JP5939965B2 - Photosensitive resin composition, resist laminate and cured product thereof - Google Patents

Description

  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, microinjection molding and hot embossing molds And image quality with good sidewall shape and resolution, useful in the manufacture of stamps, screens or stencils for micro printing applications, MEMS and semiconductor packaging components, BioMEMS and biophotonic devices, and printed wiring boards, post cure The present invention relates to a photosensitive resin composition having a low internal stress and excellent substrate adhesion after a wet heat test and a cured product thereof.

  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, a high adhesion to a substrate, and the like are required. Here, the aspect ratio is an important characteristic calculated by resist film thickness / pattern line width and showing the performance of photolithography.

  The composition mainly composed of bisphenol A type novolak epoxy resin disclosed in Patent Document 1 and Non-Patent Document 1 has very high resolution, and by using the composition, photosensitive image formation with a high aspect ratio is achieved. In addition, it is possible to form a cured photosensitive resin. However, the resulting resin cured product tends to be too brittle depending on the application, and often causes cracking (crazing) during development or when internal stress occurs, so depending on the type of substrate using the resin composition Not only decreases, but in some cases, peeling may occur between the substrate and the cured resin. All these problems occur when the composition is cured and contracted, and are caused by the stress accumulated in the resin cured product. When the curing shrinkage is large, the substrate is often bent (warped).

Furthermore, when the substrate on which the cured resin is formed is subjected to a wet heat test (80 ° C., 100%, 24 hours), which is one of the accelerated durability tests, the cured resin is peeled off from the substrate. When used in applications such as semiconductor packages and microreactor forming parts, the problem is that the durability is inferior.

Patent Document 2 discloses a photosensitive composition containing an epoxy resin having an average functional group number of 1.5 or more, a hydroxyl-containing additive, and a photocationic polymerization initiator. The document describes that the addition of a hydroxyl-containing additive increases the flexibility of the coating film up to a thickness of 100 μm and has the effect of reducing shrinkage. The resolution of the composition as a photoresist is about 90 μm, and the shape of the photosensitive image has a trailing residue at the edge of the photosensitive image after development, and the top portion of the photosensitive image is rounded. Since it was tinged, it was extremely incompatible with MEMS packages, semiconductor packages, microreactors, and the like.

US patent US4882245 US Pat. No. 4,256,828

N. LaBiancaand J.M. D. Gelorme, High Aspect Ratio Resist for Thick Film Applications ", Proc. SPIE, vol. 2438, page 846 (1995)

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 sidewall shape and fine resolution. Another object of the present invention is to provide a photosensitive image-forming resin composition having low stress, heat and humidity resistance, and high adhesion, 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.

That is, the present invention
(1) A photosensitive resin composition containing (A) an epoxy resin, (B) a polyol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing silane compound, and (E) a reactive epoxy monomer. And
The (A) epoxy resin has the 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, .R ₁ and R ₂ represents a real number in the range of 2 to 30 each independently represent a hydrogen atom, an alkyl group or a trifluoromethyl group having 1 to 4 carbon atoms X represents each independently a hydrogen atom or a glycidyl group, and at least one of a plurality of Xs is a glycidyl group), and contains (B) an epoxy resin (b) as an essential component. The polyol compound is represented by 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 divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is bonded by an oxygen atom. Or a polyester polyol represented by the following formula (4):

で表されるエポキシ化合物である前項（１）に記載の感光性樹脂組成物、
（３）（Ｅ）反応性エポキシモノマーの配合割合が、（Ａ）エポキシ樹脂及び（Ｂ）ポリオール化合物の合計質量に対して２〜１２質量％である前項（１）または（２）に記載の感光性樹脂組成物、
（４）（Ｂ）ポリオール化合物の配合割合が、（Ａ）エポキシ樹脂の合計質量に対して１〜３０質量％である前項（１）乃至（３）のいずれか一項に記載の感光性樹脂組成物、
（５）（Ｃ）光カチオン重合開始剤の配合割合が、（Ａ）エポキシ樹脂、（Ｂ）ポリオール化合物及び（Ｅ）反応性エポキシモノマーの合計質量に対して０．１〜１５質量％である前項（１）乃至（４）のいずれか一項に記載の感光性樹脂組成物、
（６）（Ｄ）エポキシ基含有シラン化合物が、エポキシ基含有アルコキシシラン化合物である前項（１）乃至（５）のいずれか一項に記載の感光性樹脂組成物、
（７）（Ｄ）エポキシ基含有シラン化合物の配合割合が、（Ａ）エポキシ樹脂、（Ｂ）ポリオール化合物、（Ｃ）光カチオン重合開始剤及び（Ｅ）反応性エポキシモノマーの合計質量に対して１〜１５質量％である前項（１）乃至（６）のいずれか一項に記載の感光性樹脂組成物、
（８）更に（Ｆ）溶剤を含有する前項（１）乃至（７）のいずれか一項に記載の感光性樹脂組成物、
（９）（Ｆ）溶剤の配合割合が、（Ｆ）溶剤以外の成分の合計質量に対して５〜９５質量％である請求項８に記載の感光性樹脂組成物、
（１０）前項（１）乃至（９）のいずれか一項に記載の感光性樹脂組成物の硬化物、
（１１）前項（１）乃至（９）のいずれか一項に記載の感光性樹脂組成物を基材で挟み込んで得られるレジスト積層体、
（１２）前項（１１）に記載のレジスト積層体から得られるドライフィルムレジストの硬化物、
に関する。 (Wherein y is an average value and represents a real number in the range of 1 to 6. R ₄ represents a trivalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is bonded by an oxygen atom. And (E) a reactive epoxy monomer is an epoxy compound which is a polycyclic saturated hydrocarbon derivative having two or more epoxy groups in one molecule. A photosensitive resin composition, wherein
(2) (E) The reactive epoxy monomer is represented by the following formula (13):

