TW201641279A - Dry film, cured product, semiconductor device, and method for forming resist pattern - Google Patents

Abstract

The purpose of the present invention is to provide a dry film capable of forming a resist pattern having excellent resolution and heat resistance, even when a photosensitive layer having a thickness exceeding 20 [mu]m is formed. Provided is a dry film provided, in the following order, with: a support body; a silicone resin layer or an alkyd resin layer; and a photosensitive layer. The photosensitive layer contains a component (A), a component (D), and at least one of a component (B) and a component (C).

Description

Dry film, cured product, semiconductor device, and method for forming resist pattern

The present disclosure relates to a method of forming a dry film, a cured product, a semiconductor device, and a resist pattern.

In the production of a semiconductor element or a printed wiring board, for example, a negative photosensitive resin composition is used in order to form a fine pattern. In the above method, by applying a photosensitive resin composition or the like, a photosensitive layer is formed on a substrate (a wafer in the case of a semiconductor element or a substrate in the case of a printed wiring board), and a predetermined pattern is transmitted. Irradiating actinic rays. Then, a resin pattern is formed on the substrate by selectively removing the unexposed portion using a developing solution. Therefore, the photosensitive resin composition is required to have a short development time (developability), sensitivity to actinic rays, and fine pattern (resolution). Therefore, a photosensitive resin composition containing a novolac resin, an epoxy resin, and a photoacid generator which are soluble in an aqueous alkaline solution, and a photosensitive resin containing an alkali-soluble epoxy compound having a carboxyl group and a photocationic polymerization initiator are proposed. A resin composition or the like (for example, refer to Patent Document 1 to Patent Document 3). With the recent increase in the density of the printed wiring board, the demand for a photosensitive resin composition capable of forming a resist pattern having excellent resolution is improved.

In addition, from the viewpoint of workability in forming a photosensitive layer on a substrate, the photosensitive resin composition is also required to have excellent adhesion to a substrate (viscosity). When a photosensitive resin composition which does not have sufficient viscosity is used, there is a tendency that the photosensitive layer of the exposed portion is easily removed by development processing, and the adhesion between the substrate and the resist pattern tends to be deteriorated.

Further, as the surface protective film and the interlayer insulating film used for the semiconductor element, insulation reliability such as heat resistance, electrical properties, and mechanical properties is required. Therefore, a photosensitive resin composition further containing a crosslinkable monomer has been proposed (for example, see Patent Document 4).

Further, by forming a thick interlayer insulating film, the insulation between the wirings in the thickness direction of the layer is improved, and the short circuit of the wiring can be prevented, so that the reliability related to the insulation between the wirings is improved. Further, when the wafer is mounted, since the semiconductor element has a thick interlayer insulating film, the stress applied to the solder bump pads can be alleviated, so that it is difficult to cause connection failure at the time of mounting. Therefore, from the viewpoint of insulation reliability and productivity in mounting a wafer, a film which can form a photosensitive resin composition having a thickness of more than 20 μm is also required. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 09-087366 (Patent Document 3) International Publication No. 2008/010521 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2003 -215802

[Problems to be Solved by the Invention] In particular, in the production of a package substrate, it is difficult to form a resist pattern having an L/S (line width/gap width) of 10/10 (unit: μm) or less. Therefore, it is strongly required to lower the resolution of the resist pattern in units of 1 μm to improve the resolution.

However, the photosensitive resin composition described in the above-mentioned prior art is excellent in insulation reliability and the like, but on the other hand, it is difficult to increase the resolution at the time of thick film formation. For example, in the photosensitive resin composition described in Patent Document 2, when the thickness of the coating film is 50 μm, the gap width is about 40 μm, which is insufficient for a highly integrated semiconductor element. Further, in the photosensitive resin composition described in Patent Document 3, sufficient heat resistance may not be exhibited. Further, in the photosensitive resin composition described in Patent Document 1 or Patent Document 4, when the thickness of the coating film is 10 μm, good resolution with a gap width of about 5 μm can be obtained, but in the case of thick film formation Unable to get good parsing.

