WO2014080976A1 - Photosensitive resin composition, resist laminate, and articles obtained by curing same (9) - 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 polyglycidyl ether of a divalent or trivalent aliphatic alcohol.

Description

Photosensitive resin composition, resist laminate and cured product thereof (9)

The present invention relates to a photosensitive resin composition capable of forming an image having excellent side wall shape and resolution, low internal stress after curing, and excellent substrate adhesion after a wet heat test, and a cured product thereof. The cured product of the photosensitive resin composition according to the present invention includes MEMS (microelectromechanical system) parts, μ-TAS (micrototal analysis system) parts, microreactor parts, insulating layers of electronic parts such as capacitors and inductors, LIGA parts. Useful in the manufacture of molds and stamps for micro-injection molding and hot embossing, screens or stencils for micro-printing applications, MEMS and semiconductor packaging parts, BioMEMS and biophotonic devices, and printed wiring boards.

Among the photosensitive resin compositions, those that can be processed by photolithography are called photoresists, and are widely used for semiconductors, MEMS / micromachine applications, and the like. In such an application, photolithography is achieved by patterning exposure on a substrate and then developing with a developer to selectively remove exposed or non-exposed areas. There are a positive type and a negative type of photoresist. A positive type is one in which an exposed portion is dissolved in a developer, and a negative type is insoluble. In advanced technology electro-package applications and MEMS applications, not only the ability to form a uniform spin coating film, but also a high aspect ratio, a vertical sidewall shape in a thick film, and a high adhesion to a substrate are required. Here, the aspect ratio is an important characteristic calculated by resist film thickness / pattern line width and showing the performance of photolithography.

According to the composition mainly composed of bisphenol A type novolac epoxy resin disclosed in Patent Document 1 and Non-Patent Document 1, photosensitive image formation and photosensitive resin having a very high resolution and a high aspect ratio. A cured product can be formed. However, the obtained cured resin tends to be too brittle depending on its use, and often causes cracking (crazing) during development or when internal stress occurs. Therefore, according to this cured resin, not only the adhesiveness is lowered depending on the type of the substrate using the resin composition, but in some cases, peeling may occur between the substrate and the cured resin. All these problems are caused by the stress that occurs when the composition shrinks and accumulates in the cured resin. When the curing shrinkage is large, the substrate is often bent (warped).

Furthermore, it was found that when the substrate on which the cured resin was formed was subjected to a wet heat test (80 ° C., 100%, 24 hours), which is one of accelerated durability tests, the cured resin was peeled from the substrate. Therefore, when this cured resin is used for applications such as a MEMS package, a semiconductor package, and a microreactor forming part, there is a disadvantage that the durability is inferior.

Patent Document 2 discloses a resin composition comprising an epoxy resin, a novolac resin, a cationic photopolymerization initiator, and a filler. It is described that by using this resin composition, the adhesion of a coating film is increased and moisture permeability is reduced. However, it has been found that, depending on the disclosed composition, there is no resolution performance as a photoresist, and a high adhesive strength cannot be realized without containing a filler. Therefore, the resin composition of Patent Document 2 cannot be adapted to a MEMS package, a semiconductor package, a microreactor, or the like.

U.S. Pat. No. 4,882,245 JP 2010-24364 A

The present invention has been made in view of the above circumstances, and is an epoxy resin composition that is cured by cationic polymerization in the field of semiconductor and MEMS / micromachine applications, and has a vertical side wall shape and fine resolution, It is an object of the present invention to provide a photosensitive resin composition capable of forming an image having low stress and heat and humidity resistance, and / or a laminate thereof, and a cured product thereof.

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.

Various aspects of the present invention are as follows.
[1].
A photosensitive resin composition containing (A) an epoxy resin, (B) a polyhydric phenol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing silane compound, and (E) a reactive epoxy monomer. And
The (A) epoxy resin is
Following formula (1)

An epoxy resin (a) obtained by the reaction of a phenol derivative represented by formula (II) with epihalohydrin, and the following formula (2)

(In the formula, m is an average value and represents a real number in the range of 2 to 30. R ₁ and R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. X represents a hydrogen atom or a glycidyl group, and at least one of a plurality of X is a glycidyl group.) And (B) a polyhydric phenol Compound is
The following formulas (3) to (6)

(In the formula, p is an average value and represents a real number in the range of 1 to 10. Each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In the formula, q is an average value and represents a real number in the range of 1 to 10.)

(In the formula, z is an average value and represents a real number in the range of 1 to 10.)

(Wherein y is an average value and represents a real number in the range of 1 to 10. R ₈ and R ₉ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Containing one or more selected from the group consisting of phenolic compounds, and
The (E) reactive epoxy monomer is
Following formula (10)

(In the formula, R ₅ represents a divalent aliphatic hydrocarbon group having 1 to 11 carbon atoms.)
And / or the following formula (11)

(In the formula, R ₆ represents a trivalent aliphatic hydrocarbon group having 1 to 11 carbon atoms.)
The photosensitive resin composition characterized by containing the epoxy compound represented by these.
[2].
(E) The photosensitive resin composition as described in the above item [1], wherein the reactive epoxy monomer contains trimethylolpropane triglycidyl ether.
[3].
(E) The photosensitive resin composition according to item [1], wherein the proportion of the reactive epoxy monomer is 2 to 12% by mass relative to the total mass of (A) the epoxy resin and (B) the polyhydric phenol compound. object.
[4].
(B) The photosensitive resin composition as described in the above item [1], wherein the blending ratio of the polyhydric phenol compound is 1 to 40% by mass relative to the mass of the (A) epoxy resin.
[5].
(C) The photosensitive composition according to item [1], wherein the proportion of the photocationic polymerization initiator is 0.1 to 15% by mass relative to the total mass of (A) the epoxy resin and (B) the polyhydric phenol compound. Resin composition.
[6].
(D) The photosensitive resin composition as described in the above item [1], wherein the epoxy group-containing silane compound is an epoxy group-containing alkoxysilane compound.
[7].
(D) The blending ratio of the epoxy group-containing silane compound is based on the total mass of (A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization initiator, and (E) reactive epoxy monomer. The photosensitive resin composition according to item [1], which is 1 to 15% by mass.
[8].
Furthermore, (G) The photosensitive resin composition as described in the said [1] item containing an acrylic resin.
[9].
(G) The photosensitive resin composition as described in the above item [8], wherein the acrylic resin is a copolymer obtained using an ethylenically unsaturated monomer having a glycidyl group.
[10].
The blending ratio of (G) acrylic resin is (A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization initiator, (D) epoxy group-containing silane compound, and (E) reactive epoxy monomer. The photosensitive resin composition as described in the above item [8], which is 1 to 20% by mass relative to the total mass.
[11].
Furthermore, (F) The photosensitive resin composition as described in the said [1] item containing a solvent.
[12].
(F) The photosensitive resin composition as described in the above item [11], wherein the blending ratio of the solvent is 5 to 95% by mass with respect to the total mass of the photosensitive resin composition containing (F) the solvent.
[13].
Hardened | cured material of the photosensitive resin composition as described in any one of said [1] thru | or [12] term.
[14].
A resist laminate obtained by sandwiching the photosensitive resin composition according to any one of [1] to [12] above between two substrates.
[15].
A cured product of a dry film resist obtained from the resist laminate according to the above item [14].

