TW201425450A - 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 polyol 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).

Description

Photosensitive resin composition, resist laminate, and hardened materials thereof

The present invention relates to a photosensitive resin composition which is excellent in the shape of a side wall and has excellent resolution, has a small internal stress after hardening, and has excellent substrate adhesion after a damp heat test, and a cured product thereof. The cured product of the photosensitive resin composition according to the present invention is used for electronic parts such as MEMS (Micro Electro Mechanical System) parts, μ-TAS (Micro Total Analysis System) parts, microreactor parts, capacitors or inductors. Insulation layer, LIGA parts, micro-injection molding and hot embossing molds and printers, screen or template for fine printing applications, MEMS and semiconductor package parts, BioMEMS and biophotonic devices, and printed wiring boards.

Among the photosensitive resin compositions, those who can perform photolithography are called photoresists, and are widely used in semiconductors or MEMS. Micromechanical applications, etc. In such an application, photolithography is performed on the substrate for pattern exposure, and then developed by developing with a developer to selectively remove the exposed or non-exposed regions. The photoresist system has positive and negative types, and is exposed. The light portion is dissolved in the developer and is positive, and the opposite is not negative. In the electrical packaging application or MEMS application of cutting-edge technology, not only the uniform rotational coating film forming ability but also the high aspect ratio, the vertical side wall shape in the thick film, the high adhesion to the substrate, and the like are required. Here, the aspect ratio is calculated by the film thickness of the resist film/line width of the pattern, and shows an important characteristic of the performance of photolithography.

According to Patent Document 1 and Non-Patent Document 1, a composition containing bisphenol A novolac epoxy resin as a main component has a very high resolution, and can form a high aspect ratio photosensitive image and a photosensitive resin hardened. Things. However, the obtained cured resin tends to be brittle depending on the application, and cracks (gap cracks) tend to occur during development or when internal stress occurs. Therefore, according to the type of the substrate using the resin composition, depending on the type of the resin cured product, not only the adhesion can be lowered, but also the peeling can be caused between the substrate and the cured resin depending on the case. All of these problems are caused by the stress generated in the cured product of the resin due to the hardening shrinkage of the composition. When the hardening shrinkage is large, buckling (warpage) of the substrate is often caused.

Further, when the substrate on which the resin cured product was formed was subjected to a damp heat test (80 ° C, 100%, 24 hours) which is one of the durability accelerated tests, it is known that the cured resin is peeled off from the substrate. Therefore, when this resin cured product is used for applications such as MEMS packaging, semiconductor packaging, and microreactor forming parts, there is a problem that durability is not good.

Patent Document 2 discloses a photosensitive composition containing an epoxy resin having an average functional group number of 1.5 or more, a hydroxyl group-containing additive, and a photocationic polymerization initiator. In the same literature, it is described that by adding a hydroxyl group The additive has the effect of increasing the flexibility of the coating film up to 100 μm and reducing the shrinkage effect. However, the composition disclosed in the same document has a resolution of about 90 μm as a photoresist, and the shape of the photosensitive image is caused by a trailing residue on the edge portion of the photosensitive image after development, and the top of the photosensitive image has a circular shape. Therefore, this photosensitive composition is not suitable as a MEMS package, a semiconductor package, a microreactor, or the like.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 4882245

[Patent Document 2] US Patent No. 4256828

[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, and its purpose is to provide a semiconductor or MEMS. In the field of micromechanical applications, an epoxy resin composition which is hardened by cationic polymerization, and which is capable of forming a vertical side wall shape and having a fine resolution, a low stress, and a moist heat resistance image. A resin composition, and/or a laminate thereof, and the cured product.

As a result of repeated efforts by the inventors of the present invention, it has been found that the photosensitive resin composition of the present invention can solve the above problems.

The various aspects of the invention are as follows.

[1].

A photosensitive resin composition comprising (A) an epoxy resin, (B) a polyol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing decane compound, and (E) a reaction The photosensitive resin composition of the epoxy monomer, characterized in that the (A) epoxy resin is contained by the following formula (1)

An epoxy resin (a) obtained by reacting a 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 from 2 to 30; R & lt lines ₁ and R ₂ each independently represent a hydrogen atom, alkyl group or a trifluoromethyl group of 1 to 4; X-lines which are independent of The hydrogen atom or the epoxy propyl group is present, and the epoxy resin (b) represented by at least one of the plurality of epoxy groups of X is present, and the (B) polyol compound contains the following formula ( 3)

(wherein, x is an average value and represents a real number in the range of 1 to 15; and R ₃ is a polyester polyol represented by a divalent aliphatic hydrocarbon group which may contain at least one ether bond in the carbon chain), and/ Or the following formula (4)

(wherein, y is an average value and represents a real number in the range of 1 to 6; and R ₄ is a polyester polyol represented by a trivalent aliphatic hydrocarbon group which may contain at least one ether bond in the carbon chain), and (E) A reactive epoxy monomer containing a bisphenol type epoxy resin.

[2].

The photosensitive resin composition according to the above [1], wherein the (E) reactive epoxy single system comprises a bisphenol F type epoxy resin and/or a bisphenol A type epoxy resin.

[3].

The photosensitive resin composition according to the above [1], wherein the blending ratio of the (E) reactive epoxy monomer is 2 with respect to the total mass of the (A) epoxy resin and the (B) polyol compound. ~12% by mass.

[4].

The photosensitive resin composition according to the above [1], wherein the blending ratio of the (B) polyol compound is from 1 to 30% by mass based on the total mass of the (A) epoxy resin.

[5].

The photosensitive resin composition according to the above [1], wherein (C) the photocationic polymerization initiator blend ratio is relative to (A) epoxy resin, (B) polyol compound, and (E) reactivity The total mass of the epoxy monomers is from 0.1 to 15% by mass.

[6].

The photosensitive resin composition according to the above [1], wherein (D) contains a ring The oxo decane compound is an alkoxy decane compound containing an epoxy group.

[7].

The photosensitive resin composition according to the above [1], wherein (D) the blend ratio of the epoxy group-containing decane compound is relative to (A) the epoxy resin, (B) the polyol compound, and (C) the photocation The total mass of the polymerization initiator and the (E) reactive epoxy monomer is from 1 to 15% by mass.

[8].

The photosensitive resin composition according to the above [1], which further contains (F) a solvent.

[9].

The photosensitive resin composition of the above item [8], wherein the blending ratio of the solvent (F) is 5 to 95% by mass based on the total mass of the photosensitive resin composition containing the (F) solvent.

[10].

A cured product of the photosensitive resin composition according to any one of the above [1] to [9].

[11].

A resist laminate obtained by sandwiching a photosensitive resin composition according to any one of the above [1] to [9] with two base materials.

[12].

A cured product of a dry film resist obtained by a resist laminate as described in the above [11].