The photosensitive resin composition according to item (1), which is an epoxy compound represented by:
(3) The blending ratio of the (E) reactive epoxy monomer is 2 to 12% by mass with respect to the total mass of the (A) epoxy resin and (B) polyol compound, as described in (1) or (2) above Photosensitive resin composition,
(4) The photosensitive resin according to any one of (1) to (3), wherein the blending ratio of the (B) polyol compound is 1 to 30% by mass with respect to the total mass of the (A) epoxy resin. Composition,
(5) The blending ratio of the (C) photocationic polymerization initiator is 0.1 to 15% by mass with respect to the total mass of the (A) epoxy resin, (B) polyol compound and (E) reactive epoxy monomer. The photosensitive resin composition according to any one of (1) to (4),
(6) The photosensitive resin composition according to any one of (1) to (5), wherein (D) the epoxy group-containing silane compound is an epoxy group-containing alkoxysilane compound,
(7) The blending ratio of (D) epoxy group-containing silane compound is based on the total mass of (A) epoxy resin, (B) polyol compound, (C) photocationic polymerization initiator and (E) reactive epoxy monomer. The photosensitive resin composition according to any one of (1) to (6), which is 1 to 15% by mass,
(8) The photosensitive resin composition according to any one of (1) to (7), further including (F) a solvent;
(9) The photosensitive resin composition according to claim 8, wherein the blending ratio of (F) solvent is 5 to 95% by mass with respect to the total mass of components other than (F) solvent.
(10) A cured product of the photosensitive resin composition according to any one of (1) to (9),
(11) A resist laminate obtained by sandwiching the photosensitive resin composition according to any one of (1) to (9) above with a base material,
(12) A cured product of a dry film resist obtained from the resist laminate according to (11) above,
About.

  The photosensitive resin composition of the present invention can form a fine and vertical sidewall pattern by photolithography, and the cured product has characteristics excellent in low stress, wet heat resistance, and high adhesion. 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 (A) epoxy resin contained in the photosensitive resin composition of the present invention is represented by the epoxy resin (a) obtained by the reaction of the phenol derivative represented by the above formula (1) and epihalohydrin and the above formula (2). Both of the epoxy resins (b) to be used are essential components. Among these, the epoxy resin (a) contributes to the vertical side wall shape and fine resolution of a cured product (pattern) obtained by photolithography using the photosensitive resin composition of the present invention. Using a phenol derivative represented by the formula (1) and an epihalohydrin, it can be obtained by a conventionally known epoxy resin synthesis method.

As a general synthesis method of the epoxy resin (a), for example, a mixed solution in which a phenol derivative represented by the formula (1) and an epihalohydrin (such as epichlorohydrin or epibromohydrin) are dissolved in a solvent that can be dissolved After adding an alkali such as sodium hydroxide and raising the temperature to the reaction temperature to carry out an addition reaction and a ring closure reaction, the reaction solution was repeatedly washed with water, separated and the aqueous layer removed, and finally the solvent was removed from the oil layer. The method of distilling off is mentioned.
It is known that an epoxy resin (a) having different main components in the epoxy resin (a) can be obtained depending on the use ratio of the phenol derivative represented by the formula (1) and the epihalohydrin used in the synthesis reaction. 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, but as the amount of epihalohydrin used with respect to the phenolic hydroxyl group decreases, the phenolic hydroxyl groups of a plurality of phenol derivatives are bonded via epihalohydrin, and the remaining phenolic hydroxyl group is epoxidized. The content of the polyfunctional epoxy resin having a large size 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 epoxy resin (a) obtained by this method is also included in the category of the epoxy resin (a) contained in the photosensitive resin of the present invention.
The reaction between the phenol derivative represented by formula (1) and epihalohydrin is usually 0.3 to 30 mol, preferably 1 to 20 mol, of epihalohydrin with respect to 1 mol of phenol derivative (corresponding to 3 mol of hydroxyl group). More preferably 3 to 15 mol is used.

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. Alternatively, an epoxy resin (a) containing any of multimeric epoxy resins of phenol derivatives as a main component can be used, but the epoxy resin (a) is excellent in solvent solubility and has a low softening point and is easy to handle. , Phenol derivative monomer epoxy resin, phenol derivative dimer epoxy resin (epoxy resin having a structure in which two phenol derivatives represented by formula (1) are bonded via epihalohydrin) or phenol derivative Trimer epoxy resin (3 phenol derivatives represented by the formula (1) are epihalohydrin An epoxy resin (a) having as a main component any one of epoxy resins having a structure bonded via an epoxy resin, and a phenol derivative monomer epoxy resin or a phenol derivative dimer epoxy resin as a main component. The epoxy resin (a) to be used is more preferable.
The term “main component” as used in the present application means an epoxy resin component having the highest content among monomeric epoxy resins and multimeric epoxy resins contained in the epoxy resin (a).

  Below, the specific structure of the monomer epoxy resin (a) of the phenol derivative represented by Formula (1) is shown in Formula (5).