The photosensitive resin composition of the present invention is capable of forming a fine and vertical sidewall shape pattern by photolithography, and the cured product has characteristics that are excellent in high resolution, low stress, and moist heat resistance. Therefore, by using the photosensitive resin composition of the present invention, a permanent resist and a cured product having characteristics required for semiconductor and MEMS / micromachine application fields, in particular, MEMS packages, semiconductor packages, and microreactor forming parts can be obtained. can get.

The present invention will be described below.
The epoxy resin (A) contained in the photosensitive resin composition of the present invention is an epoxy resin (a) obtained by a reaction between a phenol derivative represented by the above formula (1) and an epihalohydrin, and the above formula (2). Both of the represented epoxy resins (b) are included. Among these, the epoxy resin (a) contributes to the vertical sidewall shape and 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 conventionally known epoxy resin synthesis method using a phenol derivative represented by the formula (1) and epihalohydrin.

As a general synthesis method of the epoxy resin (a), for example, an alkali such as sodium hydroxide is added to a mixed solution in which a phenol derivative represented by the formula (1) and an epihalohydrin can be dissolved. A method of raising the temperature to the reaction temperature, performing an addition reaction and a ring closure reaction, repeating washing of the reaction solution with water, separation and removal of the aqueous layer, and finally evaporating the solvent from the oil layer can be mentioned. The halogen of the epihalohydrin is selected from F, Cl, Br and I, but is typically Cl or Br. The reaction between the phenol derivative represented by the formula (1) and epihalohydrin is usually 0.3 to 30 mol, preferably 1 to 20 mol, more preferably epihalohydrin with respect to 1 mol of phenol derivative (corresponding to 3 mol of hydroxyl group). Is carried out using 3 to 15 moles. Since the epoxy resin (a) is obtained by the above reaction, it usually exists as a mixture of plural kinds of products.

It is known that an epoxy resin (a) having a different main component in the epoxy resin (a) can be obtained depending on the use ratio of the phenol derivative represented by the formula (1) used in the synthesis reaction and the epihalohydrin. For example, when an excessive amount of epihalohydrin is used with respect to the phenolic hydroxyl group of the phenol derivative, an epoxy resin mainly composed of a trifunctional epoxy resin in which all three phenolic hydroxyl groups in formula (1) are epoxidized (A) is obtained. Inclusion of a polyfunctional epoxy resin having a large molecular weight, in which the phenolic hydroxyl groups of several phenol derivatives are bonded via epihalohydrin and the remaining phenolic hydroxyl groups are epoxidized as the amount of epihalohydrin used for phenolic hydroxyl groups decreases. The rate increases.

As a method of obtaining the epoxy resin (a) mainly composed of such a multimeric epoxy resin, in addition to the method of controlling by the use ratio of the phenol derivative and the epihalohydrin, a phenol derivative is further added to the epoxy resin (a). The method of making this react is also mentioned. 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 the present invention.

The epoxy resin (a) contained in the resin composition of the present invention is an epoxy resin that is a monomer of a phenol derivative as long as it is an epoxy resin obtained by a reaction between a phenol derivative represented by the formula (1) and an epihalohydrin. Or the epoxy resin (a) which contains any of the multimeric epoxy resins of a phenol derivative as a main component can also be used. Since the epoxy resin (a) is excellent in solvent solubility and has a low softening point and is easy to handle, an epoxy resin of a phenol derivative monomer and an epoxy resin of a phenol derivative dimer (represented by the formula (1)) An epoxy resin having a structure in which two phenol derivatives are bonded via epihalohydrin) or a trimer epoxy resin of a phenol derivative (a structure in which three phenol derivatives represented by the formula (1) are bonded via epihalohydrin) The epoxy resin (a) containing as a main component any one of the epoxy resins having the above component is preferable. An epoxy resin (a) mainly composed of a phenol derivative monomer epoxy resin or a phenol derivative dimer epoxy resin is more preferred.

The “main component” as used in the present application means the most content among the plural types of epoxy resins that are monomeric epoxy resins and / or multimeric epoxy resins contained in the epoxy resin (a). It means many epoxy resin components.

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

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

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

As the epoxy resin (a), those having a weight average molecular weight in the range of 500 to 12,000 are preferable, and those having a weight average molecular weight in the range of 500 to 9000 are more preferable. Preferred examples thereof include NC-6300H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 220 to 240 g / eq., Softening point of 60 to 85 ° C.). The weight average molecular weight in this application is a value calculated in terms of polystyrene based on the GPC measurement results, the epoxy equivalent is a value measured in accordance with JIS K-7236, and the softening point is in accordance with JIS K-7234. Means the measured values.

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

In the photosensitive resin composition of the present invention, the epoxy resin (b) is usually 2 to 4900% by mass, preferably 5 to 100% by mass, more preferably 10 to 70% by mass with respect to the mass of the epoxy resin (a). Use. When the usage rate of the epoxy resin (b) with respect to the mass of the epoxy resin (a) is 4900% by mass or less, the photosensitive image pattern can be easily formed into a vertical sidewall shape, and the pattern is prevented from being rounded. It becomes possible to do. Moreover, it can prevent effectively that a crack arises in the photosensitive image pattern surface because the usage-amount of the epoxy resin (b) with respect to the mass of an epoxy resin (a) is 2 mass% or more.

The epoxy resin (A) contained in the photosensitive resin composition of the present invention may be used in combination with an epoxy resin other than the epoxy resin (a) and the epoxy resin (b). The epoxy resin that can be used in combination is not particularly limited, and the blending ratio is not particularly limited as long as the effect of the present invention is not impaired. However, the category of (A) epoxy resin does not include the epoxy group-containing silane compound of component (D) and does not include the epoxy compound defined as the reactive epoxy monomer of component (E).

(B) The polyhydric phenol compound contained in the photosensitive resin composition of the present invention contains one or more selected from the group consisting of phenol compounds represented by the above formulas (3) to (6). (B) The polyhydric phenol compound is useful for curing the epoxy resin with a high crosslinking density by heating. For this reason, the (B) polyhydric phenol compound can give the resin cured product the functions of low moisture permeability, high adhesion, and toughness.