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a resist pattern excellent in resolution and heat resistance even when a photosensitive layer having a thickness of more than 20 μm is formed. membrane. Further, another object of the present disclosure is to provide a cured product obtained by using a photosensitive layer in the dry film, a semiconductor device using the cured product, and a method of forming a resist pattern using the dry film. [Means for solving the problem]

The dry film of the present disclosure comprises: a support, an oxime resin layer or an alkyd resin layer, and a photosensitive layer; the photosensitive layer contains (A) component: a resin having a phenolic hydroxyl group; and (B) component: having a fragrance selected from the group consisting of a compound having at least one of a group consisting of a ring, a heterocyclic ring and an alicyclic ring and having a methylol group or an alkoxyalkyl group, and a component (C) having two or more selected from the group consisting of acryloxy group and methacryl group An aliphatic compound having one or more functional groups of a decyloxy group, a glycidoxy group, and a hydroxyl group; and a component (D): a photo-sensitive acid generator.

The photosensitive layer may have a thickness of less than 50 μm.

The photosensitive layer may contain 20 parts by mass to 70 parts by mass of the component (C) with respect to 100 parts by mass of the component (A).

The component (C) may have three or more of the functional groups.

The present disclosure provides a cured product obtained using a photosensitive layer in the dry film. Further, the present disclosure provides a semiconductor device including the cured product as a surface protective film or an interlayer insulating film.

Further, the present disclosure provides a method of forming a resist pattern, comprising: a step of forming a photosensitive layer on a substrate using a dry film; exposing the photosensitive layer to a prescribed pattern, and performing a heat treatment after exposure A step of developing the heat-treated photosensitive layer and subjecting the obtained resin pattern to heat treatment. [Effects of the Invention]

According to the dry film of the present disclosure, even when a photosensitive layer having a thickness of more than 20 μm is formed, a resist pattern excellent in resolution and heat resistance can be formed. Further, according to the present disclosure, it is possible to provide a cured product obtained by using a photosensitive layer in the dry film, a semiconductor device using the cured product, and a method of forming a resist pattern using the dry film.

Hereinafter, an embodiment of the present disclosure will be specifically described with reference to the drawings, but the present disclosure is not limited thereto. In the following description, the same or corresponding components are designated by the same reference numerals, and the repeated description is omitted.

In the present specification, the term "EO modification" means a compound having a (poly)oxyethyl group, and the term "PO modification" means a compound having a (poly)oxypropion group. Here, the term "poly(oxy)oxy) means at least one of an oxygen-extended ethyl group or a polyoxyethylene group in which two or more ethyl groups are bonded by an ether bond. The term "poly(oxy)oxypropyl" refers to at least one of an oxygen-extended propyl group or a polyoxyl-propyl group in which two or more exopropyl groups are linked by an ether bond.

In addition, in the present specification, the term "step" is not only an independent step, but in the case where it cannot be clearly distinguished from other steps, it is included in the present term as long as the intended effect of the step can be achieved. In addition, in the present specification, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. Further, in the numerical range described in the specification, the upper limit or the lower limit of the numerical range of a certain stage may be replaced with the upper limit or the lower limit of the numerical range of the other stage. Further, in the numerical ranges described in the specification, the upper or lower limit of the numerical range may be replaced with the value shown in the embodiment. In addition, in this specification, the term "layer" includes a structure formed on a part of a surface in addition to a structure formed in a shape of the entire surface in a plan view.

In the present specification, when a plurality of substances corresponding to the respective components are present in the composition, the content of each component in the composition means the total of the plurality of substances present in the composition unless otherwise specified. the amount.

[Dry Film] The dry film of the present embodiment will be described with reference to Fig. 1 . FIG. 1 is a schematic cross-sectional view of a dry film 10 of the present embodiment. As shown in FIG. 1, the dry film of the present embodiment is provided with a support 1, an oxime resin layer, an alkyd resin layer 3, and a photosensitive layer 5 in this order. Further, the photosensitive layer 5 may further include a protective layer 7 covering the photosensitive layer 5.