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. Micro-mechanical applications, in particular MEMS packages, semiconductor packages, micro-reactors, permanent resists and hardeners necessary for the formation of parts.

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 Both of the epoxy resins (b) represented by the above formula (2). Among them, the epoxy resin (a) contributes to the vertical sidewall shape and the fine resolution of the cured product (pattern) obtained by photolithography using the photosensitive resin composition of the present invention. The epoxy resin (a) can be obtained by a method for synthesizing a conventionally known epoxy resin using a phenol derivative represented by the formula (1) and an epihalohydrin.

In a general method for synthesizing the epoxy resin (a), for example, a mixed solution of a phenol derivative represented by the formula (1) and an epihalohydrin dissolved in a solvent which can be dissolved is added, and a base such as sodium hydroxide is added. After the temperature is raised to the reaction temperature, the addition reaction and the ring closure reaction are carried out, and the water washing, separation and removal of the water layer of the reaction liquid are repeated, and finally the solvent is distilled off from the oil layer. The halogen of the epihalohydrin is selected from F, Cl, Br and I, and is typically represented by Cl or Br. a phenol derivative represented by the formula (1) and an epihalohydrin The reaction is carried out using an epihalohydrin of usually 0.3 to 30 moles, preferably 1 to 20 moles, more preferably 3 to 15 moles, per mole of the phenol derivative (corresponding to a hydroxyl group of 3 moles). Come on. Since the epoxy resin (a) is obtained by the above reaction, it is usually present as a mixture of a plurality of products.

It is known that, depending on the use ratio of the phenol derivative represented by the formula (1) and the epihalohydrin used in the above-mentioned synthesis reaction, the epoxy resin (a) having a main component different in the epoxy resin (a) is obtained. For example, when an excess amount of epihalohydrin is used with respect to the phenolic hydroxyl group of the phenol derivative, a trifunctional epoxy resin in which all three phenolic hydroxyl groups in the formula (1) are epoxidized is obtained as a main component. Epoxy resin (a). As the amount of the epihalohydrin relative to the phenolic hydroxyl group is reduced, the phenolic hydroxyl group of the plurality of phenol derivatives is bonded through the epihalohydrin, and the remaining phenolic hydroxyl group is epoxidized to have a large molecular weight polyfunctional ring. The content of the oxyresin will increase.

As a method of obtaining the epoxy resin (a) containing the epoxy resin as a main component of such a polymer, in addition to the method of controlling the use ratio of the phenol derivative and the epihalohydrin, it is also possible to further A method of reacting a phenol derivative with an epoxy resin (a). 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 a phenol derivative as long as it is an epoxy resin obtained by reacting a phenol derivative represented by the formula (1) with an epihalohydrin. Any one of the epoxy resin of the monomer or the epoxy resin of the phenol derivative Ingredients of epoxy resin (a). The epoxy resin (a) is preferably an epoxy resin of a monomer of a phenol derivative or a dimer of a phenol derivative, which is excellent in solvent solubility or low in softening point. 2 epoxy resins having a structure in which a phenol derivative represented by the formula (1) is bonded via an epihalohydrin) or a diol derivative as a trimer (having three phenol derivatives represented by the formula (1) The epoxy resin (a) which is a main component of any of the epoxy resins having a structure in which the substance is bonded to the halogenated alcohol. More preferably, it is an epoxy resin (a) which has the epoxy resin of the monomer of a phenol derivative, or the epoxy resin of the 2-mer of a phenol derivative as a main component.

In addition, the term "main component" as used in the present invention means a plurality of epoxy resins of a single epoxy resin and/or a multipolymer epoxy resin contained in the epoxy resin (a). The most abundant epoxy 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 (5).

The specific structure of the epoxy resin (a) which is a dimer of the phenol derivative represented by the formula (1) is represented by the following formula (6).

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

The epoxy resin (a) is preferably those having a weight average molecular weight in the range of 500 to 12,000, more preferably having a weight average molecular weight in the range of 500 to 9000. Specific preferred examples thereof include NC-6300H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220 to 240 g/eq., softening point 60 to 85 ° C). Further, the weight average molecular weight in the present case means a value calculated in terms of polystyrene based on the GPC measurement result, the epoxy equivalent means a value measured according to JIS K-7236, and the softening point means according to JIS K -7234 measured value.

The epoxy resin (b) is a photosensitive resin composition of the present invention, and provides a resolution and flexibility to a cured product (pattern) obtained by photolithography. As a result of the improvement of these characteristics due to the epoxy resin (b), the wet heat adhesion of the cured product is improved. Epoxy resin (b) can be obtained by further reacting epichlorohydrin with a part of an alcoholic hydroxyl group of a condensed product of bisphenols and 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 average value of m in the formula (2) representing the epoxy resin (b) means the average value of a plurality of compounds constituting the reaction product. The epoxy resin (b) preferably has an epoxy equivalent of from 250 to 400 g/eq., and preferably has a softening point of from 60 to 85 °C.

In the photosensitive resin composition of the present invention, an epoxy resin is used in an amount of 2 to 4,900% by mass, preferably 5 to 100% by mass, and more preferably 10 to 70% by mass based on the mass of the epoxy resin (a). (b). By using the epoxy resin (b) at a mass ratio of 4,900 mass% or less with respect to the mass of the epoxy resin (a), the photosensitive image pattern can be easily made into a vertical side wall shape, and the pattern is suppressed to have a circle. shape. In addition, by using the epoxy resin (b) at a mass ratio of 2% by mass or more, the surface of the photosensitive image pattern can be effectively prevented from being cracked.

In the epoxy resin (A) contained in the photosensitive resin composition of the present invention, an epoxy resin other than the epoxy resin (a) and the epoxy resin (b) may be used in combination. The epoxy resin which can be used in combination is not particularly limited, and the blending ratio thereof is not particularly limited as long as it does not impair the effects of the present invention. However, in the category of (A) epoxy resin, the epoxy group-containing decane compound of the component (D) is not contained, and the epoxy resin defined as the reactive epoxy monomer of the component (E) is not included.

The (B) polyol compound contained in the photosensitive resin composition of the present invention contains the above formula (3) and/or the above formula (4). Polyester polyol. Any one of the polyester polyols represented by the formula (3) and the formula (4) may be in the form of a single or a mixture of plural kinds. (B) The polyol compound is a hydroxyl group which reacts with the epoxy group in (A) epoxy resin under the influence of a strong acid catalyst, and acts as a reactive diluent. In particular, by using the polycaprolactone polyol represented by the formula (3) and/or the formula (4), after the resin composition is applied, the solvent component is dried as needed to soften the dried coating film. Therefore, it is possible to avoid the stress induction of the exposure hardening, the development, and the thermal hardening step in the photolithography process, reduce the shrinkage, and prevent cracking of the photosensitive image. Moreover, when it is used as a resist laminate (dry film) in which a dry coating film of a photosensitive resin composition is sandwiched on a substrate, when the resist laminate is wound around a plastic cylinder as a long roll, it is also obtained. The effect of cracking does not occur in the resist laminate.