Examples of the polyhydric phenol compound represented by the formula (3) include phenol novolac resins and cresol novolac resins. These novolac resins may be used alone or in combination of two or more. In particular, a phenol novolac resin is preferable because of excellent coating properties. As the phenol novolac resin, a phenol novolac resin having a softening point of 50 ° C. or higher and 150 ° C. or lower is preferable, and a phenol novolak resin having a softening point of 70 ° C. or higher and 100 ° C. or lower is particularly preferable. Specific examples of phenol novolac resins having a softening point of 50 ° C. or higher and 150 ° C. or lower include PN-152 (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 50 ° C., hydroxyl group equivalent 105 g / eq.), H-1 (commercial product) Name, manufactured by Meiwa Kasei Co., Ltd., softening point 80 ° C., hydroxyl equivalent weight 104 g / eq.), TD-2131 (trade name, manufactured by DIC, softening point 80 ° C., hydroxyl equivalent weight 105 g / eq.), KA-1160 (trade name) DIC Corporation, softening point 81 ° C., hydroxyl group equivalent 117 g / eq.). The hydroxyl group equivalent of the novolak resin is 80 to 130 g / eq. From the viewpoint of compatibility with the epoxy resin (A) and low moisture permeability. In the range of 100 to 120 g / eq. It is particularly preferable that the range is

Examples of the polyhydric phenol compound represented by the formula (4) include bisphenol A type novolac resins, and commercially available products are available. Specific examples of the bisphenol A type novolak resin include VH-4150 (trade name, manufactured by DIC, softening point 85 ° C., hydroxyl group equivalent 118 g / eq.), VH-4170 (trade name, manufactured by DIC, softening point 103 ° C. Hydroxyl group equivalent 118 g / eq.), MEP-6309E (trade name, manufactured by Meiwa Kasei Co., Ltd., softening point 81 ° C., hydroxyl group equivalent 116 g / eq.), And the like. These novolac resins may be used alone or in combination of two or more.

Examples of the polyhydric phenol compound represented by the formula (5) include biphenylphenol novolac resins, and commercially available products are available. Specific examples of the biphenylphenol novolak resin include KAYAHARD GPH-65 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point 65 ° C., hydroxyl group equivalent 200 g / eq.). These novolac resins may be used alone or in combination of two or more.

Examples of the polyhydric phenol compound represented by the formula (6) include phenol aralkyl resins, and commercially available products are available. Specific examples of the phenol aralkyl resin include Milex XLC-3L (trade name, manufactured by Mitsui Chemicals, softening point 77 ° C., hydroxyl group equivalent 176 g / eq.). These phenol aralkyl resins may be used alone or in combination of two or more.

The blending ratio of the (B) polyhydric phenol compound in the photosensitive resin composition of the present invention is usually 1 to 40% by mass, preferably 4 to 30% by mass, based on the total mass of the (A) epoxy resin. Preferably, it is 5 to 25% by mass. (B) When content of a polyhydric phenol compound is 40 mass% or less, the situation where development of a photosensitive image pattern becomes difficult is suppressed. (B) When content of a polyhydric phenol compound is 1 mass% or more, sufficient adhesiveness and moisture resistance are easily obtained.

In addition, the usage-amount of each polyhydric phenol compound in the case of using together the multiple of the polyhydric phenol compound represented by 1 or more types chosen from Formula (3) thru | or (6) is (A) with respect to the mass of an epoxy resin. B) The blending ratio of the polyhydric phenol compound is not particularly limited as long as it is within the above range.

In addition, the (B) polyhydric phenol compound contained in the photosensitive resin composition of the present invention is used in combination with a polyhydric phenol compound other than the polyhydric phenol compounds represented by the above formulas (3) to (6). May be. The polyhydric phenol compound that can be used in combination is not particularly limited. Further, the blending ratio of the polyhydric phenol compound that can be used in combination is not particularly limited as long as the effects of the present invention are not impaired.

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

(C) Examples of the photocationic polymerization initiator include aromatic iodonium complex salts and aromatic sulfonium complex salts. Of these, specific examples of the aromatic iodonium complex salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and triluku. Miliodonium tetrakis (pentafluorophenyl) borate (Rhodia, trade name Rhodosyl PI2074), di (4-tert-butyl) iodonium tris (trifluoromethanesulfonyl) methanide (BASF, trade name CGI BBI-C1), etc. Can be mentioned.

Specific examples of the aromatic sulfonium complex salt include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by Sun Apro, trade name CPI-101A), thiophenyldiphenylsulfonium tris (pentafluoroethyl) trifluoro Phosphate (trade name CPI-210S, manufactured by San Apro), 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (trade name SP-172, manufactured by ADEKA) A mixture of aromatic sulfonium hexafluoroantimonate containing 4-thiophenyldiphenylsulfonium hexafluoroantimonate (ACETO Corporate USA, trade name CPI-6976) and Phenylsulfonium tris (trifluoromethanesulfonyl) methanide (BASF, trade name CGI, TPS-C1), tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tris (trifluoromethylsulfonyl) methide (BASF, product) Name GSID 26-1), tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate (trade name Irgacure PAG290, manufactured by BASF) Can be mentioned.

Of these cationic photopolymerization initiators, aromatic sulfonium complex salts having high vertical rectangular workability and high thermal stability are preferred in the photosensitive image forming step. Aromatic sulfonium hexafluoroantimony containing 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate and 4-thiophenyldiphenylsulfonium hexafluoroantimonate Particularly preferred is a mixture of nates, tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate.

These (C) photocationic polymerization initiators may be used alone or in combination of two or more. (C) The cationic photopolymerization initiator component has an action of absorbing light. Therefore, in the case of a thick film (for example, 50 μm or more), the component (C) in an amount that is not excessively large (for example, an amount of 15% by mass or less) in order to sufficiently transmit the light during curing to the deep part. Is preferably used. On the other hand, in order to obtain a sufficient curing rate in the case of a thick film, it is preferable to use a certain amount (for example, 3% by mass or more) of the component (C). In the case of a thin film, the component (C) exhibits sufficient polymerization initiation performance when added in a small amount (for example, 1% by mass or more). In the case of a thin film, even if a large amount of the component (C) is used, the light transmittance to the deep part is not greatly reduced, but it is economical (preventing unnecessary use of an expensive initiator). Therefore, it is preferable to use an amount of the component (C) which is not excessively large. Although it does not necessarily limit from these points, the compounding ratio of (C) photocationic polymerization initiator in the photosensitive resin composition of this invention is (A) an epoxy resin and (B) a polyhydric phenol compound. It is usually 0.1 to 15% by mass, preferably 0.2 to 8% by mass, based on the total mass. However, when the molar absorption coefficient of the cationic photopolymerization initiator (C) at a wavelength of 300 to 380 nm is high, it is necessary to adjust the blending amount to an appropriate amount according to the film thickness when using the photosensitive resin composition.

The (D) epoxy group-containing silane compound contained in the photosensitive resin composition of the present invention is improved in adhesion to the substrate and multilayered by the composition of the present invention in the step of using the composition of the present invention. It provides improved interlayer adhesion when the structure is formed. And (D) epoxy group containing silane compound does not inhibit the storage stability of the photosensitive resin composition of this invention.

(D) A preferred specific example of the epoxy group-containing silane compound is an epoxy group-containing alkoxysilane compound. Epoxy group-containing alkoxysilane compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Examples include trimethoxysilane. These can be used alone or in combination of two or more.

The blending ratio of the (D) epoxy group-containing silane compound in the photosensitive resin composition of the present invention is as follows: (A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization initiator, and (E) reaction. The amount is usually 1 to 15% by mass, preferably 3 to 10% by mass, based on the total mass of the epoxy monomer.

