (B) polyhydric phenol compound is 0.1 to 15 quality%.

6. The photosensitive resin composition according to claim 1, wherein the (D) epoxy group-containing decane compound is an epoxy group-containing alkoxydecane compound.

7. The photosensitive resin composition according to claim 1, wherein the ratio of the (D) epoxy group-containing decane compound is relative to (A) epoxy resin, (B) polyphenol compound, and (C) photocationic polymerization. The total mass of the initiator and the (E) reactive epoxy monomer is from 1 to 15% by mass.

8. The photosensitive resin composition according to claim 1, which further comprises (G) an acrylic resin.

9. The photosensitive resin composition according to claim 8, wherein the (G) acrylic resin is a copolymer obtained by using an ethylenically unsaturated monomer having a glycidyl group.

10. The photosensitive resin composition according to claim 8, wherein the ratio of the (G) acrylic resin is relative to (A) epoxy resin, (B) The total mass of the polyhydric phenol compound, (C) photocationic polymerization initiator, (D) epoxy group-containing decane compound, and (E) reactive epoxy monomer is 1 to 20% by mass.

The photosensitive resin composition according to claim 1, which further comprises (F) a solvent.

The photosensitive resin composition according to claim 11, wherein the blending ratio of the solvent (F) is from 5 to 95% by mass based on the total mass of the photosensitive resin composition containing the (F) solvent.

A cured product of the photosensitive resin composition according to any one of claims 1 to 12.

A resist laminate obtained by sandwiching a photosensitive resin composition according to any one of claims 1 to 12 on two substrates.

A cured product of a dry film resist obtained from the resist laminate described in claim 14.

The photosensitive resin composition of the present invention can form a pattern of a fine and vertical side wall shape by photolithography, and the cured product has characteristics of high resolution, low stress, and moist heat resistance. Therefore, by using the photosensitive resin composition of the present invention, it is possible to obtain a semiconductor or MEMS. Micromechanical applications, especially permanent barriers and hardeners for the characteristics necessary for MEMS packaging, semiconductor packaging, and microreactor forming parts.

[Best Mode for Carrying Out the Invention]

The invention is described below.

The (A) epoxy resin contained in the photosensitive resin composition of the present invention contains the epoxy resin (a) obtained by the reaction of the phenol derivative represented by the above formula (1) and an epihalohydrin, and the above formula ( 2) Both of the epoxy resins (b) indicated. Among them, the epoxy resin (a) is a vertical sidewall shape and a fine resolution of a cured product (pattern) obtained by photolithography using the photosensitive resin composition of the present invention. The epoxy resin (a) can be obtained by a conventional method for synthesizing an epoxy resin using a phenol derivative represented by the formula (1) and an epihalohydrin.

A general synthesis method of the epoxy resin (a), for example, In the mixed solution in which the solvent of the phenol derivative and the epihalohydrin represented by the formula (1) is dissolved, a base such as sodium hydroxide is added, and the temperature is raised to the reaction temperature to carry out an addition reaction and a ring closure reaction, and then the reaction is repeated. The method of washing, separating and removing the water layer of the liquid, and finally distilling off the solvent from the oil layer. The halogen of the epihalohydrin is selected from the group consisting of F, Cl, Br and I, but is typically Cl or Br. The reaction of the phenol derivative represented by the formula (1) with an epihalohydrin is 1 molar (corresponding to hydroxyl 3 molar) relative to the phenol derivative, and the epihalohydrin is usually used in an amount of 0.3 to 30 mol, preferably 1 to 1. 20 moles, more preferably 3 to 15 moles. The epoxy resin (a) is usually obtained as a mixture of a plurality of products because it is obtained by the above reaction.

It is known that the above-mentioned synthesis reaction is represented by the formula (1). The ratio of use of the phenol derivative to the epihalohydrin gives an epoxy resin (a) having a main component different in the epoxy resin (a). For example, when an excessive amount of epihalohydrin is used for the phenolic hydroxyl group of the phenol derivative, the formula (1) is obtained. All of the three phenolic hydroxyl groups are epoxy resins (a) mainly composed of an epoxidized trifunctional epoxy resin. The amount of epihalohydrin with a relatively phenolic hydroxyl group is reduced, and the phenolic hydroxyl group of a plurality of phenol derivatives is bonded through an epihalohydrin, and the remaining phenolic hydroxyl group is an epoxidized large molecular weight polyfunctional epoxy. The content of the resin is increased.

As the main epoxy resin obtained with such a polymer The method of dividing the epoxy resin (a) may be carried out by, for example, a method in which the epoxy resin (a) is further reacted with a phenol derivative, in addition to the method of controlling the use ratio of the phenol derivative and the epihalohydrin. The epoxy resin (a) obtained by this method is also included in the category of the epoxy resin (a) contained in the photosensitive resin composition of this invention.

The epoxy resin (a) contained in the resin composition of the present invention may be an epoxy resin obtained by reacting a phenol derivative represented by the formula (1) with an epihalohydrin, or a phenol derivative. Any of the epoxy resins or phenol derivative polymers of the epoxy resin as the main component of the epoxy resin (a). Epoxy resin (a) is an epoxy resin of a monomeric epoxy resin of a phenol derivative or a 2-mer of a phenol derivative (having a formula (1), which is excellent in solubility in a solvent, or has a low softening point and is easy to handle. An epoxy resin having a structure in which two phenol derivatives are bonded by an epihalohydrin or an oligomer of a phenol derivative (having three phenol derivatives represented by the formula (1)) The epoxy resin (a) which is one of the main components of the epoxy resin bonded by the epihalohydrin is preferred. The epoxy resin (a) mainly composed of an epoxy resin of a monomer of a phenol derivative or a 2-mer of a phenol derivative is more preferable.

In addition, the term "main component" as used in the present invention means a ring containing the most abundant epoxy resin of an epoxy resin and/or a polymer epoxy resin of a monomer contained in the epoxy resin (a). Oxygen resin component.

The specific structure of the epoxy resin (a) of the monomer of the phenol derivative represented by the formula (1) is represented by the following formula (7).

The specific structure of the epoxy resin (a) of the dimer of the phenol derivative represented by the formula (1) is represented by the following formula (8).

The specific structure of the epoxy resin (a) of the terpolymer of the phenol derivative represented by the formula (1) is represented by the following formula (9).

Epoxy resin (a), with 500~12000 A range of weight average molecular weight is preferred, and a weight average molecular weight in the range of 500 to 9000 is more preferred. A preferred example thereof is NC-6300H (trade name, manufactured by Nippon Chemical Co., Ltd., epoxy equivalent 220 to 240 g/eq., softening point 60 to 85 ° C). In addition, the weight average molecular weight in the present invention is a value calculated in terms of polystyrene based on the measurement result of GPC, the epoxy equivalent is a value measured in accordance with JIS K-7236, and the softening point is measured in accordance with JIS K-7234. value.