In the formula (3), x is an average value, and represents a real number in the range of 1 to 15, preferably a real number in the range of 1 to 10. Further, the average value referred to herein means an average value of x described in two of the formulas (3). For example, when one of x is 4 and the other is x, the average value x is 5.

In the formula (3), R ₃ represents a divalent aliphatic hydrocarbon group which may contain at least one ether bond in the carbon chain. The aliphatic hydrocarbon group represented by R ₃ generally means a divalent aliphatic hydrocarbon group of a straight or branched chain having 1 to 15 carbon atoms, preferably a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. More preferably, it is a linear or branched aliphatic hydrocarbon group having a carbon number of 2 to 8. Specific examples thereof include a linear aliphatic hydrocarbon group such as a methylene group, an ethylidene group, a propyl group, a butyl group, and a pentyl group; or an alkyl group as a side chain bonded to the aforementioned linear aliphatic hydrocarbon group. Branched chain aliphatic hydrocarbon group.

Further, specific examples of the divalent aliphatic hydrocarbon group having at least one ether bond in the carbon chain (the group in which a plurality of aliphatic hydrocarbon portions are bonded to the oxygen atom) are exemplified by a methylene group and an extended ethyl group through an oxygen atom bond. The junction of the knot. The number of oxygen atoms (the number of ether bonds) in the linking group is not particularly limited. For example, an oxygen atom and an ethylidene group are further bonded to a linking group composed of the aforementioned methylene group, an oxygen atom and an ethyl group. The linking group is also included in the definition of R ₃ . a divalent aliphatic hydrocarbon group containing at least one ether bond in the carbon chain, preferably having a carbon number in the above range (only a carbon number of 2 or more), and all of them are linear, all branched, linear and branched Any combination of chains can be used. Further, the linking group may have a different carbon number even if the plurality of aliphatic hydrocarbon groups are different. Further, the number of oxygen atoms (the number of ether bonds) in the linking group is usually from 1 to 3, preferably from 1 to 2, more preferably one.

The polyester polyol represented by the formula (3) can be obtained from a commercially available product. Specific examples thereof include "Placcel 205" having a molecular weight of 530 and an OH value of 210 mgKOH/g, "Placcel 210" having a molecular weight of 1,000 and an OH price of 110 mgKOH/g, and "Placcel 220" having a molecular weight of 2,000 and an OH price of 56 mgKOH/g (both of them). "Product name, manufactured by Daicel Co., Ltd., or "Capa2054" having a molecular weight of 550 and an OH price of 204 mgKOH/g, "Capa2100" having a molecular weight of 1,000 and an OH price of 112 mgKOH/g, and "Capa2200" having a molecular weight of 2,000 and an OH price of 56 mgKOH/g (both) Product name, manufactured by Perstorp Corporation).

In the formula (4), y is an average value, and represents a real number in the range of 1 to 6, preferably a real number in the range of 1 to 4. In addition, the average value referred to here means the average value of the three y described in the formula (4), for example, each When y is 2, 3, and 4, the average y is 3.

R ₄ represents a trivalent aliphatic hydrocarbon group which may contain at least one ether bond in the carbon chain. The aliphatic hydrocarbon group represented by R ₄ is usually a trivalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, preferably a trivalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a trivalent fat having 2 to 8 carbon atoms. A hydrocarbon group. Among the aliphatic hydrocarbon groups, those having an alkyl group as a side chain are also included.

Specific examples of the trivalent aliphatic hydrocarbon group having at least one ether bond in the carbon chain (the group in which a plurality of aliphatic hydrocarbon portions are bonded through an oxygen atom) are exemplified by a methylene group bonded to a methine group through an oxygen atom. A linking group obtained by one bonding position. The trivalent aliphatic hydrocarbon group having at least one ether bond in the carbon chain preferably has a carbon number in the above range (only a carbon number of 2 or more). Other matters regarding the trivalent aliphatic hydrocarbon group having at least one ether bond in the carbon chain are as described above with respect to the divalent aliphatic hydrocarbon group having at least one ether bond in the carbon chain represented by R ₃ .

The polyester polyol represented by the formula (4) can be obtained from a commercially available product. Specific examples thereof include "Capa 3050" having a molecular weight of 530 to 550 and an OH value of 310 mgKOH/g, "Capa3091" having a molecular weight of 900 and an OH price of 183 mgKOH/g, and "Capa3201" having a molecular weight of 2,000 and an OH price of 84 mgKOH/g (both products). "Placcel 305" having a molecular weight of 530 to 550 and an OH value of 310 mgKOH/g, "Placcel 308" having a molecular weight of 850 and an OH price of 195 mgKOH/g, "Placcel 312 having a molecular weight of 1250 and an OH price of 135 mgKOH/g". "Placcel 320" (having a trade name, manufactured by Daicel Co., Ltd.) having a molecular weight of 2,000 and an OH price of 84 mgKOH/g.

The blending ratio of the (B) polyol compound in the photosensitive resin composition of the present invention is usually from 1 to 30% by mass, preferably from 2 to 25% by mass, based on the total mass of the (A) epoxy resin. When the blending ratio of the (B) polyol compound is 30% by mass or less, the photosensitive image pattern can be easily made into a vertical side wall shape, and the pattern is suppressed from being rounded. When the blending ratio of the (B) polyol compound is 1% by mass or more, the dilution effect or the softening effect of the dried coating film can be sufficiently obtained, and cracking of the surface of the photosensitive image pattern can be effectively prevented. Further, when the polyester polyol represented by the formula (3) and the formula (4) is used in combination, the ratio of use of the two is as long as the ratio of the (B) epoxy resin to the (B) polyol compound is Within the scope, there is no special limit.

In the (B) polyol compound contained in the photosensitive resin composition of the present invention, a polyol compound other than the polyol compound represented by the above formulas (3) and (4) may be used in combination. The polyol compound which can be used in combination is not particularly limited, and the blending ratio of the polyol compound which can be used in combination is not particularly limited as long as it does not impair the effects of the present invention.

The (C) photocationic polymerization initiator contained in the photosensitive resin composition of the present invention is irradiated with radiation such as excimer laser such as ultraviolet light, far ultraviolet ray, KrF or ArF, or X-ray or electron beam to generate cations. 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 (pentafluorophenyl) borate, diphenyl sulfonium hexafluorophosphate, diphenyl sulfonium hexafluoroantimonate, and di(4- Nonylphenyl)phosphonium hexafluorophosphate Acid salt, tolyl isopropylphenyl sulfonium (pentafluorophenyl) borate (manufactured by Rhodia Co., Ltd., trade name Rhodorsil PI 2074), bis (4-tert-butyl) hydrazine (trifluoromethanesulfonyl) methane (manufactured by BASF Corporation, trade name CGI BBI-C1).