The (E) reactive epoxy monomer contained in the photosensitive resin composition of the present invention contributes to improving the flexibility and flexibility of the uncured film and the cured film by the photosensitive resin composition of the present invention, and Contributes to improved adhesion of cured film. (E) A reactive epoxy monomer contains the epoxy compound represented by the said Formula (10) and / or the said Formula (11).

In formula (10), the divalent aliphatic hydrocarbon group represented by R ₅ means the remaining atomic group (residue) obtained by removing two hydrogen atoms from a linear or branched hydrocarbon. The number of carbon atoms is 1 to 11, preferably 1 to 8. Examples of the divalent aliphatic hydrocarbon group represented by R ₅ include linear aliphatic hydrocarbon groups such as a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group, and the above linear aliphatic hydrocarbon groups. In addition, a branched aliphatic hydrocarbon group having an alkyl group as a side chain may be mentioned.

The epoxy compound represented by the formula (10) is generally a diglycidyl ether of a divalent aliphatic alcohol. Specific examples thereof include neopentyl glycol diglycidyl ether, propylene glycol diglycidyl ether, butylethylpropane diglycidyl ether, methylpropane diglycidyl ether, trimethylpentane diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol. Examples include diglycidyl ether and 1,6-hexanediol diglycidyl ether. Among these, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether are preferable.

In formula (11), the trivalent aliphatic hydrocarbon residue represented by R ₆ means the remaining atomic group (residue) obtained by removing three hydrogen atoms from a linear or branched hydrocarbon, The number of carbon atoms is 1 to 11, preferably 1 to 8. The trivalent aliphatic hydrocarbon residue represented by R ₆ includes those having an alkyl group bonded as a side chain.

The epoxy compound represented by the formula (11) is generally a triglycidyl ether of a trivalent aliphatic alcohol. Specific examples thereof include trimethylolpropane triglycidyl ether and glycerin triglycidyl ether. Among these, trimethylolpropane triglycidyl ether is preferable.

Regarding the formulas (10) and (11), the aliphatic hydrocarbon group represented by R ₅ and R ₆ has 11 or less carbon atoms, so that compatibility with other components and, consequently, the coating quality of the resin composition is adequate. Since it is maintained and good developability is obtained, it is convenient for forming a high-definition photosensitive image.

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, preferably with respect to the total mass of (A) the epoxy resin and (B) the polyhydric phenol compound. 3 to 10% by mass.

The reactive epoxy monomer (E) contained in the photosensitive resin composition of the present invention is used in combination with a reactive epoxy monomer other than the epoxy compound represented by the formula (10) and / or the formula (11). Also good. The reactive epoxy monomer that can be used in combination is not particularly limited, and the proportion of the reactive epoxy monomer that can be used in combination is not particularly limited as long as the effects of the present invention are not impaired.

The photosensitive resin composition of the present invention may further contain (G) an acrylic resin. The (G) acrylic resin here includes a resin formed from a compound having an acrylic group and / or a compound having a methacrylic group. (G) The acrylic resin is not particularly limited, but is preferably a copolymer obtained using an ethylenically unsaturated monomer having a glycidyl group, and among them, a glycidyl methacrylate copolymer is particularly preferable. preferable. The glycidyl methacrylate copolymer is a polymer obtained by copolymerizing glycidyl methacrylate and another ethylenically unsaturated monomer, and has an epoxy group in a branched form with respect to the polymer main chain. Therefore, the glycidyl methacrylate copolymer has high compatibility with the epoxy resin, and phase separation hardly occurs, so that it can be easily mixed with the epoxy resin. Furthermore, since the glycidyl methacrylate copolymer is a soft component, flexibility can be imparted to the cured film and adhesion can be improved. Also, for the purpose of forming a good fine pattern, (G) acrylic resin, (A) epoxy resin, (B) polyhydric phenol compound and (E) reactive epoxy monomer, etc., and curing characteristics A glycidyl methacrylate copolymer which is excellent in water resistance is preferred.

The epoxy equivalent of the glycidyl methacrylate copolymer is preferably 1000 or less. The epoxy group in the molecular chain of the glycidyl methacrylate copolymer reacts with the epoxy resin at the time of curing to form a network structure. As a result, thermal expansion under high temperature and high humidity conditions can be suppressed, and long-term Contributes to improved adhesion reliability. When the epoxy equivalent of the glycidyl methacrylate copolymer is 1000 or less, a sufficient number of reaction points with the epoxy resin are ensured, a network structure is effectively formed, and deterioration of the heat and moisture resistance is prevented.

Other ethylenically unsaturated monomers constituting the glycidyl methacrylate copolymer include acrylic acid derivatives such as acrylic acid, methyl acrylate and acrylic acid esters, fumaric acid derivatives such as dimethyl fumarate and diethyl fumarate, and Examples thereof include styrene derivatives such as styrene and α-methylstyrene. It is preferable to use an acrylic acid derivative as another ethylenically unsaturated monomer because the compatibility between the glycidyl methacrylate copolymer, the (A) epoxy resin, and the (E) reactive epoxy monomer can be increased. These other ethylenically unsaturated monomers can be used alone or in admixture of two or more. The molecular weight of the glycidyl methacrylate copolymer is not particularly limited, but considering the compatibility with the epoxy resin, the weight average molecular weight is preferably 250,000 or less, more preferably 100,000 or less, and still more preferably 30,000 or less. It is.

Specific examples of commercially available copolymers having a glycidyl group include Marproof G-0150M (trade name, manufactured by NOF Corporation, a copolymer of glycidyl methacrylate and methyl methacrylate, epoxy equivalent of 310 g / eq. , Weight average molecular weight of about 10,000), Marproof G-0250S (trade name, manufactured by NOF Corporation, copolymer of glycidyl methacrylate, styrene and methyl methacrylate, epoxy equivalent of 310 g / eq., Weight average molecular weight of about 20,000), Marproof G-2050M (trade name, manufactured by NOF Corporation, copolymer of glycidyl methacrylate and methyl methacrylate, epoxy equivalent 340 g / eq., Weight average molecular weight about 200,000), and the like. .

(G) The acrylic resin can be used alone or in admixture of two or more with the photosensitive resin composition of the present invention. The blending ratio of (G) acrylic resin in the photosensitive resin composition of the present invention is as follows: (A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization initiator, (D) epoxy group-containing silane compound And (E) 1 to 20% by mass, preferably 3 to 15% by mass, based on the total mass of the reactive epoxy monomer.