Epoxy resin (b) is a photosensitive resin using the present invention The cured product (pattern) obtained by the photolithography technique imparts resolution and flexibility to the composition. As a result of the improvement of these characteristics of the epoxy resin (b), the wet heat adhesion of the cured product is enhanced. Epoxy resin (b) can be borrowed It is obtained by reacting a part of an alcoholic hydroxyl group which the polycondensate of a bisphenol and epichlorohydrin has with epichlorohydrin. Specific examples thereof include NER-7604, NER-7403, and NER-1302 (all of which are trade names, manufactured by Nippon Kayaku Co., Ltd.). The epoxy resin (b) preferably has an epoxy equivalent of 250 to 400 g/eq., and preferably has a softening point of 60 to 85 °C.

In the photosensitive resin composition of the present invention, relative epoxy tree The mass of the fat (a) and the epoxy resin (b) are usually 2 to 4,900% by mass, preferably 5 to 100% by mass, and more preferably 10 to 70% by mass. By using the epoxy resin (b) having a mass of the epoxy resin (a) at a mass ratio of 4,900 mass% or less, it is easy to make the photosensitive image pattern a vertical side wall shape, and it is possible to suppress the pattern band round. shape. In addition, when the use ratio of the epoxy resin (b) with respect to the mass of the epoxy resin (a) is 2% by mass or more, cracking on the surface of the photosensitive image pattern can be effectively prevented.

(A) ring contained in the photosensitive resin composition of the present invention As the oxygen resin, an epoxy resin other than the above epoxy resin (a) and epoxy resin (b) may be used in combination. The epoxy resin which can be used in combination is not particularly limited, and the proportion thereof is not particularly limited as long as the effect of the present invention is not impaired. However, in the category of (A) epoxy resin, the epoxy group-containing decane compound of the component (D) is not contained, and the epoxy compound of the reactive epoxy monomer defined as the component (E) is not included.

(B) plural of the photosensitive resin composition of the present invention The phenol compound contains one or more selected from the group consisting of the phenol compounds represented by the above formulas (3) to (6). (B) The polyhydric phenol compound contributes to hardening the epoxy resin at a high crosslinking density by heating. Therefore, (B) more The phenolic compound imparts a function of low moisture permeability, high adhesion, and strong enthalpy of the cured resin.

The polyphenol compound represented by the formula (3) can be exemplified Such as phenol novolac resin, cresol novolac resin. These novolac resins may be used alone or in combination of two or more. In particular, the phenol novolak resin is excellent in coating properties. In the case of the phenol novolak resin, a phenol novolak resin having a softening point of 50 ° C or more and 150 ° C or less is preferable, and a phenol novolak resin of 70 ° C or more and 100 ° C or less is particularly preferable. Specific examples of the phenol novolak resin having a softening point of 50 ° C or more and 150 ° C or less may, for example, be PN-152 (trade name, manufactured by Minwa Kasei Co., Ltd., softening point: 50 ° C, hydroxyl equivalent: 105 g/eq.), H-1 ( Product name, manufactured by Minghe Chemical Co., Ltd., softening point 80 ° C, hydroxyl equivalent 104 g / eq.), TD-2131 (trade name, DIC company, softening point 80 ° C, hydroxyl equivalent 105 g / eq.), KA-1160 (commodity Name, DIC company, softening point 81 ° C, hydroxyl equivalent 117 g / eq.). Further, the hydroxyl equivalent of the novolak resin is preferably in the range of 80 to 130 g/eq., preferably in the range of 100 to 120 g/eq., in terms of compatibility with the epoxy resin of the component (A) and low moisture permeability. .

The polyphenol compound represented by the formula (4) can be exemplified For example, bisphenol A type novolak resin can be obtained from commercially available products. Specific examples of the bisphenol A type novolac resin include, for example, VH-4150 (trade name, manufactured by DIC Corporation, softening point: 85 ° C, hydroxyl equivalent: 118 g/eq.), and VH-4170 (trade name, manufactured by DIC Corporation, softened). Point 103 ° C, hydroxyl equivalent weight 118 g / eq.), MEP-6309E (trade name, manufactured by Megumi Kasei Co., Ltd., softening point 81 ° C, hydroxyl equivalent 116 g / eq.) and the like. These novolac resins One type or two or more types can be used.

The polyphenol compound represented by the formula (5) can be exemplified For example, a biphenylphenol novolac resin can be obtained from commercially available products. Specific examples of the biphenylphenol novolak resin include, for example, KAYAHARD GPH-65 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point: 65 ° C, hydroxyl equivalent: 200 g/eq.). These novolac resins may be used alone or in combination of two or more.

The polyphenol compound represented by the formula (6) can be exemplified For example, phenol aralkyl resins can be obtained from commercially available products. Specific examples of the phenol aralkyl resin include, for example, MilexXLC-3L (trade name, manufactured by Mitsui Chemicals, Inc., softening point: 77 ° C, hydroxyl equivalent: 176 g/eq.). These phenol aralkyl resins may be used alone or in combination of two or more.

(B) polyphenol in the photosensitive resin composition of the present invention The compounding ratio of the compound is usually from 1 to 40% by mass, preferably from 4 to 30% by mass, and more preferably from 5 to 25% by mass, based on the total mass of the (A) epoxy resin. When the content of the (B) polyhydric phenol compound is 40% by mass or less, development of a photosensitive image pattern can be suppressed from becoming difficult. When the content of the (B) polyhydric phenol compound is 1% by mass or more, sufficient adhesion or moisture resistance is easily obtained.

Also, in combination with the plural (3) or (6) The ratio of use of each of the polyhydric phenol compounds in the case of the above-described polyphenol compound is not particularly limited as long as the ratio of the (B) polyphenol compound of the (A) epoxy resin is within the above range.

Moreover, it is contained in the photosensitive resin composition of this invention. (B) The polyhydric phenol compound may be a polyphenol compound other than the polyhydric phenol compound represented by the above formula (3) to (6). The polyhydric phenol compound which can be used in combination is not particularly limited. Further, the proportion of the polyphenol compound which can be used in combination is not particularly limited as long as the effect of the present invention is not impaired.

The (C) photocationic polymerization initiator contained in the photosensitive resin composition of the present invention generates cations by irradiation with excimer lasers such as ultraviolet rays, far ultraviolet rays, KrF or ArF, radiation such as X-rays and electron beams, and the like. And the cation can be a compound of a polymerization initiator.