Further, specific examples of the aromatic sulfonium salt include 4-phenylthiodiphenylphosphonium hexafluoroantimonate (manufactured by San-Apro Co., Ltd., trade name CPI-101A), and phenylthiodiphenyl hydrazine ( Pentafluoroethyl)trifluorophosphate (manufactured by San-Apro Co., Ltd., trade name CPI-210S), 4-{4-(2-chlorobenzylhydrazino)phenylthio}phenylbis(4-fluorophenyl) A mixture of hexafluoroantimonate (trade name SP-172, manufactured by ADEKA) and aromatic hexafluoroantimonate containing 4-phenylthiodiphenylphosphonium hexafluoroantimonate (made by ACETO Corporate USA) Trade name: CPI-6976) and triphenylsulfonium (trifluoromethanesulfonyl) methanide (manufactured by BASF Corporation, trade name CGI TPS-C1), ginseng [4-(4-ethylmercaptophenyl)sulfonate Phenyl phenyl] sulfhydrazine (trifluoromethylsulfonyl) methyl metalloide (manufactured by BASF Corporation, trade name GSID 26-1), ginseng [4-(4-ethylmercaptophenyl)sulfonylphenyl鋶肆(2,3,4,5,6-pentafluorophenyl)borate (manufactured by BASF Corporation, trade name Irgacure PAG290).

Among these photocationic polymerization initiators, in the photosensitive image forming step, an aromatic erroneous salt having high vertical rectangular workability and high thermal stability is preferred. Particularly preferred is 4-{4-(2-chlorobenzylidene)phenylthio}phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate containing 4-phenylthiodiphenylphosphonium hexafluoroantimony a mixture of aromatic hydrazine hexafluoroantimonate of acid salt, ginseng [4-(4-ethylmercaptophenyl)sulfonylphenyl]anthracene (2,3,4,5,6-pentafluorophenyl) Borate.

These (C) photocationic polymerization initiators may be used alone or in combination of two or more. (C) Photocationic polymerization initiator component which has the function of absorbing light. Therefore, in the case of a thick film (for example, 50 μm or more), in order to sufficiently penetrate the light at the time of hardening to the deep portion, it is preferable to use the component (C) in an amount that is not excessively large (for example, 15% by mass or less). On the other hand, in order to obtain a sufficient curing rate in a thick film, it is preferred 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) is added in a small amount (for example, 1% by mass or more), that is, sufficient polymerization initiation performance is exhibited. In the case of a film, even if the component (C) is used in a large amount, the penetration of light into the deep portion is not greatly lowered, but from the viewpoint of economy (preventing unnecessary use of a high-priced initiator), it is preferably Use an amount of (C) that is not excessively large. From these viewpoints, the blending ratio of (C) photocationic polymerization initiator in the photosensitive resin composition of the present invention is relative to (A) epoxy resin component, (B) The total mass of the polyol compound component and the (E) reactive epoxy monomer is usually 0.1 to 15% by mass, preferably 0.2 to 8% by mass. When the (C) photocationic polymerization initiator has a high molar absorption coefficient at a wavelength of 300 to 380 nm, it is necessary to adjust the film to a suitable blending amount in accordance with the film thickness when the photosensitive resin composition is used.

(D) an epoxy group-containing decane compound contained in the photosensitive resin composition of the present invention, in the step of using the composition of the present invention, the adhesion to the substrate is improved, and the composition of the present invention is The interlayer adhesion in the case of forming a multilayer structure is improved. Further, (D) an epoxy group-containing decane compound does not hinder the photosensitive resin composition of the present invention. Save stability.

Preferred examples of the (D) epoxy group-containing decane compound include an epoxy group-containing alkoxydecane compound. Examples of the alkoxydecane compound containing an epoxy group include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 3-glycidoxypropane. Propyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These may be used alone or in combination of two or more.

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

The (E) reactive epoxy monomer contained in the photosensitive resin composition of the present invention contributes to the improvement of flexibility and flexibility of the uncured film and cured film by the photosensitive resin composition of the present invention. And contribute to the improvement of the adhesion of the cured film. (E) A reactive epoxy monomer containing a bisphenol type epoxy resin.

The bisphenol type epoxy resin which is a (E) reactive epoxy monomer means a bisphenol type epoxy resin having a molecular weight of 1100 or less having two or more epoxy groups in one molecule. When the molecular weight of the bisphenol type epoxy resin is 1100 or less, it is difficult for the crack to enter the photosensitive image pattern, and the contrast between the exposed portion and the unexposed portion is suppressed from being lowered, so that the solution to the high-definition shape is obtained. Like as good.

(E) Reactive epoxy monomer bisphenol type epoxy resin Examples of the material include a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, and a bisphenol B type resin. Particularly preferred is bisphenol F type epoxy resin and bisphenol A type epoxy resin. These may be used alone or in combination of two or more.

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

In the (E) reactive epoxy monomer contained in the photosensitive resin composition of the present invention, a reactive epoxy monomer other than the bisphenol epoxy resin may be used in combination. The reactive epoxy monomer which can be used in combination is not particularly limited, and the blending ratio of the reactive epoxy monomer which can be used in combination is not particularly limited as long as it does not impair the effect of the present invention.

In the photosensitive resin composition of the present invention, in order to lower the viscosity of the resin composition and improve the coatability, a solvent (F) can be used. The solvent is not particularly limited as long as it is an organic solvent which is usually used for inks, paints, and the like, and a component which can dissolve the constituent components of the photosensitive resin composition, and does not cause chemical reaction with the constituent components. 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; Glycol ethers such as propylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether; ethyl lactate, ethyl acetate, butyl acetate, methyl-3-methoxypropionate, carbene Esters such as alcohol acetate, propylene glycol monomethyl ether acetate and γ-butyrolactone; alcohols such as methanol and ethanol; aliphatic groups such as octane and decane Hydrocarbon; petroleum-based solvent such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain.

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. The amount of the (F) solvent used to maintain the solubility of the main component of the resin composition, the volatility of each component, the liquid viscosity of the composition, etc., is usually 95% by mass in the photosensitive resin composition containing a solvent. The following can be. The amount thereof to be used is preferably from 5 to 95% by mass, more preferably from 10 to 90% by mass.

In the photosensitive resin composition of the present invention, a sensitizer may be further used in order to absorb ultraviolet rays and to impart light to the photocationic polymerization initiator, particularly an aromatic sulfonium salt. The sensitizer is preferably, for example, a thioxanthone compound or an anthracene compound having alkoxy group at the position of No. 9 and No. 10 (9,10-dialkyloxyanthracene derivative). Examples of the alkoxy group include a C1 to C4 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The 9,10-dialkoxyfluorene derivative may further 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; or an alkyl sulfonate group or a carboxylic acid alkyl ester group. The alkyl group in the alkyl sulfonate group or the alkyl carboxylate group may, for example, be a C1-C4 alkyl group. The substitution position of the substituents is preferably the position 2.