(F) A solvent can be used for the photosensitive resin composition of this invention, in order to reduce the viscosity of a resin composition and to improve applicability | paintability. The solvent is an organic solvent that is usually used for ink, paint, etc., and can dissolve each constituent component of the photosensitive resin composition and does not cause a chemical reaction with the constituent component. Can be used without limitation. (F) Specific examples of the solvent include ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, and cyclopentanone, aromatic hydrocarbons such as toluene, xylene, and methoxybenzene, dipropylene glycol dimethyl ether, and dipropylene glycol. Glycol ethers such as diethyl ether and propylene glycol monomethyl ether, esters such as ethyl lactate, ethyl acetate, butyl acetate, methyl-3-methoxypropionate, carbitol acetate, propylene glycol monomethyl ether acetate and γ-butyrolactone, methanol And alcohols such as ethanol, aliphatic hydrocarbons such as octane and decane, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

These solvents can be used alone or in admixture of two or more. (F) A solvent is added for the purpose of adjusting the film thickness and application property when applied to a substrate. The amount of the (F) solvent used to properly 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 in the photosensitive resin composition containing the solvent. It may be 95% by mass or less. The amount used is preferably 5 to 95% by mass, more preferably 10 to 90% by mass.

In the photosensitive resin composition of the present invention, a sensitizer is further used to absorb ultraviolet light and donate the absorbed light energy to the photocationic polymerization initiator, in particular, an aromatic iodonium complex salt. Also good. As the sensitizer, for example, thioxanthones and anthracene compounds having an alkoxy group at the 9th and 10th positions (9,10-dialkoxyanthracene derivatives) are preferable. Examples of the alkoxy group include C1-C4 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The 9,10-dialkoxyanthracene derivative may further have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, C1-C4 alkyl group, sulfonic acid alkyl ester group, carboxylic acid alkyl ester group and the like. Examples of the alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester group include C1-C4 alkyl. The substitution position of these substituents is preferably the 2-position.

Specific examples of thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, and the like. 2,4-diethylthioxanthone (trade name Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) and 2-isopropylthioxanthone are preferable.

Examples of the 9,10-dialkoxyanthracene derivative include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dimethoxy-2. -Ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-dimethoxyanthracene-2-sulfonic acid methyl ester 9,10-diethoxyanthracene-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene-2-carboxylic acid methyl ester, and the like.

These sensitizers can be used singly or in combination of two or more, but the use of 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene is most preferable. Since the sensitizer exhibits an effect in a small amount, its use ratio 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, an ion catcher may be added as necessary in order to reduce the adverse effect caused by the ions derived from the (C) photocationic polymerization initiator. Specific examples of the ion catcher include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, isopropoxydiethoxyaluminum, trisbutoxyaluminum and other alkoxyaluminum, trisphenoxyaluminum and trisparamethylphenoxyaluminum Acetoxyaluminum, trisstearatoaluminum, trisbutyratoaluminum, trispropionatoaluminum, trisacetylacetonatoaluminum, tristrifluoroacetylacetonatoaluminum, trisethylacetoacetoaluminum, diacetylacetonatodipivaloylmethanatoaluminum and di Isopropoxy (ethylacetoacetato) al Organoaluminum compounds such as benzalkonium, and the like. These components can be used alone or in combination of two or more. Moreover, the compounding quantity is the sum total of (A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization initiator, (D) epoxy group containing silane compound, and (E) reactive epoxy monomer. It may be 10% by mass or less based on the 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 necessary. Examples of the thermoplastic resin include polyethersulfone, polystyrene, and polycarbonate. Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, anthraquinone red, quinacridone red, diketopyrrolopyrrole red, and the like. As for the usage-amount of these additives, in the photosensitive resin composition of this invention except a solvent, for example, 0 mass% or more and 30 mass% or less are respectively a temporary standard. However, the amount of these used can be appropriately increased or decreased depending on the purpose of use and the required function of the cured film.

Examples of the thickener include olben, benton and montmorillonite. Examples of the antifoaming agent include silicone-based, fluoroalkyl-based, and polymer-based antifoaming agents. As for the usage-amount of these additives, in the photosensitive resin composition of this invention except a solvent, for example, 0 mass% or more and 10 mass% or less are respectively a temporary standard. However, the amount used can be appropriately increased or decreased depending on the purpose of use and coating quality.

Further, the photosensitive resin composition of the present invention includes, for example, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, montmorillonite, mica powder, etc. Any inorganic filler can be used. The usage-amount of an inorganic filler may be 0 mass% or more and 60 mass% or less with respect to the mass of the photosensitive resin composition of this invention except a solvent normally. However, the amount used can be appropriately increased or decreased depending on the purpose of use and the required function of the cured film. Similarly, organic fillers such as polymethyl methacrylate, rubber, fluoropolymer, and polyurethane powder can be incorporated into the photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention comprises (A) an epoxy resin, (B) a polyhydric phenol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing silane compound, and (E) a reactive epoxy monomer. (G) Acrylic resin, (F) Solvent, Sensitizer, Ion catcher, Thermoplastic resin, Colorant, Thickener, Antifoaming agent, Leveling agent and Inorganic filler which are essential components and optional components as necessary Etc. can be prepared by mixing and stirring by a usual method. When mixing and stirring, if necessary, a disperser such as a dissolver, a homogenizer, or a three roll mill may be used. Moreover, after mixing, you may filter using a mesh, a membrane filter, etc. further.

A method for forming a cured resist film from the photosensitive resin composition of the present invention will be described below.
The photosensitive resin composition of the present invention may be preferably used in a liquid form to which a solvent is added for application to a substrate. A process of dispensing a photosensitive resin composition of the present invention diluted to a desired viscosity with a solvent onto a substrate, accelerating the substrate to a constant rotational speed, and maintaining the rotational speed constant to obtain a desired film thickness Application can be performed by a spin coating method comprising: Spin coating can be performed at various rotational speeds to control film thickness. Alternatively, the photosensitive resin composition is applied to the substrate using other coating methods such as roller coating, doctor knife coating, slot coating, dip coating, gravure coating, spray coating, etc. it can.

After coating, dry baking (pre-baking) can be performed to evaporate the solvent. Dry bake conditions can be selected to form a semi-cured dry coating of the photoresist. Typical conditions include the use of a hot plate with a smooth surface, with the coating in contact with or close to the surface, coating thickness, solvent volatility, and substrate thermal conductivity. Depending on the thickness of the substrate, drying can be performed at 65 ° C. for 1 to 15 minutes, followed by 90 to 125 ° C. for 5 to 120 minutes. Alternatively, the dry bake can be performed in a convection oven. Next, exposure to a dry photosensitive resin composition coating film through a photomask on which a desired mask pattern is drawn, with a bright line having a near ultraviolet wavelength of 300 to 500 nm from an intermediate or ultrahigh pressure mercury lamp, a synchrotron radiation source A photosensitive image can be formed by irradiating an energy beam with X-ray radiation from the laser beam or irradiating an electron beam radiation directly or through patterned exposure. Contact, proximity, or projection prints can be used. Subsequent to exposure, post-exposure baking may be performed to accelerate the polymerization reaction by acid catalysis of the exposed areas of the coating. Typical conditions are 65 ° C. for 1-5 minutes, then 95 ° C. for 1-60 minutes, depending on the thickness of the coating on the hot plate as well as the thermal conductivity and thickness of the substrate.