(C) The photocationic polymerization initiator may, for example, be an aromatic sulfonium salt or an aromatic sulfonium salt. Specific examples of the aromatic sulfonium salt include diphenyl sulfonium tetrakis(pentafluorophenyl) borate, diphenyl sulfonium hexafluorophosphate, diphenyl sulfonium hexafluoroantimonate, and di(4). -nonylphenyl)phosphonium hexafluorophosphate, tolylpyridinium tetrakis(pentafluorophenyl)borate (manufactured by Rhodia Co., Ltd., trade name RHODORSILPI2074), bis(4-tert-butyl)pyrene Trifluoromethanesulfonyl) methanide (manufactured by BASF Corporation, trade name CGI BBI-C1).

Further, specific examples of the aromatic sulfonium salt include 4-thiophenyldiphenylphosphonium hexafluoroantimonate (manufactured by San-apro Co., Ltd., trade name CPI-101A), and thiophenyl diphenyl group. Tris(pentafluoroethyl)trifluorophosphate (manufactured by San-apro Co., Ltd., trade name CPI-210S), 4-{4-(2-chlorobenzhydrazide)phenylthio}phenyl bis(4- Fluorophenyl) hexafluoroantimonate (trade name SP-172, manufactured by Adeka Co., Ltd.), a mixture of aromatic hexafluoroantimonate containing 4-thiophenyldiphenylphosphonium hexafluoroantimonate ( ACETO Corporate USA, trade name CPI-6976) and triphenyl Tris(trifluoromethanesulfonyl) methanide (manufactured by BASF Corporation, trade name CGI TPS-C1), tris[4-(4-ethylmercaptophenyl)sulfonylphenyl]phosphonium tris(trifluoromethyl) Methylsulfonyl) methide (manufactured by BASF Corporation, trade name GSID 26-1), tris[4-(4-ethylmercaptophenyl)sulfonylphenyl]phosphonium tetra(2,3,4,5 , 6-pentafluorophenyl) borate (manufactured by BASF Corporation, trade name: IRGACUREPAG290).

Photosensitive image shape in such photocationic polymerization initiators In the step, an aromatic sulfonium salt having high vertical workability and high thermal stability is preferred. 4-{4-(2-chlorobenzindole)phenylthio}phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate containing 4-thiophenyldiphenylphosphonium hexafluoroantimonate a mixture of esters of aromatic hexafluoroantimonate, tris[4-(4-ethylmercaptophenyl)sulfonylphenyl]phosphonium tetra(2,3,4,5,6-pentafluorophenyl) Borate is especially preferred.

Such (C) photocationic polymerization initiators may be used alone or Two or more types are used together. (C) The photocationic polymerization initiator component has an effect of absorbing light. Therefore, in the case of a thick film (for example, 50 μm or more), in order to sufficiently transmit the light during curing to the deep portion, it is preferable to use the component (C) which is not excessively large (for example, 15% by mass or less). On the other hand, in the case of a thick film, in order to obtain a sufficient hardening speed, it is preferable to use a certain amount (for example, 3% by mass or more) of the component (C). In the case of a film, the component (C) exhibits sufficient polymerization initiation performance in a small amount (for example, 1% by mass or more). In the case of a film, even if the component (C) is used in a large amount, the light transmittance to the deep portion is not largely lowered, but it is economical (preventing unnecessary use of a high-priced initiator), but it is used. A large amount of the component (C) is preferred. The ratio of (C) photocationic polymerization initiator in the photosensitive resin composition of the present invention is relatively the same as that of (A) epoxy resin and (B) polyphenol compound. The total mass is usually 0.1 to 15% by mass, preferably 0.2 to 8% by mass. However, when the (C) photocationic polymerization initiator has a high molar absorption coefficient in the wavelength range of 300 to 380 nm, it is necessary to adjust the film thickness in accordance with the use of the photosensitive resin composition to an appropriate amount.

(D) ring-containing contained in the photosensitive resin composition of the present invention In the step of using the composition of the present invention, the oxydecane compound imparts improved adhesion to the substrate and improves interlayer adhesion in the case where the composition of the present invention forms a multilayer structure. Further, the (D) epoxy group-containing decane compound does not hinder the storage stability of the photosensitive resin composition of the present invention.

(D) a preferred specific example of the epoxy group-containing decane compound, For example, an epoxy group-containing alkoxydecane compound is contained. Examples of the epoxy group-containing alkoxydecane compound include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 3-epoxypropyl. Oxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These may be used alone or in combination of two or more.

(D) epoxy-containing in the photosensitive resin composition of the present invention The total ratio of the proportion of the decane compound to the (A) epoxy resin, (B) polyphenol compound, (C) photocationic polymerization initiator, and (E) reactive epoxy monomer is usually 1~ 15% by mass, preferably 3 to 10% by mass.

(E) reaction contained in the photosensitive resin composition of the present invention The epoxy monomer imparts flexibility and flexibility to the uncured film and the cured film of the photosensitive resin composition of the present invention, and improves adhesion to the cured film. (E) The reactive epoxy monomer contains the epoxy compound represented by the above formula (12).

Represented by the formula (12) as the (E) reactive epoxy monomer The epoxy compound is an epoxy compound represented by the formula (12) and having a molecular weight of 1,000 or less calculated in terms of polystyrene based on the measurement result of GPC. When the molecular weight of the epoxy compound represented by the formula (12) is 1,000 or less, the compatibility with other components and the coating film quality of the resin composition can be appropriately maintained, and good developability can be obtained, and high-definition photosensitive image formation can be achieved. It is better.

(E) a ring represented by the formula (12) of a reactive epoxy monomer The oxygen compound is generally a polyalkylene glycol diepoxypropyl ether. Preferred are poly-n-propylene glycol diepoxypropyl ether, polyisopropylene glycol diepoxypropyl ether, and polyethylene glycol diepoxypropyl ether. These may be used alone or in combination of two or more.

(E) reactivity in the photosensitive resin composition of the present invention The blending ratio of the epoxy monomer is usually 2 to 12% by mass, preferably 3 to 10% by mass based on the total mass of the (A) epoxy resin and the (B) polyhydric phenol compound.

(E) anti-reflection contained in the photosensitive resin composition of the present invention As the reactive epoxy monomer, a reactive epoxy monomer other than the epoxy compound represented by the above formula (12) may be used in combination. The reactive epoxy monomer which can be used in combination is not particularly limited, and the proportion of the reactive epoxy monomer which can be used in combination is not particularly limited as long as the effect of the present invention is not impaired.