Below, the specific structure of the epoxy resin (a) of the dimer of the phenol derivative represented by Formula (1) is shown in the following Formula (6).

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

As an epoxy resin (a), what has the weight average molecular weight of the range of 500-12000 is preferable, and what has the weight average molecular weight of the range of 500-9000 is more preferable. Specific 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.). In addition, the weight average molecular weight in this application is a value calculated in terms of polystyrene based on the measurement result of GPC, the epoxy equivalent is a value measured in accordance with JIS K-7236, and the softening point is in accordance with JIS K-7234. Means the measured values.

In addition, 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. 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. It is preferable that the softening point is 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) exceeds 4900% by mass, the photosensitive image pattern does not have a vertical side wall shape, tends to be rounded, and is less than 2% by mass. Tends to cause cracks on the surface of the photosensitive image pattern.

  The (A) epoxy resin 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). Although the epoxy resin which can be used together is not specifically limited, The epoxy resin contained in the definition of the (E) reactive epoxy monomer mentioned later shall not be contained in the category of the epoxy resin which can be used together. The blending ratio of the epoxy resin that can be used in combination is not particularly limited as long as the effects of the present invention are not impaired.

The (B) polyol compound contained in the photosensitive resin composition of the present invention contains the polyester polyol represented by the above formula (3) and / or the above formula (4) as an essential component. The (B) polyol compound contains a hydroxy group that reacts with the epoxy group in the (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), the dried coating film obtained by drying the solvent component if necessary after applying the resin composition is softened. It is possible to avoid stress induction in exposure curing, development, and thermal curing processes during lithography processing, reduce shrinkage, and prevent cracking of a photosensitive image.
In addition, when using as a resist laminate (dry film) in which a dry coating film of the photosensitive resin composition is sandwiched between substrates, the resist laminate is rolled into a plastic cylinder as a long roll. The effect that a crack does not arise in a coating film is also acquired.

In 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. In addition, the average value here means the average value of two described in Formula (3), for example, when one x is 4 and the other x is 6. The average value x is 5.
R ₃ represents a divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group may be bonded with an oxygen atom. The aliphatic hydrocarbon residue represented by R ₃ is usually a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, preferably a linear or branched chain having 1 to 10 carbon atoms. Divalent aliphatic hydrocarbon group, more preferably a divalent linear or branched aliphatic hydrocarbon group having 2 to 8 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, and a propylene group. , A straight-chain aliphatic hydrocarbon group such as a butylene group or a pentylene group, or a branched-chain aliphatic hydrocarbon group in which an alkyl group is bonded as a side chain to the straight-chain aliphatic hydrocarbon group.
In addition, the aliphatic hydrocarbon residue represented by R ₃ may be bonded with an oxygen atom. The aliphatic hydrocarbon group bonded here by an oxygen atom means a divalent linking group in which a divalent aliphatic hydrocarbon group is bonded through an oxygen atom. Specifically, for example, a methylene group And a linking group in which an ethylene group is bonded via an oxygen atom. The number of oxygen in the linking group is not particularly limited. For example, a linking group in which an oxygen atom and an ethylene group are further bonded to the linking group composed of the methylene group, the oxygen atom and the ethylene group is also included in the definition of R _3. .
The divalent aliphatic hydrocarbon group bonded by an oxygen atom is not particularly limited as long as the number of carbon atoms in the linking group is within the above range, and may be linear, branched, linear and branched. Any combination may be used, and the number of carbon atoms may be different. In addition, the number of oxygen atoms in the linking group is usually 1 to 3, preferably 1 to 2, and more preferably 1.

A commercially available product is available for the polyester polyol represented by the formula (3). Specific examples thereof include “PLAXEL 205” having a molecular weight of 530 and an OH value of 210 mgKOH / g, “PLAXEL 210” having a molecular weight of 1000 and an OH value of 110 mgKOH / g, and a molecular weight of 2000 and an OH value of 56 mgKOH / g. “Placcel 220” (both trade names, manufactured by Daicel), “Capa2054” with a molecular weight of 550 and an OH value of 204 mgKOH / g, “Capa2100” with a molecular weight of 1000 and an OH value of 112 mgKOH / g, OH with a molecular weight of 2000 “Capa2200” (both trade names, manufactured by Perstorp) having a value of 56 mgKOH / g can be mentioned.

In 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 here means the average value of three described in Formula (4), for example, when each y is 2, 3, and 7. The average value y is 4.
R ₄ represents a trivalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group may be bonded with an oxygen atom. The aliphatic hydrocarbon residue represented by R ₄ is usually a branched trivalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, preferably a branched trivalent aliphatic group having 1 to 10 carbon atoms. It is a hydrocarbon group, more preferably a trivalent branched aliphatic hydrocarbon group having 2 to 8 carbon atoms, and these aliphatic hydrocarbon groups include those having an alkyl group as a side chain.
In addition, the aliphatic hydrocarbon residue represented by R ₄ may be bonded with an oxygen atom. The aliphatic hydrocarbon group bonded by an oxygen atom here is a trivalent linking group in which an aliphatic hydrocarbon group is bonded through an oxygen atom, and bonded by an oxygen atom represented by R ₃ described above. This is in accordance with the explanation of the aliphatic hydrocarbon group.