Specific examples of the thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2, 4-diisopropylthioxanthone and the like. Preferred is 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYACURE DETX-S), and 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 alone or in combination of two or more, but are preferably used as 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylhydrazine. The sensitizer is effective in a small amount, and the use ratio thereof is usually 30% by mass or less, preferably 20% by mass or less based on the mass of the (C) photocationic polymerization initiator component.

In the resin composition of the present invention, in order to reduce the adverse effects caused by the ions of the (C) photocationic polymerization initiator, an ion scavenger may be added as needed. Specific examples of the ion scavenger include aluminum alkoxides such as trimethoxy aluminum, triethoxy aluminum, triisopropoxy aluminum, isopropoxy diethoxy aluminum, and tributoxy aluminum; Phenoxy aluminum such as aluminum phenoxide and tri-p-methylphenoxy aluminum; aluminum triethyl decoxide, aluminum tristearate, aluminum tributyrate, aluminum tripropionate, aluminum triethyl phthalate , aluminum tris-trifluoroacetate, aluminum triethylacetate, aluminum di-trimethylethylammonium methanesulfonate and diisopropoxy (ethylacetonitrile) An organoaluminum compound such as aluminum. These components may be used alone or in combination of two or more. Further, the blending amount thereof is usually 10 in terms of the total mass of the (A) epoxy resin, (B) polyol compound, (C) photocationic polymerization initiator, and (E) reactive epoxy monomer. Below mass%.

In the photosensitive resin composition of the present invention, various additives such as a thermoplastic resin, a colorant, a thickener, an antifoaming agent, and a leveling agent can be used as needed. Examples of the thermoplastic resin include polyether oxime, polystyrene, polycarbonate, and the like. Examples of the coloring agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, ruthenium, quinacridone red, pyrrolopyrrolodione red, and the like. The amount of the additive to be used is basically 0% by mass or more and 30% by mass or less, respectively, in the photosensitive resin composition of the present invention other than the solvent. However, the amount of such use may be appropriately increased or decreased depending on the purpose of use and the required function of the cured film.

Examples of the tackifier include orben, organic bentonite, montmorillonite, and the like. Examples of the antifoaming agent include antifoaming agents such as polyfluorene-based, fluoroalkyl-based, and polymeric. The amount of the additives to be used is basically 0% by mass or more and 10% by mass or less, respectively, in the photosensitive resin composition of the present invention other than the solvent. However, the amount of such use may be appropriately 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, for example, barium sulfate, barium titanate, cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and Mongolian may be used. Any inorganic filler such as desilted or mica powder. The amount of the inorganic filler to be used is usually 0 or more and 60% by mass or less based on the mass of the photosensitive resin composition of the present invention other than the solvent. However, the amount of use can be appropriately increased according to the purpose of use and the required function of the cured film. Less. Similarly, an organic filler such as polymethyl methacrylate, rubber, fluoropolymer or polyurethane powder may be used in the photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention can be obtained by (A) an epoxy resin, (B) a polyol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing decane compound, and (E) An essential component of the reactive epoxy monomer; (F) a solvent, a sensitizer, an ion scavenger, a thermoplastic resin, a colorant, a tackifier, an antifoaming agent, a leveling agent, and any optional component as needed The inorganic filler or the like is prepared by mixing and stirring in a usual manner. When mixing and stirring, a disperser such as a dissolver, a homogenizer, or a 3-roll mill can be used as needed. Further, after mixing, it may be further filtered using a mesh, a membrane filter or the like.

A method of forming a resist cured film from the photosensitive resin composition of the present invention will be described below.

The photosensitive resin composition of the present invention is preferably used in the form of a liquid in which a solvent is added in order to coat the substrate. The photosensitive resin composition of the present invention diluted with a solvent to a desired viscosity can be dose-distributed onto a substrate, the substrate can be accelerated to a constant rotation speed, and the rotation speed can be kept constant to obtain a desired film thickness. The coating was carried out by a spin coating method. In order to control the film thickness, spin coating can be performed at various rotation speeds. As another method, the photosensitive resin composition can be applied to the substrate by other coating methods such as roll coating, doctor blade coating, slit coating, dip coating, gravure coating, and blow coating.

After coating, it can be dried and baked (pre-baked) to dissolve The agent evaporates. Dry baking conditions may be selected as a semi-hardened dried coating film forming a photoresist. As a typical condition, a smooth surface heating plate can be used to bring the coating film into contact with or close to the surface, 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. Dry at °C for 1 to 15 minutes, followed by drying at 90 to 125 °C for 5 to 120 minutes. As another method, dry baking can be carried out in a convection oven. Next, the coating film of the dried photosensitive resin composition is exposed by a bright line having a near-ultraviolet wavelength of 300 to 500 nm from a medium-pressure or ultra-high pressure mercury lamp by drawing a mask having a desired mask pattern. The light beam irradiation by the X-ray radiation of the radiation source or the irradiation of the electron beam radiation directly or through the patterning exposure can form a photosensitive image. Close, close, or projection printing can be used. After the exposure, in order to promote the polymerization reaction by the acid catalyst action in the exposed region of the coating film, post-exposure baking can be performed. Typical conditions may be 1 to 5 minutes at 65 ° C and 1 to 60 minutes at 95 ° C depending on the thickness of the coating film on the hot plate and the thermal conductivity of the substrate or the thickness of the substrate.

Next, in order to dissolve and remove the unexposed portion, it may be immersed in the organic solvent developing solution for 2 to 30 minutes, depending on the thickness of the coating film and the solvent strength of the developer solvent. Further, the developed image can be removed by applying a washing solvent to remove the developer attached to the cured film. The attached developer contains a dissolved photoresist component, and when dried, it tends to cause residue on the photosensitive image to cause contamination. Therefore, it is desirable to remove the adhered developer. In the case of the dipping method, multi-stage development is performed by preparing a clean developing solution tank, thereby preventing adhesion of the residue.

As another method, any of the explosion-proof atomizing spray nozzle or the explosion-proof type small shower head spray nozzle may be used, and the developer solvent may be applied by blowing. Further, as another development method, a method of applying a developer using a paddle method is exemplified. In general, the paddle method includes placing a substrate to be developed on a rotating tool head, and then metering the developing solution in an amount sufficient to form a layer or a paddle on the entire substrate area, and metering the substrate on the substrate rotating at a low speed. After the rotation of the substrate is stopped and the formed developer paddle is allowed to stand on the substrate for a predetermined period of time, the rotation of the substrate is accelerated, and the used developer is rotated and removed, and the rotation is stopped until the rotation is stopped. It is usually necessary to repeat the procedure several times as needed until a clear photographic image is obtained.