The photosensitive resin composition of the present invention may further contain (G) Acrylic. Here, the (G) acrylic resin contains a resin formed of a compound having a propenyl group and/or a compound having a methacryl group. (G) Acrylic resin is not particularly limited, but a copolymer obtained by using an ethylenically unsaturated monomer having a glycidyl group is preferable, and a glycidyl methacrylate copolymer is particularly preferable. good. The glycidyl methacrylate copolymer is a polymer in which a glycidyl methacrylate is copolymerized with another ethylenically unsaturated monomer, and has an epoxy group in a branched form relative to the polymer main chain. Therefore, the glycidyl methacrylate copolymer has a high compatibility with an epoxy resin and is less likely to cause phase separation, and is easily mixed with an epoxy resin. Further, since the glycidyl methacrylate copolymer is a soft component, flexibility can be imparted to the cured film, and the adhesion can be improved. Further, for the purpose of forming a fine micropattern, the (G) acrylic resin is also compatible with (A) an epoxy resin, (B) a polyphenol compound, and (E) a reactive epoxy monomer. A glycidyl methacrylate copolymer which is excellent in hardening properties is preferred.

Epoxy equivalent of methacrylic acid glycidyl ester copolymer It is preferably 1000 or less. The epoxy group in the molecular chain of the glycidyl methacrylate copolymer polymer reacts with the epoxy resin to form a mesh structure during curing, and as a result, thermal expansion under high temperature and high humidity conditions can be suppressed, and long-term reliability is imparted. Upgrade. When the epoxy equivalent of the glycidyl methacrylate copolymer is 1000 or less, a reaction point with a sufficient amount of epoxy resin is ensured, a mesh structure is effectively formed, and deterioration of moist heat resistance is prevented.

Others constituting a glycidyl methacrylate copolymer Examples of the ethylenically unsaturated monomer include an acrylic acid derivative such as acrylic acid, methyl acrylate or acrylate, a dimethyl fumarate, and a fumaric acid derivative such as diethyl fumarate. Styrene derivatives such as styrene and α-methylstyrene. Other ethylenically unsaturated monomers, by using an acrylic acid derivative, because the compatibility of the epoxypropyl methacrylate copolymer with (A) epoxy resin and (E) reactive epoxy monomer can be achieved. Better and better. These other ethylenically unsaturated monomers may be used singly or in combination of two or more kinds. The molecular weight of the glycidyl methacrylate copolymer is not particularly limited, but the compatibility with the epoxy resin is considered, and the weight average molecular weight is preferably 250,000 or less, more preferably 100,000 or less, and further preferably Less than 30,000.

Specifics of commercial products having a copolymer of epoxy propyl groups For example, MARPROOF G-0150M (trade name, manufactured by Nippon Oil Co., Ltd., copolymer of glycidyl methacrylate and methyl methacrylate, epoxy equivalent 310 g/eq., weight average molecular weight) About 10,000), MARPROOF G-0250S (trade name, manufactured by Nippon Oil Co., Ltd., epoxy propyl methacrylate and a copolymer of styrene and methyl methacrylate, epoxy equivalent 310 g / eq., A weight average molecular weight of about 20,000), MARPROOF G-2050M (trade name, manufactured by Nippon Oil Co., Ltd., a copolymer of glycidyl methacrylate and methyl methacrylate, epoxy equivalent of 340 g / eq., The weight average molecular weight is about 200,000) and the like.

(G) Acrylic resin The photosensitive resin composition of the present invention may be used singly or in combination of two or more kinds. The ratio of the (G) acrylic resin in the photosensitive resin composition of the present invention is relative to the (A) ring The total mass of the oxygen resin, (B) polyphenol compound, (C) photocationic polymerization initiator, (D) epoxy group-containing decane compound, and (E) reactive epoxy monomer is usually 1 to 20% by mass. Preferably, it is 3 to 15% by mass.

In the photosensitive resin composition of the present invention, in order to make the resin group The viscosity of the product is lowered and the coating property is improved, and (F) a solvent can be used. The solvent is not particularly limited as long as it can dissolve the respective constituent components of the photosensitive resin composition and does not chemically react with the constituent components, and can be used. Specific examples of the solvent (F) include ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, and cyclopentanone, and aromatic hydrocarbons such as toluene, xylene, and methoxybenzene. Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, glycol ether such as propylene glycol monomethyl ether, ethyl lactate, ethyl acetate, butyl acetate, methyl-3-methoxypropionic acid Esters such as esters, carbitol acetate, propylene glycol monomethyl ether acetate and γ-butyrolactone, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as octane and decane, petroleum ether, Petroleum-based solvents such as naphtha, hydrogenated naphtha, and petroleum-soluble petroleum spirit.

These solvents may be used alone or in combination of two or more. (F) The solvent is added for the purpose of adjusting the film thickness or coatability at the time of coating the substrate. In order to maintain the solubility of the main component of the appropriate resin composition, the volatility of each component, the liquid viscosity of the composition, etc., the amount of the solvent used is usually 95 mass in the solvent-containing photosensitive resin composition. %the following. The amount thereof is preferably 5 to 95% by mass, more preferably 10 to 90% by mass.

In the photosensitive resin composition of the present invention, in order to absorb The sensitizer can be used by collecting ultraviolet rays and supplying the absorbed light energy to a photocationic polymerization initiator, particularly an aromatic sulfonium salt. The sensitizer is preferably, for example, a thioxanthone, an an alkoxy group-containing oxime compound (9,10-dialkoxyfluorene derivative) at the 9-position and the 10-position. The alkoxy group may, for example, be a C1 to C4 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group. The 9,10-dialkoxyfluorene derivative may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group of C1 to C4, an alkyl sulfonate group or an alkyl carboxylate group. The alkyl group in the alkyl sulfonate group or the alkyl carboxylate group may, for example, be a C1 to C4 alkyl group. The substitution position of these substituents is preferably 2 positions.

Specific examples of thioxanthones are 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4 - Diisopropyl thioxanthone and the like. It is preferably 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name Kayacure DETX-S) or 2-isopropylthioxanthone.

The 9,10-dialkoxypurine derivative may, for example, be 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Butoxy oxime, 9,10-dimethoxy-2-ethyl hydrazine, 9,10-diethoxy-2-ethyl hydrazine, 9,10-dipropoxy-2-ethyl hydrazine, 9,10-Dimethoxy-2-chloropurine, 9,10-dimethoxyindole-2-sulfonic acid methyl ester, 9,10-diethoxyindole-2-sulfonic acid methyl ester, 9,10-dimethoxyindole-2-carboxylic acid methyl ester and the like.

These sensitizers may be used singly or in combination of two or more, but the use of 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylhydrazine is optimal. The sensitizer is used in a small amount, and its use ratio is usually 30% by mass relative to the mass of the (C) photocationic polymerization initiator component. Hereinafter, it is preferably 20% by mass or less.