The polyester polyol represented by the formula (4) is available as a commercial product. Specific examples thereof include “Capa3050” 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 value of 183 mgKOH / g, and a molecular weight of 2000 and an OH value of 84 mgKOH / g. “Capa3201” (both trade names, manufactured by Perstorp), “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 value of 195 mgKOH / g, and a molecular weight of 1250 Examples thereof include “Placcel 312” having an OH value of 135 mgKOH / g and “Placcel 320” having a molecular weight of 2000 and an OH value of 84 mgKOH / g (both trade names, manufactured by Daicel Corporation).
The blending ratio of the (B) polyol compound in the photosensitive resin composition of the present invention is usually 1 to 30% by mass, preferably 2 to 25% by mass, and more preferably 3 to 3% by mass with respect to the total mass of the (A) epoxy resin. 15% by mass. (B) When the blending ratio of the polyol compound exceeds 30% by mass, the photosensitive image pattern does not have a vertical side wall shape and tends to be rounded, and when it is less than 1% by mass, a sufficient dilution effect and a dry coating film are obtained. The softening effect cannot be obtained, and cracks are likely to occur on the surface of the photosensitive image pattern.
In addition, when using together the polyester polyol represented by Formula (3) and Formula (4), the use ratio of both is (A) If the compounding ratio of the (B) polyol compound with respect to an epoxy resin is in said range. There is no particular limitation.

  The polyol compound (B) contained in the photosensitive resin composition of the present invention may be used in combination with a polyol compound other than the polyol compounds represented by the above formulas (3) and (4). The polyol compound that can be used in combination is not particularly limited, and the blending ratio of the polyol 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. Examples of the (C) 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-tertiarybutyl) 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 (trade name CPI-6976, manufactured by ACETO Corporation USA) and Phenylsulfonium tris (trifluoromethanesulfonyl) methanide (manufactured by BASF, trade name CGI TPS-C1), tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tris (trifluoromethylsulfonyl) methide (manufactured by 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) Preferably used. Among the above cationic photopolymerization initiators, in the present invention, an aromatic sulfonium complex salt having high vertical rectangular workability and high thermal stability is preferable in the photosensitive image forming step, and 4- {4- (2-chlorobenzoyl) Phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, a mixture of aromatic sulfonium hexafluoroantimonate containing 4-thiophenyldiphenylsulfonium hexafluoroantimonate, tris [4- (4- Acetylphenyl) sulfonylphenyl] sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate is particularly preferred.

These (C) photocationic polymerization initiators may be used alone or in combination of two or more. (C) Since the cationic photopolymerization initiator component has an action of absorbing light, when a large amount of component (C) is used in the case of a thick film (for example, 50 μm or more) (for example, an amount exceeding 15% by mass)
However, it becomes difficult to obtain a sufficient curing rate when a small amount is used (for example, less than 3% by mass) while light at the time of curing cannot be sufficiently transmitted to the deep part. In the case of a thin film, sufficient performance is exhibited by addition of a small amount (for example, 1% by mass or more). On the contrary, when the component (C) is used in a large amount, there is no problem with respect to light transmission to the deep part, but an expensive initiator is used unnecessarily, which is not economical. From these points, the blending ratio of the (C) photocationic polymerization initiator component in the photosensitive resin composition of the present invention is the total mass of (A) the epoxy resin, (B) the polyol compound and (E) the reactive epoxy monomer. The content is usually 0.1 to 15% by mass, preferably 0.2 to 8% by mass. However, when the molar absorption coefficient of the photocationic polymerization initiator (C) at a wavelength of 300 to 380 nm is high, it is necessary to adjust to an appropriate blending 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 the storage stability of the photosensitive resin composition of this invention is not inhibited. (D) Preferable specific examples of the epoxy group-containing silane compound include an epoxy group-containing alkoxysilane compound. Examples of the epoxy group-containing alkoxysilane compound 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 (D) epoxy group-containing silane compound in the photosensitive resin composition of the present invention is as follows: (A) epoxy resin, (B) polyol compound, (C) photocationic polymerization initiator, and (E) reactive epoxy monomer. It is 1-15 mass% normally with respect to the total mass of, Preferably it is 3-10 mass%.

  The (E) reactive epoxy monomer contained in the photosensitive resin composition of the present invention improves the flexibility, flexibility, moisture resistance, and water resistance of the uncured film and the cured film of the photosensitive resin composition of the present invention. And contributes to improving the adhesion of the cured film. In the present invention, an epoxy compound having two or more epoxy groups in one molecule and having 20 or less carbon atoms contained in the polycyclic saturated hydrocarbon derivative skeleton is used as a reactive epoxy monomer. In the case of one epoxy group compound per molecule, the crosslink density is extremely small, and the flexibility, moisture resistance and water resistance of the cured film are not sufficiently satisfied. (E) A photosensitive resin composition excellent in the above-mentioned effects such as flexibility by using a polycyclic saturated hydrocarbon derivative having two or more epoxy groups in one molecule as a reactive epoxy monomer as an essential component. A thing is obtained. As the polycyclic saturated hydrocarbon derivative having two or more epoxy groups in one molecule, a compound containing a 5-membered ring structure or a 6-membered ring structure is usually used. By including a 5-membered ring structure or a 6-membered ring structure, the heat resistance can be increased. The 6-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. The number of carbon atoms contained in the polycyclic saturated hydrocarbon derivative skeleton is usually 4 to 20, preferably 5 to 14.