Examples of the suitable developer include propylene glycol monomethyl ether acetate, γ-butyrolactone, acetone, cyclopentanone, diacetone alcohol, tetrahydrofuran methanol, N-methylpyrrolidone, anisole, and lactic acid. Ethyl ester, but is not limited thereto. Particularly preferred is a relatively low-cost propylene glycol monomethyl ether acetate which dissolves the unexposed portion satisfactorily.

Examples of the suitable washing liquid include any of the above developing solution solvents, and methanol, ethanol, isopropyl alcohol, and n-butyl acetate. Among them, acetone, ethanol and isopropanol which can be quickly washed and rapidly dried can be quickly washed.

After the washing step, as a final step in the production of the cured film, heat treatment (hard baking) may be applied at a temperature of 130 to 200 ° C in accordance with the heat resistance of the substrate. By thermally hardening the film, a permanent cured film (resist) which satisfies various characteristics can be obtained.

Among the substrate materials that can be used, it contains bismuth and dioxane. Antimony, antimony, lithium niobate, tantalum nitride, alumina, glass, glass-ceramic, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper-bismuth alloy, indium-tin oxide An organic thin film such as glass, polyimide or polyester, or any substrate of a patterned region of a metal, a semiconductor, or an insulating material is coated, but is not limited thereto.

The photosensitive resin composition of the present invention can also be used as a resist laminate by sandwiching two substrates. For example, a solvent-diluted photosensitive resin composition can be coated on a base film (substrate) 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 film (substrate) or the like is laminated to obtain a resist laminate. At this time, the thickness of the resist on the base film can be adjusted to 2 to 100 μm. As the base film and the film of the substrate, for example, a film of polyester, polypropylene, polyethylene, TAC, or polyimide can be used. In these films, a film which is subjected to mold release treatment such as a polyfluorene-based release treatment agent or a non-polyoxygen-based release treatment agent may be used as needed. When such a resist laminate is used, for example, the 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 roller, a laminator, or the like, and the liquid photosensitive resin. The composition may be subjected to exposure, post-exposure baking, development, and heat treatment in the same manner.

When the photosensitive resin composition is used in the form of a dry film resist by the resist laminate of the present invention, the coating and drying steps on the support or the substrate can be omitted. Thereby, a fine pattern using the photosensitive resin composition of the present invention can be formed more easily.

Use the cured film for MEMS packaging, semiconductor packaging, When the microreactor is formed into a part, the photosensitive resin composition of the present invention can be applied onto a substrate and dried to form a photosensitive resin coating film of the first layer, and the first layer is exposed, followed by exposure and post-baking. After baking, the photosensitive resin composition is further coated and dried to form a photosensitive resin coating film of the second layer, and then the second layer is exposed, followed by post-exposure baking. By repeating this step and finally performing development and hard baking treatment, a complicated multilayer structure pattern can be formed. Alternatively, the first layer may be repeatedly developed and hard baked, and then the second layer may be applied and dried, subjected to alignment exposure through a photomask, developed, and hard baked to form a multilayer structure pattern. Further, the formation of each photosensitive resin layer may be formed by laminating dry film resists.

In addition, "package" means a sealing method or a sealed object for blocking the penetration of an external gas or a liquid in order to maintain the stability of a substrate, a wiring, a component, or the like. The package described in the present specification refers to a hollow package for packaging a vibrator such as a MEMS device having a driver or a SAW device; or a surface protection for preventing deterioration of a semiconductor substrate, a printed wiring board, wiring, or the like; Or in order to form the microreactor into a part, the resin is sealed by a sealing of the sky plate. "Wafer-level package" refers to the formation of a protective film in a wafer state, terminal and wiring processing, to packaging, and then dicing the wafer to form a single piece, and means that the micron to nano flow path or The orifice plate is a three-dimensional processing method in the wafer.

By using the photosensitive resin composition of the present invention, a fine and vertical sidewall shape pattern can be formed by photolithography. The cured product has excellent low stress and heat and humidity resistance. According to the present invention, it can be obtained to satisfy semiconductor or MEMS. Micromechanical applications, especially for MEMS seals Permanently resistive and hardened materials that are necessary for forming components, semiconductor packages, and microreactors to form parts are of great utility in these fields.

[Examples]

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

Examples 1 to 6 and Comparative Examples 1 to 7 (Preparation of photosensitive resin composition solution (liquid resist))

The (A) epoxy resin, (B) polyol compound, and (C) photocationic polymerization are carried out in accordance with the blending amount (unit: mass parts (for the solution product, based on the solid content of the component)) in Table 1) The initiator, (D) an epoxy group-containing decane compound, and (E) a reactive epoxy monomer are diluted to a concentration of 65 mass% and 34 mass% by cyclopentanone (referred to as a dilution of 65 mass%) "Liquid Resist-A", which is referred to as "Liquid Resist-B" when diluted to 34% by mass), and stirred in a flask with a stirrer at 60 ° C for 1 hour to dissolve and dissolve. After cooling, the pore size is obtained. The membrane filter of 1.0 μm was filtered to obtain a photosensitive resin composition solution (liquid resist) of the present invention and comparative use.

(Charming of photosensitive resin composition)

The liquid resist-A obtained in Examples 1 to 6 and Comparative Examples 1 to 7 was applied onto a tantalum wafer by a spin coater, and then prebaked for 10 minutes by a hot plate at 95 ° C. A photosensitive resin composition layer having a dried film thickness of 25 μm after coating was obtained. After that, the coating film ridge portion of the wafer end face is dissolved and removed, and after drying, an i-ray exposure device (photomask alignment exposure machine: manufactured by Ushio Electric Co., Ltd.) is used, and a ray mask with a gray scale for resolution evaluation is passed through The exposure amount was 500 mJ/cm ² (soft contact, i line) and irradiation was performed. Next, post-exposure baking (hereinafter referred to as "PEB") was carried out for 5 minutes by a hot plate at 95 °C. Then, it was immersed and developed at 23 ° C for 3 minutes by SU-8 Developer (trade name, manufactured by Microchem Co., Ltd., propylene glycol monomethyl ether acetate as a main component), rinsed with isopropyl alcohol, and dried to obtain 矽. Resin pattern on the wafer.

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

In the above-described patterning, the sensitivity of each of the photosensitive resin compositions was evaluated by using the optimum exposure amount of the mask transfer as the optimum exposure amount. The smaller the value of the optimum exposure, the higher the sensitivity. The results are shown in Table 1 below.