In the resin composition of the present invention, in order to obtain light from (C) The negative effect of the ions of the cationic polymerization initiator is reduced, and an ion trapping agent may be added as necessary. Specific examples of the ion scavenger include alkoxy aluminum such as trimethoxy aluminum, triethoxy aluminum, triisopropoxy aluminum, isopropoxy diethoxy aluminum, and tributoxy aluminum. Phenylene aluminum such as triphenyloxy aluminum and tri-p-methylphenoxy aluminum, triethoxy aluminum, tristea aluminum, tributyl aluminum, tripropyl aluminum, aluminum triacetate, An organoaluminum compound such as trifluoroacetic acid aluminum acetonate, aluminum triethyl acetonitrile acetate, diethyl acetonide dimethylene pentyl methane aluminum or diisopropoxy (ethyl acetonitrile acetic acid) aluminum. These components may be used alone or in combination of two or more. Further, the amount thereof is usually relative to (A) epoxy resin, (B) polyphenol compound, (C) photocationic polymerization initiator, (D) epoxy group-containing decane compound, and (E) reactive epoxy sheet. The total mass of the bodies is 10% by mass or less.

In the photosensitive resin composition of the present invention, if necessary, Various additives such as a thermoplastic resin, a colorant, a tackifier, an antifoaming agent, and a flat agent can be used. The thermoplastic resin may, for example, be polyether oxime, polystyrene or polycarbonate. The coloring agent may, for example, be phthalocyanine blue, phthalocyanine, or iodine. Green, crystal violet, titanium oxide, carbon black, naphthalene black, ruthenium, quinacridone red, diketopyrrolopyrrole, and the like. The amount of the additive used in the photosensitive resin composition of the present invention other than the solvent is preferably, for example, 0% by mass or more and 30% by mass or less. However, the amount of such use may be appropriately increased or decreased depending on the purpose of use and the function of the cured film.

Adhesives, such as Orben, Penton, montmorillonite Wait. Examples of the antifoaming agent include antifoaming agents such as an anthrone, a fluoroalkyl group, and a polymer. The amount of the additive to be used is preferably 0% by mass or more and 10% by mass or less, for example, each of the photosensitive resin compositions of the present invention other than the solvent. However, the amount of such use may be increased or decreased depending on the purpose of use and the quality of the coating.

Further, in the photosensitive resin composition of the present invention, it can be used. For example, any inorganic filler such as barium sulfate, barium titanate, cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, montmorillonite, mica powder or the like. The amount of the inorganic filler to be used is usually from 0 to 60% by mass based on the mass of the photosensitive resin composition of the present invention excluding the solvent. However, the amount of use can be increased or decreased depending on the purpose of use and the required function of the cured film. Similarly, an organic filler such as polymethyl methacrylate, rubber, fluoropolymer or polyurethane powder may be added to the photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention can be obtained by (A) An essential component of the epoxy resin, (B) polyphenol compound, (C) photocationic polymerization initiator, (D) epoxy group-containing decane compound, and (E) reactive epoxy monomer, and optional components necessary for the reaction (G) Acrylic resin, (F) solvent, sensitizer, ion scavenger, thermoplastic resin, coloring agent, thickener, antifoaming agent, flat agent, inorganic filler, etc. are prepared by mixing and stirring by a general method. When mixing and stirring, a dispersing machine such as a dissolving device, a homogenizer, or a three-roll mill may be used as necessary. Further, after mixing, filtration can be carried out using a sieve, a membrane filter or the like.

The resistive hardening is formed by the photosensitive resin composition of the present invention The method of the film is explained below.

The photosensitive resin composition of the present invention is preferably used in the form of a liquid in which a solvent is added for application to a substrate. The step of obtaining a desired film thickness can be carried out by metering and dispensing the photosensitive resin composition of the present invention diluted to a desired viscosity with a solvent onto the substrate, accelerating the substrate to a constant rotation speed, and maintaining a constant rotation speed. The coating was carried out by a spin coating method. Spin coating can be carried out at various rotation speeds in order to control the film thickness. As another method, the photosensitive resin composition can be applied to the substrate by another coating method such as roll coating, blade coating, slit coating, dip coating, gravure coating, or spray coating.

After coating, it can be dried and baked (pre-baked) to make solvent evaporation. The dry baking conditions can be selected in such a manner that a semi-hardened dried coating film of the photoresist is formed. For typical conditions, a smooth surface heating plate can be used to bring the coating film into contact with the surface or close to the contact state, depending on the thickness of the coating film or the volatility of the solvent, and the thermal conductivity of the substrate or the thickness of the substrate at 65 ° C. , 1 to 15 minutes, followed by drying at 90 to 125 ° C for 5 to 120 minutes. As an additional method, dry baking can be carried out in a convection oven. Next, the coating film of the dried photosensitive resin composition is exposed to a light beam having a desired mask pattern, and is exposed to a near-ultraviolet wavelength of 300 to 500 nm from a medium-pressure or ultra-high pressure mercury lamp. Irradiation of the energy rays of the X-ray radiation of the synchrotron line source, or direct or transmission through the patterned exposure electron beam radiation, can form a photosensitive image. Close, close, or projection printing can be used. After exposure, in order to promote the polymerization reaction of the acid catalyst in the exposure field in the coating film, exposure may be performed. Bake after light. Typical conditions are 1 to 5 minutes at 65 ° C and then 1 to 60 minutes at 95 ° C depending on the thickness of the coating film and the thermal conductivity of the substrate or the thickness of the substrate on the hot plate.

Next, in order to dissolve and remove the unexposed part, the coating film is applied. The thickness and the solvent strength of the developer solvent are typically immersed in an organic solvent developer for 2 to 30 minutes. Further, the developed image is removed by applying a washing solvent to remove the developer adhered to the cured film. The adhered developer contains a dissolved photoresist component, and drying causes a residue on the photosensitive image, which is liable to cause contamination. Therefore, it is preferable to remove the adhered developer. In the case of the immersion method, by preparing a clean developing solution tank, multi-stage development can prevent the residue from adhering.

As an alternative method, an explosion-proof atomizing spray can be used. Any one of the mouth or the explosion-proof type of tiny shower head spray nozzle to spray the developer solvent. As for other development methods, for example, a method of applying a developer using a paddle method can be mentioned. In general, the paddle method includes placing a substrate to be developed on a rotating tool head, and then depositing a layer on the entire substrate area or a developer having a sufficient amount of paddle on a substrate rotating at a low speed to stop the rotation of the substrate. After the formed developer paddle is allowed to stand on the substrate for a predetermined period of time, the rotation of the substrate is accelerated to remove the used developer solution, and the rotation is stopped until the rotation stops. In order to obtain a vivid photographic image, it is usually necessary to use a method of performing several procedures.

Suitable developing solutions include, for example, propylene glycol monomethyl ether acetate, γ-butyrolactone, acetone, cyclopentanone, diacetone alcohol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, anisole, and lactic acid. Ethyl ester, but not limited to They are waiting. Propylene glycol monomethyl ether acetate is preferably used in which the unexposed portion is well dissolved and relatively low in cost.

Suitable washing liquid, for example, any of the above developing solutions And methanol, ethanol, isopropanol and n-butyl acetate. Among them, acetone, ethanol and isopropyl alcohol which can be quickly washed and rapidly dried are particularly preferred.