Specific examples of the polycyclic saturated hydrocarbon derivative having two epoxy groups in one molecule include dimethylol tricyclodecane diglycidyl ether, 1,3-adamantanediol diglycidyl ether, 1,3-adamantane dimethanol dimer. Glycidyl ether, 2,6-decalin dimethanol diglycidyl ether, 1,5-decalin dimethanol diglycidyl ether, 2,3-decalin dimethanol diglycidyl ether, 2,3-norbornane dimethanol diglycidyl ether, 2,5 -Norbornane dimethanol diglycidyl ether etc. are mentioned, It is preferable that it is the dimethylol tricyclodecane diglycidyl ether represented by the said Formula (13). These can 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, preferably 3 to the total mass of the (A) epoxy resin and (B) polyol compound. 10% by mass.

  The reactive epoxy monomer (E) contained in the photosensitive resin composition of the present invention may be used in combination with a reactive epoxy monomer other than a polycyclic saturated hydrocarbon derivative having two epoxy groups in one molecule. . 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.

(F) 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 coating-film property. 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) The solvent component is added for the purpose of adjusting the film thickness and applicability when applied to the base material, and properly maintains the solubility of the main component, the volatility of the component, the liquid viscosity of the composition, etc. The amount used is preferably 95% by mass or less, particularly preferably 10 to 90% by mass in the photosensitive resin composition containing the solvent.

  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 derivative) 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 a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a C1-C4 alkyl group, a sulfonic acid alkyl ester group, a 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 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, 2,4-diisopropylthioxanthone, etc., and 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) , Trade name Kayacure DETX-S) 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 may be used alone or in combination of two or more, but the use of 2,4-diethylthioxanthone and 9,10-dimethoxy-2-ethylanthracene is most preferred. Since a sensitizer component exhibits an effect in a small amount, its use ratio is preferably 30% by mass or less, particularly 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 when it is necessary to reduce the adverse effect of ions derived from the (C) photocationic polymerization initiator. Specific examples of the ion catcher include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, isopropoxydiethoxyaluminum and trisbutoxyaluminum and other alkoxyaluminums, trisphenoxyaluminum and trisparamethylphenoxyaluminum and other phenoxyaluminums, tris Acetoxyaluminum, trisstearatoaluminum, trisbutyratealuminum, trispropionatoaluminum, trisacetylacetonatoaluminum, tristrifluoroacetylacetonatoaluminum, trisethylacetoacetatoaluminum, diacetylacetonatodipivaloylmethanatoaluminum and di Isopropoxy (ethyl acetoacetate) aluminum Organoaluminum compounds such as Um like. These components can be used alone or in combination of two or more. Moreover, the compounding quantity is 10 mass% or less with respect to the total mass of (A) epoxy resin, (B) polyol compound, (C) photocationic polymerization initiator, and (E) reactive epoxy monomer.

  Various additives, such as a thermoplastic resin, a coloring agent, a thickener, an antifoamer, and a leveling agent, can be used for the photosensitive resin composition of this invention as needed. 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. When these additives are used, the amount of the photosensitive resin composition material of the present invention excluding the solvent is, for example, 30% by mass or less for each purpose. The number can be appropriately increased or decreased according to the required function. Examples of the thickener include olben, benton and montmorillonite, and examples of the antifoaming agent include antifoaming agents such as silicone, fluoroalkyl and polymer. When these additives are used, the amount used is 10% by weight or less, for example, based on the amount of the photosensitive resin composition material of the present invention excluding the solvent. Depending on the quality, it can be increased or decreased as appropriate.

  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 amount used is 60% by mass or less based on the amount of the photosensitive resin composition material of the present invention excluding the solvent, but 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 polymethylmethacrylate, rubber, fluoropolymer, polyurethane powder can be incorporated.

  The photosensitive resin composition of the present invention comprises (A) an epoxy resin, (B) a polyol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing silane compound, and (E) an essential component of a reactive epoxy monomer. If necessary, (F) solvent, sensitizer, ion catcher, thermoplastic resin, colorant, thickener, antifoaming agent, leveling agent, inorganic filler, etc., which are optional components, are mixed in the usual way. It is adjusted by stirring. When mixing and stirring, a disperser such as a dissolver, a homogenizer, or a three roll mill may be used as necessary. Moreover, after mixing, you may filter using a mesh, a membrane filter, etc. further.

  The photosensitive resin composition of the present invention is preferably used in a liquid form to which a solvent is added for coating on a substrate. The photosensitive resin composition of the present invention diluted to a desired viscosity with a solvent is dispensed onto a substrate, the substrate is accelerated to a certain rotation speed, and the rotation speed is kept constant to obtain a desired film thickness. It can apply | coat by the spin coat method which consists of a process. Spin coating can be performed at various rotational speeds to control film thickness. Alternatively, the photoresist composition can be applied to the substrate using other coating methods such as roller coating, doctor knife coating, slot coating, dip coating, gravure coating, spray coating, etc. . After coating, dry baking is performed to evaporate the solvent. Dry bake conditions are selected to form a semi-cured dry film of the photoresist, and typical conditions include using a smooth surface hot plate and either touching or approaching the surface. Drying is performed at 65 ° C. for 1 to 15 minutes, and subsequently at 90 to 125 ° C. for 5 to 120 minutes, depending on the thickness of the film, the volatility of the solvent, the thermal conductivity of the substrate, and the substrate thickness. Alternatively, the dry bake can be performed in a convection oven. Next, the dried photosensitive resin composition coating film is passed through a photomask on which a desired mask pattern is drawn, exposed to near ultraviolet light from a medium-pressure or ultrahigh-pressure mercury lamp, 300 to 500 nm emission line, or a synchrotron radiation source. A photosensitive image can be formed by irradiation with energy rays from X-ray radiation from, or irradiation with electron beam directly or through patterned exposure. Contact, proximity, or projection prints can be used. Subsequent to exposure, post-exposure baking is performed on the exposed areas of the coating to promote the polymerization reaction by acid catalysis. Typical conditions are 65 ° C. for 1-5 minutes and 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.