. Resolution

For each of the liquid resist-A, after performing the above-described prebaking, the steps of dissolving and removing the coating film on the end face of the wafer, and drying, the line width and line spacing of 1 to 100 μm are used. Space) and the circular pattern of the through hole pattern, the optimum exposure amount of each composition (soft contact, i line, exposure amount of Table 1) is irradiated by a heating plate of 95 ° C 5 minutes of PEB. It was immersed and developed at 23 ° C for 3 minutes by SU-8 Developer (trade name, manufactured by Microchem Co., Ltd., propylene glycol monomethyl ether acetate as a main component), washed with isopropyl alcohol, and then dried. In the resist pattern in which no residue and bending were observed and the image was resolved as a vertical side wall shape, the resolution of the smallest pattern width of the substrate adhesion was evaluated. The results are shown in Table 1 below.

. Rift assessment

Further, evaluation was made on the occurrence of cracks in the resin pattern obtained by the respective liquid-resistance-A by the above-described prebaking, the dissolution removal, drying, and exposure of the coating film embossed portion of the wafer end face. The state in which the film has cracks in all directions (discontinuous fracture to the bottom of the film) is "××", and cracks are generated only in the corners of the rectangular through-hole pattern (refer to a fracture state occurring at the pole surface portion of the film). The state of "×" and all cracks is "○". The results are shown in Table 1 below.

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

The liquid resist-A obtained in Examples 1 to 6 and Comparative Examples 1 to 7 was applied onto a tantalum wafer by a spin coater, and then prebaked for 10 minutes by a hot plate at 95 ° C. A photosensitive resin composition layer having a dried film thickness of 25 μm after coating was obtained. After that, the coating film embossed portion of the wafer end surface was dissolved and removed, and dried, and then the i-ray exposure apparatus (mask alignment machine: manufactured by Ushio Electric Co., Ltd.) was used to transmit the pattern mask by the wet heat adhesion evaluation. The optimum exposure of the composition (soft contact, i-line, reference table 1) Exposure amount), PEB was carried out for 5 minutes by a hot plate at 95 °C. It was immersed and developed at 23 ° C for 3 minutes by SU-8 Developer (trade name, manufactured by Microchem Co., Ltd., propylene glycol monomethyl ether acetate as a main component), rinsed with isopropyl alcohol, and dried in an oven at 200 ° C. After 60 minutes of hard baking, a hardened resin pattern was obtained on the wafer. The wafer with the resin pattern was cut, and the aqueous solution of the water-soluble organic solvent-A (composition: 2-imidazole ketone 10% by mass, 2, 2') was placed in a sealed container made of PTFE inner cylinder type. - sulfonic acid diethanol 7.5% by mass, glycerin 5 mass %, pentanediol 5 mass %, ethylene oxide modified acetylene alcohol 0.4 mass %), and the same -B (composition: γ-butyrolactam 30% by mass, 2,2'-oxydiethanol 10% by mass, hexamethylene glycol 5 mass%, ethylene oxide modified acetylene alcohol 0.2% by mass), homo-C (composition: glycerin 15% by mass, polyethylene glycol In each of the solutions of #400 5 mass% and polyoxyethylene lauryl ether 3 mass%), each of the cut pieces was individually immersed, 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 it was "○" when there was no deterioration of the adhesion force, "X" when the adhesion was deteriorated, or when the pattern was floated or peeled off after the test. ××”. The results are shown in Table 1 below.

(Measurement of internal stress of substrate with film)

"The internal stress of the substrate with a film" is measured by a stylus type surface measuring device Dektak8 (trade name, manufactured by Veeco Co., Ltd.), and the wafer substrate (100 mm in diameter and 0.5 mm in thickness) supported by three points is measured. The amount of warpage of the substrate before and after the film formation is converted into a stress by the change in the amount of warpage before and after. In general, the stress of the film is not formed by the film. The shape of the wood. Material is affected. Therefore, a film is formed on the wafer substrate, and the amount of warpage of the substrate before and after the formation is measured, and the internal stress is exhibited. When the resin film hardens and contracts, a compressive stress is generated. As the stress is increased, the pressure of the cured film increases the warpage of the substrate, and the film itself also cracks such as cracks or cracks. The smaller the internal stress, the lower the warpage of the substrate, and the cracking of the film itself is also eliminated.

Each of the liquid resists-B obtained in Examples 1 to 6 and Comparative Examples 1 to 7 was applied to each of the tantalum wafers (diameter: 100 mm, thickness: 0.5 mm) having a measured amount of warpage by a spin coater. Prebaking was carried out for 5 minutes by a hot plate at 95 ° C to obtain a photosensitive resin composition layer having a dried film thickness of 2.0 μm after coating. After that, the coating film embossed portion of the wafer end face was dissolved and removed, and dried, and then an i-line exposure apparatus (mask alignment machine: manufactured by Ushio Electric Co., Ltd.) was used to optimize the exposure amount of each composition (soft contact, i-line). The exposure amount of Table 1 was irradiated to the entire film, and PEB was performed for 5 minutes by a hot plate at 95 °C. Next, a 60-minute hard baking treatment was performed in an oven at 200 ° C to obtain a cured resin film-attached wafer. Each sample of the film-attached substrate was sufficiently cooled at 23 ° C, and the amount of warpage was measured to calculate the compressive stress. The results are shown in Table 1 below.

Further, (A-1) to (Ei'-1) in Table 1 indicate the following.

(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 the formula (2) are a hydrogen atom, and an epoxy resin (b) of m≒6, an epoxy equivalent of 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 a hydrogen atom, and an epoxy resin (b) of m≒4, an epoxy equivalent of 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): ERL-4221 (trade name, manufactured by Polysciences Co., Ltd., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylic acid, epoxy equivalent 126 g/eq. )

(A'-3): EHPE-3150 (trade name, 1,2-epoxy-4-(2-epoxyethyl) of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Corporation Base) cyclohexane adduct, epoxy equivalent 180g/eq.)

(A'-4): XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene phenol condensation type epoxy resin, epoxy equivalent 253 g/eq.)