<Photosensitive Resin Composition> The photosensitive resin composition for forming the photosensitive layer 5 of the present embodiment contains one or both of the component (A), the component (B), and the component (C), and the component (D). . Here, the component (A) is a resin having a phenolic hydroxyl group, and the component (B) is at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and has a methylol group or an alkoxy group. The alkyl compound and the component (C) are an aliphatic compound having two or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group, and the component (D) is light. Inductive acid generator. Further, the photosensitive resin composition may further contain: (E) component: solvent, (F) component: inorganic filler, (G) component: decane coupling agent, (H) component: sensitizer, and (I) component. : Amine, (J) component: organic peroxide, (K) component: leveling agent, etc.

The reason why the resin pattern having excellent resolution and heat resistance can be formed by the above-mentioned photosensitive resin composition is as follows. When the component (C) is contained, the solubility of the component (A) in the developer is significantly higher than that of the component (C) in the unexposed portion. When the component (B) is contained, the hydroxymethyl group or the alkoxyalkyl group in the component (B) is reacted with the phenolic hydroxyl group of the component (A) in the exposed portion by the acid generated by the component (D), and the photosensitive layer is exposed. The solubility of the resin composition in the developer is greatly lowered. When both the component (B) and the component (C) are contained, the methylol group or the alkoxyalkyl group in the component (B) may be reacted together with the component (C). By including the component (B) and/or the component (C), sufficient resolution can be obtained due to a significant difference in solubility of the unexposed portion and the exposed portion to the developer during development. Further, due to the structure of the component (C), the photosensitive resin composition can form a negative pattern even if the component (B) is not contained. In addition, the heat resistance of the resin pattern can be improved by including either of the component (B) and the component (C). However, from the viewpoint of forming a negative pattern having higher heat resistance, the photosensitive resin composition is also Both the component (B) and the component (C) may be contained. For this reason, the inventors of the present invention have estimated that the reaction of the component (B) with the component (C) or the component (A) can be further carried out by heat treatment of the resin pattern after development to obtain a cured product having sufficient heat resistance. .

<Component (A)> The resin having a phenolic hydroxyl group as the component (A) is not particularly limited, and may be a resin which can be dissolved in an alkaline aqueous solution or a novolak resin. Such a novolak resin can be obtained by condensing a phenol with an aldehyde in the presence of a catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-. Butyl phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-dimethyl Phenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, and the like.

Further, examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

Specific examples of such a novolak resin include a phenol/formaldehyde condensed novolac resin, a cresol/formaldehyde condensed novolac resin, a phenol-naphthol/formaldehyde condensed novolac resin, and the like.

Further, examples of the component (A) other than the novolac resin include polyhydroxystyrene and a copolymer thereof, a phenol-benzene dimethanol condensation resin, a cresol-benzene dimethanol condensation resin, and phenol-dicyclopentadiene. Condensation resin, etc. The component (A) may be used alone or in combination of two or more. The component (A) other than the novolak resin may be less than 50% by mass, 30% by mass or less, 10% by mass or less, or 5% by mass or less based on the total amount of the component (A). Or 1% by mass or less. Further, the component (A) other than the novolak resin may not be substantially contained.

The weight average molecular weight of the component (A) may be 100,000 or less, 1,000 to 80,000, 2,000 to 50,000, and 2,000 to 20,000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance, and the like of the obtained resin pattern. Or 5000~15000. The "weight average molecular weight" refers to a value measured by a gel permeation chromatography (GPC) method using a calibration curve of standard polystyrene, and more specifically, as a GPC measuring device, a pump is used (Hitachi Manufacturing Co., Ltd. has limited shares). Manufactured by the company, L-6200 type), pipe column (TSKgel-G5000HXL and TSKgel-G2000HXL, manufactured by Tosoh Co., Ltd., trade name) and detector (manufactured by Hitachi, Ltd., L-3300RI type) As a washing liquid, it was measured using tetrahydrofuran under the conditions of a temperature of 30 ° C and a flow rate of 1.0 mL / min.

In the photosensitive resin composition, the total amount of the photosensitive resin composition (excluding the component (E) when the component (E) is used) is 100 parts by mass, and the content of the component (A) may be 30. Parts by mass to 90 parts by mass, or 40 parts by mass to 80 parts by mass. When the content of the component (A) is within the above range, the film formed using the obtained photosensitive resin composition tends to be more excellent in developability by an aqueous alkaline solution.