Next, in order to dissolve and remove the unexposed area, the film is typically immersed in an organic solvent developer 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 is rinsed by applying a rinsing solvent, and the developer adhering to the cured film is removed. 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 necessary 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 the paddle method, the substrate to be developed is placed on a rotating tool head, and then a sufficient amount of developer solution to form a paddle or a layer stagnant on the entire substrate area is metered onto the substrate that rotates slowly. After distributing and stopping the rotation, the formed developer paddle is allowed to stand on the substrate for a certain period of time, and then the rotation of the substrate is accelerated to remove the used developer by spin removal, and the rotation is decelerated until the rotation 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. Propylene glycol monomethyl ether acetate, which dissolves unexposed portions well and is relatively low in cost, is particularly preferred.
Suitable rinsing liquids include any of the above developer solvents, and methanol, ethanol, isopropanol, and n-butyl acetate. Of these, acetone, ethanol, and isopropanol are particularly preferable because they can be washed quickly and dried quickly. Finally, depending on the heat resistance of the substrate, a heat treatment is performed under a temperature condition of 130 to 200 ° C. to thermally cure the film, thereby obtaining a permanent protective film satisfying various characteristics.

Substrate materials that can be used include 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, metals, semiconductors, and any substrate containing a patterned region of insulating material.

The photosensitive resin composition of the present invention can be sandwiched between substrates and used as a resist laminate. 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., the temperature is 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) or the like as necessary. At this time, the thickness of the resist on the base film is 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, are used, for example. As these films, a film 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 resist laminate of the present invention is used as a photosensitive resin composition dry film resist, the steps of coating on a support or substrate and drying can be omitted, and the photosensitive layer of the present invention can be simplified. It becomes possible to form a fine pattern using the conductive resin composition.

  When used as 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. The first layer is exposed and baked after exposure. Furthermore, after applying and drying the photosensitive resin composition of the present invention to form a photosensitive resin coating film of the second layer, the second layer is exposed and baked after exposure. 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 the present invention is performed in order to prevent deterioration of a package having a driving unit such as a MEMS, a hollow package for packaging a vibrator such as a SAW device, a semiconductor substrate, a printed wiring board, wiring, or the like. Surface protection, microreactor forming parts and resin sealing for sealing them with a top plate. “Wafer level package” means that the protective film, terminals, wiring processing and package are performed in the state of the wafer, then cut into chips and separated into individual pieces, and fine micro or nano channels and orifice plates are formed in the wafer. Represents a method of three-dimensional processing in a lump.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, these Examples are only the illustrations for demonstrating this invention suitably, and do not limit this invention at all.

Examples 1-6 and Comparative Examples 1-7
(Preparation of photosensitive resin composition solution (liquid resist))
(A) epoxy resin, (B) polyol compound, (C) photocationic polymerization initiator, (D) according to the blending amounts shown in Table 1 (units are parts by mass and solution products are solid parts by mass of the main body) ) "Liquid resist-A" obtained by diluting the epoxy group-containing silane compound and (E) reactive epoxy monomer with cyclopentanone to a concentration of 65% by mass, and diluting to a concentration of 34% by mass This was designated as “Liquid Resist-B”, stirred and dissolved in a flask equipped with a stirrer at 60 ° C. for 1 hour, allowed to cool, and then filtered through a membrane filter having a pore size of 1.0 μm. A resin composition solution (liquid resist) was obtained.

(Patterning of photosensitive resin composition)
Each liquid resist-A obtained in Examples 1 to 6 and Comparative Examples 1 to 7 was coated on a silicon wafer with a spin coater, then pre-baked for 10 minutes on a 95 ° C. hot plate, and dried 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 a dose of 500 mJ / g via a photomask with a gray scale for resolution evaluation using an i-line exposure apparatus (mask aligner: manufactured by USHIO INC.). Irradiated with cm ² (soft contact, i-line). 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, Inc., main component of propylene glycol monomethyl ether acetate), rinsing with isopropanol and drying. Got.

(Sensitivity, resolution, crack evaluation of photosensitive resin composition)
In the patterning test, the exposure amount with the best mask transfer accuracy was set as the optimum 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 1 below.
Also, using a photomask in which 1 to 100 μm line and space and a perfectly circular hole pattern are arranged, the optimal exposure amount of each composition (soft contact, i-line, see exposure amount in Table 1) is irradiated. PEB was performed for 5 minutes on a hot plate at 95 ° C. It was immersed and developed at 23 ° C. for 3 minutes with SU-8 Developer (trade name, manufactured by Microchem, principal 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 bends. The results are shown in Table 1 below.
Moreover, the crack generation of the obtained photosensitive image pattern was evaluated. The state where there is a crack (discontinuous tearing to the bottom of the film) on the entire surface of the film is “XX”, and cracks are generated only at the corners of the rectangular hole pattern (pointing to the tearing state occurring on the extreme surface of the film) The state where “X” is present and the state where no crack is generated is “O”. The results are shown in Table 1 below.