(B-1): Capa 3050 (trade name, manufactured by Perstorp Co., Ltd., trivalent polyol in which y is 1 to 2, R ₄ is a carbon number 6 trivalent aliphatic hydrocarbon group, molecular weight 540, OH equivalent in the formula (4) 310mgKOH/g)

(B-2): Placcel 308 (trade name, manufactured by Daicel Co., Ltd., a trifunctional polyol in which y is 2 to 3 in the formula (4), R ₄ is a trivalent aliphatic hydrocarbon group having a carbon number of 6, a molecular weight of 850, OH Equivalent to 195mgKOH/g)

(B-3): Placcel 312 (trade name, manufactured by Daicel Co., Ltd., tri-functional polyol in which y is 3 to 4 in the formula (4), R ₄ is a trivalent aliphatic hydrocarbon group having 6 carbon atoms, molecular weight 1250, OH Equivalent 135mgKOH/g)

(B-4): in the Placcel 205 (trade name, of Daicel Corporation, of Formula (3) x is 1 ~ _3, R 3 is a C 4-6 of divalent aliphatic hydrocarbon group of the difunctional polyol, molecular weight 530 , OH equivalent 210mgKOH / g)

(B-5): Placcel 220 (trade name, manufactured by Daicel Co., Ltd., di-functional polyol in which x is 8 to 9 in the formula (3), R ₃ is a divalent aliphatic hydrocarbon group having a carbon number of 5, molecular weight 2000, OH Equivalent 56mgKOH/g)

(B'-1): Polyethylene glycol 1000 (molecular weight 1000)

(C-1): SP-172 (trade name, manufactured by ADEKA, 50 wt% propylene carbonate solution, and the blending amount described in the table indicates the solid content value)

(C-2): CPI-6976 (trade name, manufactured by ACETO Co., Ltd., 50 wt% propylene carbonate solution, and the blending amount described in the table indicates the solid content value)

(C-3): Irgacure PAG290 (trade name, manufactured by BASF Corporation)

(D-1): 3-glycidoxypropyltrimethoxydecane

(D-2): 3-glycidoxypropylmethyldimethoxydecane

(Ei-1): Epotohto YDF-8170 (trade name, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol F type epoxy resin, epoxy equivalent 157 g/eq., molecular weight 320)

(Ei-2): Epotohto YD-8125 (trade name, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol A epoxy resin, epoxy equivalent 170 g/eq., molecular weight 340)

(Ei'-1): jER1003 (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type long-lock epoxy resin, epoxy equivalent 720 g/eq., molecular weight 1300)

As can be seen from the results of Table 1, the characteristics of the composition obtained by each example, the optimum exposure amount is small, and the high sensitivity, the resolution size of the photosensitive pattern is For high resolution, the internal stress is also low, no cracks appear in the pattern, and the adhesion after damp heat is also maintained.

Example 25 (Resistant laminate composed of the photosensitive resin composition of the present invention)

In the blending composition ratio of the first embodiment of Table 1, the ethylene glycol dimethyl ether was further blended, and the mixture was stirred at 60 ° C for 1 hour in a mixer with a stirrer to dissolve and dissolve, and the solution viscosity diluted to 25 ° C became 3 Pa. . s, after cooling, it was filtered through a membrane having a pore size of 1.0 μm to obtain a paint for dry film of the photosensitive resin composition of the present invention. This varnish was uniformly applied to a base film (made of polypropylene, manufactured by Mitsubishi Plastics Co., Ltd., film thickness: 38 μm), and dried by a warm air convection dryer at 65 ° C for 5 minutes and at 80 ° C for 15 minutes. A film (polypropylene, manufactured by Mitsubishi Plastics Co., Ltd., film thickness: 38 μm) was laminated on the surface to obtain a resist laminated body (photosensitive resin composition laminate) in which a dry film resist having a film thickness of 25 μm was interposed.

(Drawing of dry film resist)

The film was peeled off from the resist laminate of the photosensitive resin composition obtained above, and the film was laminated on a tantalum wafer at a roll temperature of 70 ° C, an air pressure of 0.2 MPa, and a speed of 0.5 m/min, and then the base film was peeled off to obtain 25 μm. Photosensitive resin composition layer (dry film resist). The photosensitive resin composition layer was subjected to contact exposure using an i-ray exposure apparatus (mask alignment machine: manufactured by Ushio Electric Co., Ltd.). Thereafter, the PEB was dried on a hot plate at 95 ° C for 5 minutes, and immersed and developed at 23 ° C for 3 minutes by SU-8 Developer (trade name, manufactured by Microchem Co., Ltd., propylene glycol monomethyl ether acetate as a main component). The propanol rinse is washed and dried to obtain a hardened resin pattern on the substrate. Even when a resist laminate is used, a cured product having an optimum exposure amount of 125 mJ/cm ² , no residue and cracks, and a vertical side wall having a fine line adhesion pattern width of 3 μm can be obtained.

[Industrial availability]

The photosensitive resin composition of the present invention can form a fine and vertical sidewall shape pattern by photolithography. The cured product has characteristics of low stress and excellent heat and humidity resistance. Available with semiconductor or MEMS. Micro-mechanical applications, in particular MEMS packages, semiconductor packages, micro-reactors, permanent resists and hardeners necessary for the formation of parts.

Claims (12)

A photosensitive resin composition comprising (A) an epoxy resin, (B) a polyol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing decane compound, and (E) a reaction The photosensitive resin composition of the epoxy monomer, characterized in that the (A) epoxy resin is contained by the following formula (1) An epoxy resin (a) obtained by reacting a 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 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group; and the X system is independently The hydrogen atom or the epoxy propyl group is present, and the epoxy resin (b) represented by at least one of the plurality of epoxy groups of X is present, and the (B) polyol compound contains the following formula ( 3) (In the formula, x is an average value and represents a real number in the range of 1 to 15; R ₃ represents a system inside the carbon chain may contain at least one divalent aliphatic hydrocarbon group of ether bond) is the polyester polyol and / Or the following formula (4) (wherein, y is an average value and represents a real number in the range of 1 to 6; and R ₄ is a polyester polyol represented by a trivalent aliphatic hydrocarbon group which may contain at least one ether bond in the carbon chain), and (E) A reactive epoxy monomer containing a bisphenol type epoxy resin. The photosensitive resin composition of claim 1, wherein (E) is reacted The epoxy single system comprises a bisphenol F type epoxy resin and/or a bisphenol A type epoxy resin. The photosensitive resin composition of claim 1, wherein the blending ratio of the (E) reactive epoxy monomer is 2 to 12 with respect to the total mass of the (A) epoxy resin and the (B) polyol compound. quality%. The photosensitive resin composition of claim 1, wherein the blending ratio of the (B) polyol compound is from 1 to 30% by mass based on the total mass of the (A) epoxy resin. The photosensitive resin composition of claim 1, wherein (C) the photocationic polymerization initiator blend ratio is relative to (A) epoxy resin, (B) polyol compound, and (E) reactive epoxy The total mass of the monomers is 0.1 to 15% by mass. The photosensitive resin composition of claim 1, wherein (D) an epoxy group-containing decane compound is an epoxy group-containing alkoxydecane compound. The photosensitive resin composition of claim 1, wherein (D) the blend ratio of the epoxy group-containing decane compound is relative to (A) epoxy resin, (B) polyol compound, (C) photocationic polymerization The total mass of the initiator and the (E) reactive epoxy monomer is from 1 to 15% by mass. The photosensitive resin composition of claim 1, which further contains (F) a solvent. The photosensitive resin composition of claim 8, wherein the blending ratio of the solvent (F) 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 9. A resist laminate obtained by sandwiching a photosensitive resin composition according to any one of claims 1 to 9 with two substrates. A cured product of a dry film resist obtained by the resist laminate of claim 11.