<Component (B)> The photosensitive resin composition may contain, as the component (B), at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having a hydroxyl group. Methyl or alkoxyalkyl. Here, the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring refers to a cyclic group having at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), and examples thereof include a pyridine ring, an imidazole ring, and a pyrrole group. A ketone ring, an oxazolidinone ring, an imidazolidinone ring, and a pyrimidinone ring. In addition, the alicyclic ring means a cyclic hydrocarbon group which does not have aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), and examples thereof include a cyclopropane ring, a cyclobutane ring, and a cyclopentane ring. Cyclohexane ring. The alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group via an oxygen atom. Further, the two alkyl groups may be the same or different from each other. The alkyl group is, for example, an alkyl group having 1 to 10 carbon atoms.

When the photosensitive layer formed by the resin pattern is cured and cured by the component (B), the component (B) reacts with the component (A) to form a crosslinked structure, thereby preventing the resin pattern from being weakened and the resin. The pattern is deformed and heat resistance is improved. Further, the component (B) can be specifically used: a compound further having a phenolic hydroxyl group, a compound further having a hydroxymethylamino group, or a compound further having an alkoxymethylamino group, excluding the component (A) and (C) )ingredient. The component (B) may be used alone or in combination of two or more.

As described later, the component (D) is contained in the photosensitive resin composition, and an acid is generated by irradiation with actinic rays or the like. The alkoxyalkyl group in the component (B) or the alkoxyalkyl group in the component (B) and the component (A) are subjected to dealcoholization by the catalytic action of the generated acid. The reaction, whereby a negative pattern can be formed. Further, the hydroxymethyl group in the component (B) or the methylol group in the component (B) and the component (A) are reacted with dealcoholization by the catalytic action of the generated acid. A negative pattern can be formed.

The "compound having a phenolic hydroxyl group" as the component (B), by having a methylol group or an alkoxyalkyl group, can be reacted not only with the component (C) or the component (A) but also by borrowing The dissolution rate of the unexposed portion when developing from the alkaline aqueous solution is increased, and the resolution is improved. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000, 108 to 2000, or the weight average molecular weight, in view of improving the solubility, the analytical property, the mechanical properties, and the like in the alkaline aqueous solution. 108 to 1500. Further, when a compound having a low molecular weight is difficult to measure by the method for measuring the weight average molecular weight, the molecular weight may be measured by another method, and the average value thereof may be calculated.

As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but the effect of promoting dissolution of the unexposed portion is excellent in balance with the effect of preventing melting during curing (heat treatment) of the resin pattern after development. Further, it may be a compound represented by the following formula (1). [Chemical 1]

In the formula (1), Z represents a single bond or a divalent organic group, and R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ²⁶ and R ²⁷ each independently represent a monovalent organic group, a and b each independently represents an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. Here, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group; and a phenyl group. An aryl group having 6 to 30 carbon atoms; a group obtained by substituting a part or all of hydrogen atoms of the hydrocarbon groups with a halogen atom such as a fluorine atom. When a plurality of R ²⁴ to R ²⁷ are present, they may be the same or different from each other.

The compound represented by the formula (1) may also be a compound represented by the following formula (2). [Chemical 2]

In the formula (2), X ¹ represents a single bond or a divalent organic group, and a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

Further, as the compound further having a phenolic hydroxyl group, a compound represented by the following formula (3) can be used. [Chemical 3]

In the formula (3), a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

Further, in the formula (1), the compound in which Z is a single bond is a biphenyldiol (dihydroxybiphenyl) derivative. Further, examples of the divalent organic group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylidene group and a propyl group; and an ethylene group having 2 to 10 carbon atoms. An alkylene group; a aryl group having 6 to 30 carbon atoms such as a phenyl group; a group obtained by substituting a part or the whole of a hydrogen atom of the hydrocarbon group with a halogen atom such as a fluorine atom; a sulfonyl group; ; ether bond; thioether bond; guanamine bond. In the above, Z may be a divalent organic group represented by the following formula (4). [Chemical 4]

In the formula (4), X ² represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylene group (for example, an alkylene group having 2 to 10 carbon atoms), and A group obtained by substituting a part or all of the hydrogen atoms with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond or a guanamine bond. R ²⁸ represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a halogenated alkyl group, and e represents an integer of 1 to 10. The plurality of R ²⁸ and X ² may be the same or different from each other. Here, the halogenated alkyl group means an alkyl group substituted by a halogen atom.