Then, in order to dissolve and remove the unexposed portion, it can be immersed in an organic solvent developer typically for 2 to 30 minutes depending on the thickness of the coating film and the solvent titer of the developer solvent. Further, the developed image can be rinsed by applying a rinsing solvent to remove the developer attached to the cured film. The attached developer contains a dissolved photoresist component, and when dried, it becomes a residue on the photosensitive image and easily causes contamination. Therefore, it is desirable to remove the attached developer. In the case of the dipping method, it is possible to prevent adhesion of residues by preparing a clean developer tank and performing development in multiple stages.

Alternatively, the developer solvent can be applied by spraying using either an explosion-proof atomizing spray nozzle or an explosion-proof micro shower head spray nozzle. Furthermore, as another developing method, a method of applying a developer using a paddle method can be mentioned. In general, in the paddle method, a substrate to be developed is placed on a rotating tool head, and then a sufficient amount of developer solution to form a stagnant layer or paddle on the entire substrate area is rotated at a low speed. Distribute the sample to the top, stop the rotation of the substrate, let the formed developer paddle stand on the substrate for a certain period of time, then accelerate the rotation of the substrate to remove the used developer by spin removal. Including slowing down until it stops. It is usual to use a method of repeating the sequence several times as necessary until a clear photosensitive image is obtained.

Suitable developers include, but are not limited to, propylene glycol monomethyl ether acetate, γ-butyrolactone, acetone, cyclopentanone, diacetone alcohol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, anisole, and ethyl lactate. Not. Particularly preferred is propylene glycol monomethyl ether acetate which dissolves unexposed portions well and is relatively low in cost.

Suitable rinses include any of the above developer solvents, and methanol, ethanol, isopropanol and n-butyl acetate. Of these, acetone, ethanol and isopropanol are particularly preferred because they can be washed quickly and can be dried quickly.

After the rinsing step, as a final step of manufacturing the cured film, heat treatment (hard baking) can be performed at a temperature of 130 to 200 ° C. according to the heat resistance of the substrate. By thermally curing the film, a permanent cured film (resist) that satisfies various characteristics can be obtained.

Substrate materials that can be used are silicon, silicon dioxide, tantalum, lithium tantalate, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper -Including but not limited to silicon alloys, indium-tin oxide coated glass, organic films such as polyimide and polyester, any substrate containing patterned regions of metal, semiconductor, and insulating material.

The photosensitive resin composition of the present invention can also be used as a resist laminate by being sandwiched between two substrates. For example, after coating a photosensitive resin composition diluted with a solvent on a base film (base material) using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., set to 45 to 100 ° C. The resist laminate can be obtained by removing the solvent with a drying oven and laminating a cover film (base material) and the like. At this time, the thickness of the resist on the base film may be adjusted to 2 to 100 μm. As a base film and a cover film which are base materials, films, such as polyester, a polypropylene, polyethylene, TAC, a polyimide, may be used, for example. As these films, a film that has been subjected to a release treatment with a silicone-type release treatment agent, a non-silicone-type release treatment agent, or the like may be used as necessary. In order to use such a resist laminate, for example, the cover 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, a laminator, etc., and the liquid photosensitive resin is used. Similar to the composition, exposure, post-exposure baking, development, and heat treatment may be performed.

If the photosensitive resin composition is used in the form of a dry film resist according to the resist laminate of the present invention, the steps of coating on a support or a substrate and drying can be omitted. This makes it possible to more easily form a fine pattern using the photosensitive resin composition of the present invention.

When the cured film is used for a MEMS package, a semiconductor package, and / or a microreactor-forming component, the photosensitive resin composition of the present invention is applied to a substrate and dried to form a first layer photosensitive resin coating film. Forming, exposing the first layer, post-exposure baking, applying a photosensitive resin composition and drying to form a second photosensitive resin coating, and then exposing the second layer. And post-exposure baking. It is possible to form a complicated multilayer structure pattern by repeating this process and finally performing development and hard baking at the end. Alternatively, the first layer is developed, hard baked, the second layer is applied and dried, alignment exposure is performed through a photomask, and development and hard baking are repeated to form a multilayer structure pattern. Good. Each photosensitive resin layer may be formed by laminating a dry film resist.

Note that the “package” is a sealing method or a sealed one used to block the ingress of gas or liquid in the outside air in order to maintain the stability of the substrate, wiring, elements, and the like. The package described in this specification is a hollow package for packaging a vibrator such as a MEMS or a SAW device, or a semiconductor substrate, a printed wiring board, a wiring, or the like. This refers to surface protection to be performed or resin sealing for sealing the microreactor forming component with a top plate. “Wafer level package” means that a protective film is formed in the wafer state, terminals and wiring are processed up to the package, and then cut into chips and separated into individual pieces, and fine micro or nano channels and orifice plates are formed on the wafer. This represents a method of three-dimensional processing in a batch.

By using the photosensitive resin composition of the present invention, it is possible to form a fine and vertical sidewall shape pattern by photolithography. The cured product has characteristics that are excellent in low stress and moisture and heat resistance. According to the present invention, permanent resists and cured products that satisfy the characteristics required for semiconductor and MEMS / micromachine application fields, in particular, MEMS packages, semiconductor packages, and microreactor forming parts can be obtained. It is.

Hereinafter, the present invention will be described in detail with reference to examples. These examples are merely examples for describing the present invention, and do not limit the present invention.

Examples 9 to 16 and Comparative Examples 6 to 10
(Preparation of photosensitive resin composition solution (liquid resist))
(A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization start according to the blending amounts shown in Table 2 (units are parts by mass (in terms of solution products, solid content conversion of the component)) The agent, (D) epoxy group-containing silane compound, (E) reactive epoxy monomer and (G) acrylic resin are diluted with cyclopentanone to a concentration of 65% by mass, and the mixture is stirred at 60 ° C. in a flask equipped with a stirrer. The mixture was dissolved by stirring for a period of time, allowed to cool, and then filtered through a membrane filter having a pore size of 1.0 μm to obtain a photosensitive resin composition solution (liquid resist) for comparison with the present invention.

(Patterning of photosensitive resin composition)
Each liquid resist obtained in Examples 9 to 16 and Comparative Examples 6 to 10 was coated on a silicon wafer with a spin coater and then pre-baked on a hot plate at 95 ° C. for 10 minutes, and the dried film after coating. A photosensitive resin composition layer having a thickness of 25 μm was obtained. Thereafter, the film swell portion on the wafer end surface is dissolved and removed, dried, and then exposed to 500 mJ / cm ² through a photomask with a gray scale for resolution evaluation using an i-line exposure apparatus (mask aligner: manufactured by USHIO INC.). (Soft contact, i-line) was irradiated. Subsequently, post-exposure baking (hereinafter referred to as “PEB”) for 5 minutes was performed on a hot plate at 95 ° C. Next, a resin pattern cured on a silicon wafer by immersion development at 23 ° C. for 3 minutes with SU-8 Developer (trade name, manufactured by Microchem Corp., main component of propylene glycol monomethyl ether acetate), rinsing with isopropanol and drying. Got.