(Evaluation of wet heat adhesion of cured product of photosensitive resin composition)
Each liquid resist-A obtained in Examples 1 to 6 and Comparative Examples 1 to 7 was coated on a silicon wafer with a spin coater, then pre-baked for 10 minutes on a 95 ° C. hot plate, and dried 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 the optimal exposure amount of each composition is passed through a pattern photomask for adhesion evaluation using an i-line exposure apparatus (mask aligner: manufactured by USHIO INC.). (Soft contact, i-line, exposure amount in Table 1) was irradiated, and PEB was performed for 5 minutes on a hot plate at 95 ° C. Immerse and develop with SU-8 Developer (trade name, manufactured by Microchem, Propylene glycol monomethyl ether acetate) at 23 ° C. for 3 minutes, 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), the same -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 deterioration of the adhesive strength, “×” when there was deterioration, and there was pattern lifting or peeling after the test. The case was designated as “XX”. The results are shown in Table 1 below.

(Internal stress measurement of substrate with film)
The “internal stress of the substrate with film” means a silicon wafer substrate (diameter 100 mm, supported by three points by a stylus type surface shape measuring instrument Dektak 8 (trade name, manufactured by Veeco).
The amount of warpage of the substrate before and after the formation of a 0.5 mm thick film was measured, and the change in the amount of warpage before and after conversion was converted to stress. In general, the stress of the film is not affected by the shape and material of the base material on which the film is formed, so the film was formed on a silicon wafer substrate and obtained by measuring the amount of substrate warpage before and after formation. Things show internal stress. When the resin film cures and shrinks, it becomes a compressive stress, and the stress of the cured film increases the warpage of the substrate with the magnitude of the stress, and the film itself also generates cracks such as crazing and cracks. As the internal stress is smaller, the warpage of the substrate is reduced and the crack of the film itself is also eliminated.
Each liquid resist-B obtained in Examples 1 to 6 and Comparative Examples 1 to 7 was coated on each silicon wafer (diameter 100 mm, thickness 0.5 mm) whose warping amount had been measured by a spin coater, and then 95 ° C. Was pre-baked for 5 minutes using a hot plate, and a photosensitive resin composition layer having a dry film thickness of 2.0 μm was obtained after coating. Thereafter, the film swell portion on the wafer end surface is dissolved and removed, dried, and then subjected to an optimum exposure dose (soft contact, i-line, Table 1) of each composition using an i-line exposure apparatus (mask aligner: manufactured by USHIO INC.). The entire surface of the film was irradiated, and PEB was performed for 5 minutes with a hot plate at 95 ° C., followed by hard baking in a 200 ° C. oven for 60 minutes to obtain a cured silicon wafer with a resin film. After each sample of the substrate with film was sufficiently cooled to 23 ° C., the amount of warpage was measured and the compressive stress was calculated. The results are shown in Table 1 below.

In Table 1, (A-1) to (E′-1) 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), epoxy equivalent 330 g / eq.)
(A-3): NER-7403 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy resin (b), 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): ERL-4221 (trade name, manufactured by Polysciences, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, epoxy equivalent 126 g / eq.)
(A′-3): EHPE-3150 (trade name, manufactured by Daicel Corporation, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, epoxy Equivalent 180 g / 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): Capa3050 (trade name, Perstorp Corp., y is 1-2 in the formula (4), trifunctional polyol _{R 4} is a trivalent aliphatic hydrocarbon group of 6 carbon atoms, molecular weight 540, OH equivalent 310mgKOH / g)
(B-2): Plaxel 308 (trade name, manufactured by Daicel Corporation, trifunctional polyol in which y in Formula (4) is 2 to 3, R ₄ is a trivalent aliphatic hydrocarbon group having 6 carbon atoms, molecular weight 850 OH equivalent 195 mg KOH / g)
(B-3): Plaxel 312 (trade name, manufactured by Daicel Corp., trifunctional polyol in which y is 3 to 4 and R ₄ is a trivalent aliphatic hydrocarbon group having 6 carbon atoms in formula (4), molecular weight 1250 OH equivalent 135 mg KOH / g)
(B-4): Plaxel 205 (trade name, manufactured by Daicel Corporation, x in Formula (3) is 1 to 3, and R ₃ is a divalent aliphatic hydrocarbon group having 4 to 6 carbon atoms, (Molecular weight 530, OH equivalent 210mgKOH / g)
(B-5): PLACCEL 220 (trade name, manufactured by Daicel Corporation, x is 8 to 9, and R ₃ is a divalent aliphatic hydrocarbon group having 5 carbon atoms in the formula (3), molecular weight 2000 OH equivalent 56 mg KOH / g)
(B′-1): Polyethylene glycol 1000 (molecular weight 1000)
(C-1): SP-172 (trade name, manufactured by ADEKA, 50 wt% propylene carbonate solution, but the compounding amount in the table represents the solid content value)
(C-2): CPI-6976 (trade name, manufactured by ACETO, 50 wt% propylene carbonate solution, but the amount shown in the table represents the solid content value)
(C-3): Irgacure PAG290 (trade name, manufactured by BASF)
(D-1): 3-glycidoxypropyltrimethoxysilane (D-2): 3-glycidoxypropylmethyldimethoxysilane (E-1): Adekaresin EP-4088L (trade name, manufactured by ADEKA, dimethylol Tricyclodecane diglycidyl ether, epoxy equivalent of 177 g / eq., 10 carbon atoms contained in the polycyclic saturated hydrocarbon derivative skeleton)
(E-2): 1,3-adamantane dimethanol diglycidyl ether (epoxy equivalent 154 g / eq., 10 carbon atoms contained in the polycyclic saturated hydrocarbon derivative skeleton)
(E′-1): Adamantanol monoglycidyl ether (epoxy equivalent 207 g / eq., Carbon number 10 contained in monofunctional, polycyclic saturated hydrocarbon derivative skeleton)
As shown in Table 1, the characteristics of the composition obtained from each example are as follows: the optimum exposure amount is small and the sensitivity is high; the resolution dimension of the photosensitive pattern is high; the internal stress is low; It did not occur, and it was found that the adhesion after wet heat was maintained.