After the washing step, the final step in the manufacture of the cured film, According to the heat resistance of the substrate, heat treatment (hard baking) can be carried out at a temperature of 130 to 200 °C. By thermally hardening the film, a permanent cured film (resistance) satisfying various characteristics can be obtained.

Substrate materials that can be used, including antimony, cerium oxide, Bismuth, lithium niobate, tantalum nitride, alumina, glass, glass-ceramic, gallium antimonide, indium antimonide, copper, aluminum, nickel, iron, steel, copper-bismuth alloy, indium-tin oxide coated glass, poly Organic thin films, metals, semiconductors, and insulating materials such as phthalimide and polyester include any substrate in the field of patterning, but are not limited thereto.

The photosensitive resin composition of the present invention can also be used as two substrates It is used as a resist laminate. For example, a photosensitive resin composition diluted with a solvent is applied onto a substrate film (substrate) by using a roll coater, a die coater, a knife coater, a bar coater, a gravure coater, or the like. Thereafter, the solvent is removed in a drying oven set at 45 to 100 ° C, and then a coated film (substrate) or the like is laminated to obtain a resist laminate. At this time, the thickness of the resist on the substrate film can be adjusted to 2 to 100 μm. As the base film and the coating film of the substrate, for example, a film of polyester, polypropylene, polyethylene, TAC, or polyimide can be used. These films, if necessary, can be used with fluorenone A film obtained by removing a film such as a release treatment agent or a non-fluorenone release treatment agent. When such a resist laminate is used, for example, the coated film is peeled off, and transferred to a substrate at a temperature of 40 to 100 ° C and a pressure of 0.05 to 2 MPa by a hand roll or a press machine, and the liquid photosensitive material. The resin composition may be subjected to exposure, post-exposure baking, development, and heat treatment in the same manner.

According to the resist laminate of the present invention, the photosensitive resin composition is used in the form of a dry film resist, and the application to the support or the substrate and the drying step can be omitted. Thereby, the photosensitive resin composition of the present invention can be more easily used to form a fine pattern.

When the cured film is used for a MEMS package, a semiconductor package, and/or a microreactor to form a component, the photosensitive resin composition of the present invention is applied onto a substrate and dried to form a photosensitive resin coating film of the first layer. Exposing the first layer, followed by post-exposure baking, further coating the photosensitive resin composition, drying, forming a second layer of the photosensitive resin coating film, and then exposing the second layer, followed by exposure bake. This step is repeated, and finally, development and hard baking treatment are performed to form a complicated multilayer structure pattern. Alternatively, the first layer may be developed by repeated repetition, and after hard baking, the second layer is applied, dried, and subjected to alignment exposure, development, and hard baking through a light mask to form a multilayer structure pattern. Further, the formation of each photosensitive resin layer may be formed by laminating a dry film resist.

In addition, "package" refers to a sealing method or a closed method used to block the intrusion of outside air and liquid in order to maintain the stability of the substrate, wiring, components, and the like. The package described in the present specification refers to a hollow seal for a vibrator package such as a MEMS-like drive unit or a SAW device. The surface protection by the semiconductor substrate, the printed wiring board, the wiring, or the like is prevented, or the resin for forming the microreactor is sealed by the top plate. "Wafer-level package" refers to the formation of a protective film in a wafer state, terminal and wiring processing, and packaging, and then cutting into wafers, and showing fine micro-nano flow paths or orifice plates. A method of three-dimensional processing together in a wafer.

By using the photosensitive resin composition of the present invention, The photolithography technique forms a fine and vertical sidewall shape pattern. This cured product has characteristics of low stress and excellent heat and humidity resistance. According to the present invention, it is possible to obtain a semiconductor or MEMS. Micromechanical applications, particularly MEMS packaging, semiconductor packaging, and microreactors, form permanent resists and hardeners for the necessary properties of parts, and are of great use in such fields.

[Examples]

Hereinafter, the invention will be described in detail by way of examples. The examples are not intended to limit the invention, but are not intended to limit the invention.

Examples 17 to 24 and Comparative Examples 11 to 15 (Preparation of photosensitive resin composition solution (liquid resist))

(A) epoxy resin, (B) polyphenol compound, (C) photocationic polymerization initiator, according to the collocation amount (unit: mass parts (the solution product is a solid content conversion)) (D) contains an epoxy group The decane compound, the (E) reactive epoxy monomer, and the (G) acrylic resin were diluted with cyclopentanone to a concentration of 65% by mass, and the mixture was stirred and dissolved at 60 ° C for 1 hour in a flask equipped with a stirrer, and then allowed to cool. Filtration was carried out using a membrane filter having a pore size of 1.0 μm to obtain a photosensitive resin composition solution (liquid resist) for use in the present invention and for comparison.

(Picture of photosensitive resin composition)

Each of the liquid resists obtained in Examples 17 to 24 and Comparative Examples 11 to 15 was applied by spin coating on a tantalum wafer, and then prebaked on a hot plate at 95 ° C for 10 minutes to obtain a coating. A photosensitive resin composition layer having a dried film thickness of 25 μm after the cloth. After that, the coating film on the end surface of the wafer was swelled and removed, and after drying, an i-ray exposure apparatus (mask aligner: manufactured by Ushio Inc.) was used, and a gray scale-scale light mask was passed through the resolution evaluation to irradiate the exposure amount. 500mJ/cm ² (soft contact, i-line). Next, post-exposure baking (hereinafter referred to as "PEB") was carried out for 5 minutes on a hot plate at 95 °C. Subsequently, SU-8 Developer (trade name, manufactured by MICROCHEM Co., Ltd., propylene glycol monomethyl ether acetate main component) was immersed and developed at 23 ° C for 3 minutes, washed with isopropyl alcohol, and dried to obtain a ruthenium wafer. Upper hardened resin pattern.

(sensitivity, resolution, and crack evaluation of photosensitive resin composition) . Sensitivity

In the above-described patterning, the sensitivity of each photosensitive resin composition is evaluated by using the exposure amount at which the mask transfer accuracy is optimal as the optimum exposure amount. estimate. The smaller the value of the optimum exposure amount, the higher the sensitivity. The results are shown in Table 3 below.

. Resolution

With respect to each of the liquid resists, after the steps of pre-baking, dissolution and removal of the coating film on the wafer end surface, and drying, a light pattern of a hole pattern of 1 to 100 μm in line and pitch and a perfect circle is used. The cover was irradiated with an optimum exposure amount (soft contact, i-line, and exposure amount of Table 3) for each composition, and PEB was performed for 5 minutes on a hot plate at 95 °C. SU-8 Developer (trade name, manufactured by MICROCHEM Co., Ltd., propylene glycol monomethyl ether acetate main component) was immersed and developed at 23 ° C for 3 minutes, washed with isopropyl alcohol, and then dried. In the resist pattern having no residue and warping and resolved as a vertical side wall shape, the finest pattern width of the substrate adhesion was measured, and the resolution was evaluated. The results are shown in Table 3 below.