(Sensitivity, resolution, crack evaluation of photosensitive resin composition)
Sensitivity In the above patterning, the exposure amount with the best mask transfer accuracy was set as the optimal exposure amount, and the sensitivity of each photosensitive resin composition was evaluated. The smaller the optimum exposure value, the higher the sensitivity. The results are shown in Table 2 below.

・ Resolution For each liquid resist, after the above-mentioned pre-bake, dissolution and removal of the swelled film on the edge of the wafer, and drying, use a photomask with 1-100μm line and space and a true circular hole pattern. Each composition was irradiated with an optimum exposure amount (soft contact, i-line, exposure amount in Table 2), and subjected to PEB for 5 minutes on a 95 ° C. hot plate. It was developed by immersion for 3 minutes at 23 ° C. with SU-8 Developer (trade name, manufactured by Microchem Corp., main component of propylene glycol monomethyl ether acetate), rinsed with isopropanol, and dried. The resolution was evaluated by measuring the finest pattern width in close contact with the substrate in the resist pattern resolved to a vertical sidewall shape without residue and bending. The results are shown in Table 2 below.

-Crack evaluation Moreover, it evaluated about the crack generation | occurrence | production of the resin pattern obtained through various processes, such as said prebaking, melt | dissolution removal of the coating film rising part of a wafer end surface, drying, and exposure from each liquid resist. “XX” indicates that the entire surface of the film has crazing (same meaning as a crack, and a discontinuous break occurs to the bottom of the film). The state in which a fractured state generated on the pole surface portion is generated is indicated by “X”, and the state in which no crack is generated is indicated by “◯”. The results are shown in Table 2 below.

(Evaluation of wet heat adhesion of cured product of photosensitive resin composition)
Each liquid resist obtained in Examples 9 to 16 and Comparative Examples 6 to 10 was coated on a silicon wafer with a spin coater and then pre-baked on a hot plate at 95 ° C. for 10 minutes, and the dried film after coating. A photosensitive resin composition layer having a thickness of 25 μm was obtained. Thereafter, the film swell portion on the wafer end surface is dissolved and removed, dried, and then optimally exposed to each composition through a pattern photomask for wet heat adhesion evaluation using an i-line exposure apparatus (mask aligner: manufactured by USHIO INC.). The amount (soft contact, i-line, exposure amount in Table 2) was irradiated, and PEB was performed for 5 minutes on a 95 ° C. hot plate. Immerse and develop at 23 ° C for 3 minutes with SU-8 Developer (trade name, manufactured by Microchem Corp., main component of propylene glycol monomethyl ether acetate), rinse with isopropanol, dry, and hard-bake in an oven at 200 ° C for 60 minutes. A resin pattern cured on the silicon wafer was obtained. The wafer with the resin pattern was cut, and in a PTFE inner cylindrical sealed container, an aqueous solution containing a water-soluble organic solvent-A (composition: 2-imidazolidinone 10 mass%, 2,2′-sulfonyldiethanol 7.5 mass) %, Glyceritol 5% by mass, pentylene glycol 5% by mass, ethylene oxide-modified acetylenol 0.4% by mass), -B (composition: gamma-butyrolactam 30% by mass, 2,2′-oxydiethanol 10% by mass, Hexamethylene glycol 5% by mass, ethylene oxide-modified acetylenol 0.2% by mass), -C (composition: glyceritol 15% by mass, polyethylene glycol # 400 5% by mass, polyoxyethylene lauryl ether 3% by mass) Each piece was individually immersed and subjected to a wet heat test at 80 ° C. for 24 hours. The adhesive strength of the resin pattern before and after the test was measured with a shear strength tester. When there was no adhesive strength degradation, “○”, when there was adhesive strength degradation, “X”, The case where peeling occurred was defined as “XX”. The results are shown in Table 2 below.

In Table 2, (A-1) to (G-2) are 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., epoxy resin (b) in which R ₁ and R ₂ in formula (2) are hydrogen atoms and m≈6, epoxy equivalent 330 g / Eq.)
(A-3): NER-7403 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy resin (b) in which R ₁ and R ₂ in formula (2) are hydrogen atoms and m≈4, epoxy equivalent 250 g / Eq.)
(A′-1): EPON SU-8 (trade name, manufactured by Momentive, bisphenol A novolac type epoxy resin, epoxy equivalent of 213 g / eq.)
(A′-2): EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent of 197 g / eq.)
(A′-3): Celoxide 2021P (trade name, manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (alicyclic epoxy compound), epoxy equivalent 126 g / eq.)
(A′-4): jER YL-983U (trade name, manufactured by Mitsubishi Chemical Corporation, an epoxy resin (bisphenol F type) in which R ₁ and R ₂ in formula (2) are hydrogen atoms and X is all hydrogen atoms Epoxy resin), epoxy equivalent 170 g / eq.)
(B-1): PN-152 (trade name, manufactured by Meiwa Kasei Co., Ltd., R in formula (3) is a hydrogen atom and p≈4, softening point 50 ° C., hydroxyl group equivalent 105 g / eq.)
(B-2): H-1 (trade name, manufactured by Meiwa Kasei Co., Ltd., R in formula (3) is a hydrogen atom and p≈5, softening point 80 ° C., hydroxyl group equivalent 104 g / eq.)
(B-3): Millex XLC (trade name, manufactured by Mitsui Chemicals, polyhydric phenol compound in which R ₈ and R ₉ in Formula (6) are hydrogen atoms and y≈3.2, softening point 77 ° C. , Hydroxyl equivalent 176 g / eq.)
(B-4): KAYAHARD GPH-65 (trade name, manufactured by Nippon Kayaku Co., Ltd., polyhydric phenol compound with Z≈1.5 in formula (5), softening point 65 ° C., hydroxyl group equivalent 200 g / eq.)
(B-5): MEP-6309E (trade name, manufactured by Meiwa Kasei Co., Ltd., polyhydric phenol compound q≈5 in formula (4), softening point 81 ° C., hydroxyl group equivalent 116 g / eq.)
(C-1): SP-172 (trade name, manufactured by ADEKA, 50 wt% propylene carbonate solution, but the compounding amounts in the table represent solid content values)
(C-2): CPI-6976 (trade name, manufactured by ACETO, 50 wt% propylene carbonate solution, but the compounding amount shown in the table is a solid content value)
(C-3): Irgacure PAG290 (trade name, manufactured by BASF)
(D-1): 3-glycidoxypropyltrimethoxysilane (D-2): 3-glycidoxypropylmethyldimethoxysilane (Eii-1): Denacol EX-321L (trade name, manufactured by Nagase ChemteX Corporation, Trimethylolpropane triglycidyl ether, epoxy equivalent 160 g / eq., Epoxy compound in which R ₆ in formula (11) has ₆ carbon atoms)
(Eii-2): SR-NPG (trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., neopentyl glycol diglycidyl ether, epoxy equivalent 146 g / eq., Epoxy compound in which R ₅ in formula (10) has ₅ carbon atoms)
(Eii'-1): Octadecanediol diglycidyl ether (epoxy equivalent 199 g / eq., Epoxy compound in which R ₅ in formula (10) has 18 carbon atoms)
(G-1): Marproof G-0150M (trade name, manufactured by NOF Corporation, copolymer of glycidyl methacrylate and methyl methacrylate, epoxy equivalent of 310 g / eq., Weight average molecular weight of about 10,000)
(G-2): Marproof G-0250S (trade name, manufactured by NOF Corporation, copolymer of glycidyl methacrylate, styrene and methyl methacrylate, epoxy equivalent of 310 g / eq., Weight average molecular weight of about 20,000)

As shown in Table 2, the characteristics of the compositions obtained from the examples are such that the resolution dimension of the photosensitive pattern is higher than that of the comparative example, and cracks are generated in the developed film. Further, it was found that no cracks were generated in the hole pattern and the adhesion after wet heat was maintained.