Example 7 (resist laminate comprising the photosensitive resin composition of the present invention)
Furthermore, ethylene glycol dimethyl ether was further added to the composition ratio of Example 1 in Table 1, and the mixture was stirred and dissolved in a flask with a stirrer at 60 ° C. for 1 hour, and diluted so that the solution viscosity at 25 ° C. was 3 Pa · s. After cooling, membrane filtration with a pore size of 1.0 μm was performed to obtain a lacquer for the dry film of the photosensitive resin composition of the present invention. This lacquer is uniformly applied on a base film (made of polypropylene, manufactured by Mitsubishi Plastics Co., Ltd., film thickness 38 μm), dried by a hot air convection dryer at 65 ° C. for 5 minutes and at 80 ° C. for 15 minutes, and then on the exposed surface. A cover film (made of polypropylene, manufactured by Mitsubishi Plastics, Inc., film thickness: 38 μm) was laminated to obtain a resist laminate (photosensitive resin composition laminate) with a dry film resist having a film thickness of 25 μm sandwiched therebetween.

(Pattern of dry film resist)
After peeling the cover film from the photosensitive resin composition laminate 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 base film is peeled off. 25 μm photosensitive resin composition layer (dry film resist) was obtained. This photosensitive resin composition layer was subjected to contact exposure using an i-line exposure apparatus (mask aligner: manufactured by Ushio Inc.). Thereafter, PEB is performed for 5 minutes on a 95 ° C. hot plate, developed by immersion with SU-8 Developer (trade name, manufactured by Microchem, propylene glycol monomethyl ether acetate) at 23 ° C. for 3 minutes, rinsed with isopropanol, A resin pattern cured by drying was obtained. A cured product having an optimum exposure dose of 125 mJ / cm ² , no residue and cracks, and a vertical side wall with a fine line adhesion pattern width of 3 μm was obtained.

The photosensitive resin composition of the present invention can form a fine and vertical sidewall shape pattern by a photolithography technique, and the cured product has characteristics excellent in low stress, moist heat resistance and high adhesion. 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 (12)

A photosensitive resin composition comprising (A) an epoxy resin, (B) a polyol compound, (C) a photocationic polymerization initiator, (D) an epoxy group-containing silane compound, and (E) a reactive epoxy monomer,
The (A) epoxy resin has the 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, .R ₁ and R ₂ represents a real number in the range of 2 to 30 each independently represent a hydrogen atom, an alkyl group or a trifluoromethyl group having 1 to 4 carbon atoms X represents each independently a hydrogen atom or a glycidyl group, and at least one of a plurality of Xs is a glycidyl group), and contains (B) an epoxy resin (b) as an essential component. The polyol compound is represented by 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 divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is bonded by an oxygen atom. Or a polyester polyol represented by the following formula (4):

(Wherein y is an average value and represents a real number in the range of 1 to 6. R ₄ represents a trivalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is bonded by an oxygen atom. And (E) a reactive epoxy monomer that is a polycyclic saturated hydrocarbon derivative having two or more epoxy groups in one molecule. A photosensitive resin composition characterized by the above. (E) The reactive epoxy monomer is represented by the following formula (13)

The photosensitive resin composition of Claim 1 which is an epoxy compound represented by these. (E) The photosensitive resin composition of Claim 1 or 2 whose compounding ratio of a reactive epoxy monomer is 2-12 mass% with respect to the total mass of (A) epoxy resin and (B) polyol compound. (B) The photosensitive resin composition as described in any one of Claims 1 thru | or 3 whose compounding ratio of a polyol compound is 1-30 mass% with respect to the total mass of (A) epoxy resin. (C) The compounding ratio of a photocationic polymerization initiator is 0.1-15 mass% with respect to the total mass of (A) epoxy resin, (B) polyol compound, and (E) reactive epoxy monomer. The photosensitive resin composition as described in any one of thru | or 4. (D) The photosensitive resin composition according to any one of claims 1 to 5, wherein the epoxy group-containing silane compound is an epoxy group-containing alkoxysilane compound. (D) The mixing ratio of the epoxy group-containing silane compound is 1 to 15 with respect to the total mass of (A) epoxy resin, (B) polyol compound, (C) photocationic polymerization initiator and (E) reactive epoxy monomer. It is the mass%, The photosensitive resin composition as described in any one of Claims 1 thru | or 6. The photosensitive resin composition according to claim 1, further comprising (F) a solvent. (F) The photosensitive resin composition of Claim 8 whose compounding ratio of a solvent is 5-95 mass% with respect to the total mass of components other than (F) solvent. Hardened | cured material of the photosensitive resin composition as described in any one of Claims 1 thru | or 9. The resist laminated body obtained by pinching the photosensitive resin composition as described in any one of Claims 1 thru | or 9 with a base material. The hardened | cured material of the dry film resist obtained from the resist laminated body of Claim 11.