. Crack assessment

Moreover, the evaluation of the crack occurrence of the resin pattern obtained by the steps of the above-mentioned prebaking, the dissolution removal of the wafer end face coating film, drying, exposure, and the like was performed. The membrane has cleansing in its entirety (the same meaning as cracking, which means a state of discontinuous fracture until the bottom of the membrane.) The state is evaluated as "××", and cracks are generated only at the corners of the rectangular pattern (the surface of the membrane) The state of the partially generated fracture state is "x", and the state of no crack occurrence is "○". The results are shown in Table 3 below.

(Evaluation of wet heat adhesion of cured product of photosensitive resin composition)

Each of the liquid resists obtained in Examples 17 to 24 and Comparative Examples 11 to 15 was applied by spin coating on a tantalum wafer, and then prebaked on a hot plate at 95 ° C for 10 minutes to obtain a coating. A photosensitive resin composition layer having a dried film thickness of 25 μm after the cloth. After that, the coating film on the end surface of the wafer was swelled and removed, and after drying, an i-ray exposure apparatus (mask aligner: manufactured by Ushio Inc.) was passed through the pattern mask for wet heat adhesion evaluation, and the components were irradiated. The optimum exposure amount of the material (soft contact, i-line, exposure amount of Table 3 as a reference) was carried out for 5 minutes with a hot plate of 95 ° C. SU-8 Developer (trade name, manufactured by MICROCHEM Co., Ltd., propylene glycol monomethyl ether acetate main component), immersed and developed at 23 ° C for 3 minutes, washed with isopropyl alcohol, dried, and passed through an oven at 200 ° C. Minute hard bake treatment to obtain a resin pattern hardened on a tantalum wafer. The resin-patterned wafer was cut, and an aqueous solution-A (composition: 2-imidazolidinone 10% by mass, 2, 2'-) was added to a PTFE inner cylinder type closed container to which a water-soluble organic solvent was added. 7.5 mass% of sulfonyl diethanol, 5% by mass of glycerin, 5% by mass of pentanediol, 0.4 mass% of ethylene oxide modified Asertino, and the same -B (composition: 30% by mass of γ-butyrolactam, 2,2'-oxydiethanol 10% by mass, hexamethylene glycol 5 mass%, ethylene oxide modified Asertino 0.2% by mass), homo-C (composition: glycerin 15% by mass, polyethylene Each of the solutions of diol #400 5 mass% and polyoxyethylene lauryl ether 3 mass% was immersed in each of the cut pieces, and subjected to a damp heat test at 80 ° C for 24 hours. The adhesion force of the resin pattern before and after the test was measured by a shear strength tester, and when the adhesive strength was not deteriorated, it was "○", and when the adhesion force was deteriorated, "X" and the case where the pattern is floated or peeled off after the test is "××". The results are shown in Table 3 below.

Further, each of (A-1) to (G-2) in Table 3 is as follows.

(A-1): NC-6300H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy resin (a), epoxy equivalent 225 g/eq.)

(A-2): NER-7604 (trade name, manufactured by Nippon Kayaku Co., Ltd., R ₁ and R ₂ in formula (2) are hydrogen atoms and m≒6 epoxy resin (b), epoxy equivalent 330 g/ Eq.)

(A-3): NER-7403 (trade name, manufactured by Nippon Kayaku Co., Ltd., R ₁ and R ₂ in the formula (2) are hydrogen atoms and m≒4 epoxy resin (b), epoxy equivalent 250 g/ Eq.)

(A'-1): EPON SU-8 (trade name, manufactured by Momentive Co., Ltd., bisphenol A novolac type epoxy resin, epoxy equivalent 213 g/eq.)

(A'-2): EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd., o-cresol novolak type epoxy resin, epoxy equivalent 197 g/eq.)

(A'-3): Celloxide 2021P (trade name, manufactured by Dicel, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (alicyclic epoxy compound), epoxy equivalent 126g/eq.)

(A'-4): jER YL-983U (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin in which R ₁ and R ₂ in the formula (2) are a hydrogen atom and X is a hydrogen atom (bisphenol F ring) Oxygen resin), epoxy equivalent 170g/eq.)

(B-1): PN-152 (trade name, manufactured by Minwa Kasei Co., Ltd., wherein R in the formula (3) is a hydrogen atom and a polyphenol compound of p≒4, a softening point of 50 ° C, and a hydroxyl group equivalent of 105 g/eq.)

(B-2): H-1 (product name, Minghe Chemical Co., Ltd., formula (3) A polyphenol compound in which R is a hydrogen atom and p≒5, a softening point of 80 ° C, and a hydroxyl equivalent of 104 g/eq.

(B-3): MilexXLC (trade name, manufactured by Mitsui Chemicals Co., Ltd., R ₈ and R ₉ in the formula (6) are a hydrogen atom and a polyphenol compound of y ≒ 3.2, a softening point of 77 ° C, and a hydroxyl equivalent of 176 g / eq. )

(B-4): KAYAHARD GPH-65 (trade name, manufactured by Nippon Kayaku Co., Ltd., Z ≒ 1.5 polyphenol compound in formula (5), softening point 65 ° C, hydroxyl equivalent 200 g / eq.)

(B-5): MEP-6309E (trade name, manufactured by Minghe Chemical Co., Ltd., polyhydric phenol compound of q≒5 in formula (4), softening point 81 ° C, hydroxyl equivalent 116 g/eq.)

(C-1): SP-172 (trade name, ADEKA company, 50 wt% propylene carbonate solution, but the amount shown in the table is the solid value)

(C-2): CPI-6976 (trade name, ACETO company, 50 wt% propylene carbonate solution, but the amount shown in the table is the solid value)

(C-3): IRGACUREPAG290 (trade name, manufactured by BASF Corporation)

(D-1): 3-glycidoxypropyltrimethoxydecane

(D-2): 3-glycidoxypropylmethyldimethoxydecane

(Eiii-1): EPOTOTEPG-207GS (trade name, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., polypropylene glycol diepoxypropyl ether, epoxy equivalent 317 g/eq., molecular weight 634)

(Eiii-2): ADEKAGlycilol ED-506 (trade name, manufactured by ADEKA, polypropylene glycol diglycidyl ether, epoxy equivalent) 310g/eq., molecular weight 620)

(Eiii'-1): EPIOLE-1000 (trade name, manufactured by Nippon Oil Co., Ltd., diglycidyl ether of PEG-1000, epoxy equivalent 571 g/eq., molecular weight 1142)

(G-1): MARPROOF G-0150M (trade name, manufactured by Nippon Oil Co., Ltd., copolymer of glycidyl methacrylate and methyl methacrylate, epoxy equivalent 310 g/eq., weight average molecular weight About 10,000)

(G-2): MARPROOF G-0250S (trade name, manufactured by Nippon Oil Co., Ltd., glycidyl methacrylate, copolymer of styrene and methyl methacrylate, epoxy equivalent 310 g/eq., Weight average molecular weight of about 20,000)

As a result of Table 3, it was found that the characteristics of the composition obtained in each of the examples were higher in the resolution of the photosensitive pattern than in the comparative example, and the film after development was free from cracking and the hole pattern was not cracked. And the adhesion after damp heat is also maintained.