Examples 35 to 36 (resist laminate comprising the photosensitive resin composition of the present invention)
In addition, ethylene glycol dimethyl ether was further added to the blending composition ratios of Example 9 and Example 15 in Table 2, and mixed and dissolved by stirring at 60 ° C. for 1 hour in a flask with a stirrer. The solution viscosity at 25 ° C. was 3 Pa. Diluted to s, allowed to cool, and then subjected to membrane filtration with a pore size of 1.0 μm to obtain a lacquer for the photosensitive resin composition dry film of the present invention. These lacquers are uniformly applied on a base film (made of polypropylene, Mitsubishi Plastics, 38 μm thick), dried with a hot air convection dryer at 65 ° C. for 5 minutes and at 80 ° C. for 15 minutes, and then exposed surface. A cover film (made of polypropylene, manufactured by Mitsubishi Plastics Co., Ltd., film thickness: 38 μm) was laminated thereon to obtain resist laminates (photosensitive resin composition laminates) sandwiching a dry film resist with a film thickness of 25 μm.

(Pattern of dry film resist)
After peeling the cover film from the resist laminate of each photosensitive resin composition obtained above and laminating it on a silicon wafer at a roll temperature of 70 ° C., an air pressure of 0.2 MPa, and a speed of 0.5 m / min, The film was peeled off to obtain a photosensitive resin composition layer (dry film resist) of 25 μm. This photosensitive resin composition layer was subjected to contact exposure using an i-line exposure apparatus (mask aligner: manufactured by Ushio Inc.). After that, PEB was performed for 5 minutes on a hot plate at 95 ° C, developed by immersion with SU-8 Developer (trade name, manufactured by Microchem, propylene glycol monomethyl ether acetate) at 23 ° C for 3 minutes, and rinsed with isopropanol. Each of the resin patterns was dried and cured on the substrate.

In the case of using the resist laminate comprising the photosensitive resin composition of Examples 9 and 15, cured products having vertical sidewalls with no residue and cracks and a fine wire adhesion pattern width of 5 μm were obtained.

The photosensitive resin composition of the present invention can form a fine and vertical sidewall shape pattern by a photolithography technique. The cured product has characteristics that are excellent in low stress and moisture and heat resistance. Permanent resists and cured products having characteristics required for semiconductor and MEMS / micromachine application fields, in particular, MEMS packages, semiconductor packages, and microreactor forming parts can be obtained.

Claims (15)

1. A photosensitive resin composition containing (A) an epoxy resin, (B) a polyhydric phenol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing silane compound, and (E) a reactive epoxy monomer. And
   The (A) epoxy resin is
   Following formula (1)
   

   

   
   An epoxy resin (a) obtained by the reaction of a phenol derivative represented by formula (II) with epihalohydrin, and the following formula (2)
   

   

   
   (In the formula, m is an average value and represents a real number in the range of 2 to 30. R ₁ and R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. X represents a hydrogen atom or a glycidyl group, and at least one of a plurality of X is a glycidyl group.) And (B) a polyhydric phenol Compound is
   The following formulas (3) to (6)
   

   

   
   (In the formula, p is an average value and represents a real number in the range of 1 to 10. Each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
   

   

   
   (In the formula, q is an average value and represents a real number in the range of 1 to 10.)
   

   

   
   (In the formula, z is an average value and represents a real number in the range of 1 to 10.)
   

   

   
   (Wherein y is an average value and represents a real number in the range of 1 to 10. R ₈ and R ₉ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Containing one or more selected from the group consisting of phenolic compounds, and
   The (E) reactive epoxy monomer is
   Following formula (10)
   

   

   
   (In the formula, R ₅ represents a divalent aliphatic hydrocarbon group having 1 to 11 carbon atoms.)
   And / or the following formula (11)
   

   

   
   (In the formula, R ₆ represents a trivalent aliphatic hydrocarbon group having 1 to 11 carbon atoms.)
   The photosensitive resin composition characterized by containing the epoxy compound represented by these.
2. (E) The photosensitive resin composition of Claim 1 in which a reactive epoxy monomer contains a trimethylol propane triglycidyl ether.
3. The photosensitive resin composition according to claim 1, wherein the blending ratio of the (E) reactive epoxy monomer is 2 to 12% by mass with respect to the total mass of (A) the epoxy resin and (B) the polyhydric phenol compound.
4. The photosensitive resin composition according to claim 1, wherein the blending ratio of the (B) polyhydric phenol compound is 1 to 40% by mass with respect to the mass of the (A) epoxy resin.
5. The photosensitive resin according to claim 1, wherein the blending ratio of (C) the photocationic polymerization initiator is 0.1 to 15% by mass with respect to the total mass of (A) the epoxy resin and (B) the polyhydric phenol compound. Composition.
6. (D) The photosensitive resin composition according to claim 1, wherein the epoxy group-containing silane compound is an epoxy group-containing alkoxysilane compound.
7. (D) The blending ratio of the epoxy group-containing silane compound is based on the total mass of (A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization initiator, and (E) reactive epoxy monomer. The photosensitive resin composition according to claim 1, which is 1 to 15% by mass.
8. The photosensitive resin composition according to claim 1, further comprising (G) an acrylic resin.
9. The photosensitive resin composition according to claim 8, wherein (G) the acrylic resin is a copolymer obtained using an ethylenically unsaturated monomer having a glycidyl group.
10. The blending ratio of (G) acrylic resin is (A) epoxy resin, (B) polyhydric phenol compound, (C) photocationic polymerization initiator, (D) epoxy group-containing silane compound, and (E) reactive epoxy monomer. The photosensitive resin composition according to claim 8, which is 1 to 20% by mass relative to the total mass.
11. The photosensitive resin composition according to claim 1, further comprising (F) a solvent.
12. The photosensitive resin composition according to claim 11, wherein the blending ratio of the (F) solvent is 5 to 95% by mass with respect to the total mass of the photosensitive resin composition containing the (F) solvent.
13. A cured product of the photosensitive resin composition according to any one of claims 1 to 12.
14. A resist laminate obtained by sandwiching the photosensitive resin composition according to any one of claims 1 to 12 between two substrates.
15. A cured product of a dry film resist obtained from the resist laminate according to claim 14.