Examples 37 to 38 (resistant laminate formed of the photosensitive resin composition of the present invention)

In the composition ratio of Example 17 and Example 23 of Table 3, ethylene glycol dimethyl ether was additionally added, and the mixture was stirred and dissolved at 60 ° C for 1 hour in a flask equipped with a stirrer, and the mixture was dissolved at 25 ° C. The solution viscosity was diluted to 3 Pa ‧ and after cooling, the membrane was filtered at a pore size of 1.0 μm to obtain a base paint for a dry film of the photosensitive resin composition of the present invention. These base paints are applied to a base film (made of polypropylene, Mitsubishi Plastics, and film thickness). 38 μm) was uniformly applied, and dried in a warm air convection dryer at 65 ° C, 5 minutes, and 80 ° C for 15 minutes, and then the coated film (polypropylene, manufactured by Mitsubishi Plastics Co., Ltd., film thickness: 38 μm) was laminated on the exposed surface. A resist laminate (photosensitive resin composition laminate) obtained by holding a dry film resist having a film thickness of 25 μm was obtained.

(patterning of dry film resist)

The resist laminated body of each photosensitive resin composition obtained above peeled off the coating film, and after laminating on the crucible wafer at a roll temperature of 70 ° C, an air pressure of 0.2 MPa, and a speed of 0.5 m/min, the base film was peeled off. A 25 μm photosensitive resin composition layer (dry film resist) was obtained. The photosensitive resin composition layer was subjected to contact exposure using an i-ray exposure apparatus (mask aligner: manufactured by Ushio Inc.). After that, the PEB was dried on a hot plate at 95 ° C for 5 minutes, and immersed and developed at 23 ° C for 3 minutes with SU-8 Developer (trade name, manufactured by MICROCHEM Co., Ltd., propylene glycol monomethyl ether acetate main component). The alcohol was washed, washed, and dried to obtain a resin pattern hardened on the substrate.

Using the photosensitive resin compositions of Examples 17 and 23 In the case of a resist laminate, a cured product having no side walls and a crack and a fine line-fixed pattern having a width of 6 μm and having vertical side walls can be obtained.

[industrial use]

The photosensitive resin composition of the present invention can form a fine and vertical sidewall shape pattern by photolithography. The hardened material has a low Excellent characteristics of stress and heat and humidity resistance. Available with semiconductor or MEMS. Micromechanical applications, especially MEMS packaging, semiconductor packaging, microreactors form permanent resists and hardeners for the necessary properties of parts.

Claims (15)

A photosensitive resin composition comprising (A) an epoxy resin, (B) a polyhydric phenol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing decane compound, and (E) reactivity A photosensitive resin composition of an epoxy monomer characterized in that the (A) epoxy resin contains the following formula (1) The epoxy resin (a) obtained by the reaction of the represented phenol derivative with an epihalohydrin, and the following formula (2) (wherein m is an average value, and represents a real number in the range of 2 to 30, and R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group, and X is independent. The hydrogen atom or the epoxy propyl group, at least one of the plurality of X present is an epoxy resin (b) represented by a glycidyl group, and the (B) polyphenol compound contains the following formula (3) or even (6) ) (wherein p is an average value, and represents a real number in the range of 1 to 10, and R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) (where q is the average value, indicating a real number in the range of 1 to 10) (where z is the average value, indicating a real number in the range of 1 to 10) (wherein, y is an average value, and a real number in the range of 1 to 10, and R ₈ and R ₉ are each independently, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) is selected from the group of phenol compounds. One or more, and the (E) reactive epoxy monomer contains the following formula (12) (In the formula, n is an average value, and is an epoxy compound represented by a real number in the range of 1 to 20 (except 1), and R ₇ is a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms). The photosensitive resin composition according to claim 1, wherein the (E) reactive epoxy monomer comprises poly n-propylene glycol diepoxypropyl ether, and/or polyisopropylene glycol diepoxypropyl ether, and/or Or polyethylene glycol diepoxypropyl ether. The photosensitive resin composition according to claim 1, wherein the ratio of the ratio of the (E) reactive epoxy monomer to the total mass of the (A) epoxy resin and the (B) polyhydric phenol compound is 2 to 12% by mass. . The photosensitive resin composition according to claim 1, wherein (B) the proportion of the polyphenol compound is relative to (A) the quality of the epoxy resin The amount is 1 to 40% by mass. The photosensitive resin composition according to claim 1, wherein the ratio of the ratio of the (C) photocationic polymerization initiator to the total mass of the (A) epoxy resin and the (B) polyhydric phenol compound is 0.1 to 15% by mass. . The photosensitive resin composition according to claim 1, wherein the (D) epoxy group-containing decane compound is an epoxy group-containing alkoxydecane compound. The photosensitive resin composition according to claim 1, wherein (D) the ratio of the epoxy group-containing decane compound is relative to (A) epoxy resin, (B) polyphenol compound, and (C) photocationic polymerization initiator And (E) the total mass of the reactive epoxy monomer is 1 to 15% by mass. The photosensitive resin composition according to claim 1, further comprising (G) an acrylic resin. The photosensitive resin composition according to claim 8, wherein the (G) acrylic resin is a copolymer obtained by using an ethylenically unsaturated monomer having a glycidyl group. The photosensitive resin composition according to claim 8, wherein the ratio of the (G) acrylic resin is relative to (A) epoxy resin, (B) polyphenol compound, (C) photocationic polymerization initiator, (D) The total mass of the epoxy group-containing decane compound and the (E) reactive epoxy monomer is 1 to 20% by mass. The photosensitive resin composition according to claim 1, which further contains (F) a solvent. The photosensitive resin composition as recited in claim 11, wherein (F) The mixing ratio of the solvent is 5 to 95% by mass based on the total mass of the photosensitive resin composition containing the (F) solvent. A cured product of the photosensitive resin composition according to any one of claims 1 to 12. A resist laminate obtained by sandwiching a photosensitive resin composition according to any one of claims 1 to 12 on two substrates. A cured product of a dry film resist obtained from the resist laminate described in claim 14.