Examples of the compound further having a hydroxymethylamino group include (poly)(N-hydroxymethyl)melamine, (poly)(N-hydroxymethyl)glycolil, and (poly)(N-hydroxymethyl group). Benzyl melamine, (poly) (N-hydroxymethyl) urea, and the like. Further, a nitrogen-containing compound obtained by alkylating all or a part of the hydroxymethylamino group of the compound may be used. Here, examples of the alkyl group as the alkyl ether include a methyl group, an ethyl group, a butyl group, a group obtained by mixing the groups, and the like, and a part of the oligomer component obtained by self-condensation may be contained. . Specific examples thereof include hexa(methoxymethyl)melamine, hexakis(butoxymethyl)melamine, tetrakis(methoxymethyl)glycoluril, tetrakis(butoxymethyl)glycoluril, and tetrakis(methoxy). Methyl) urea and the like.

Specifically, the compound having an alkoxymethylamino group may be a compound represented by the following formula (5) or a compound represented by the following formula (6). [Chemical 5]

In the formula (5), a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). [Chemical 6]

In the formula (6), a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

The component (B) may contain both the compound represented by the formula (5) and the compound represented by the formula (6) from the viewpoint of further excellent characterization and heat resistance. When the component represented by the formula (5) is contained in the component (B), the heat resistance can be further improved, and by including the compound represented by the formula (6), the resolution can be further improved. When the component (B) contains both the compound represented by the formula (5) and the compound represented by the formula (6), the resolution and heat resistance can be improved at a higher level and balance.

The content of the compound represented by the formula (5) in the component (B) is 20% by mass or more and 35 mass based on the total amount of the component (B). % or more, 45% by mass or more, or 60% by mass or more, and may be 100% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less. The content of the compound represented by the formula (6) in the component (B) is preferably 5 mass% or more and 10 mass based on the total amount of the component (B), from the viewpoint of further improvement in the resolution and heat resistance. % or more or 15% by mass or more, and may be 100% by mass or less, 80% by mass or less, 65% by mass or less, or 55% by mass or less.

The content of the component (B) may be 5 parts by mass to 60 parts by mass, 10 parts by mass to 45 parts by mass, or 10 parts by mass to 35 parts by mass per 100 parts by mass of the component (A). When the content of the component (B) is 5 parts by mass or more, the reaction in the exposed portion is sufficient, the resolution is less likely to be lowered, and the chemical resistance and the heat resistance tend to be good. When the amount is 60 parts by mass or less, It is easy to form a photosensitive resin composition on a desired support, and the analytical property tends to be good.

<Component (C)> Component (C): an aliphatic compound having two or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group, may be composed of a photosensitive resin. The adhesion of the object to the support, that is, the viscosity, becomes good. Further, the dissolution rate of the unexposed portion when developing by the alkaline aqueous solution can be increased, and the resolution can be improved. Further, the component (C) may have two or more different functional groups, and may have two or more functional groups. From the viewpoint of viscosity and solubility in an aqueous alkaline solution, the molecular weight of the component (C) may be 92 to 2000, 106 to 1,500, or 134 to 1300 in terms of weight average molecular weight in view of balance. When the compound having a low molecular weight is difficult to measure by the method for measuring the weight average molecular weight, the molecular weight may be measured by another method, and the average value thereof may be calculated. In addition, the "aliphatic compound" means a compound whose main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic hetero ring.

The functional group as the component (C) may be a glycidoxy group, an acryloxy group or a methacryloxy group, or a glycidoxy group or an acrylonitrile group, or may be an acryloxy group. Further, the component (C) may have three or more of the above functional groups. The upper limit of the number of functional groups is not particularly limited and is, for example, 12. Specific examples of the component (C) include a compound represented by the following formula (7) to formula (10). [Chemistry 7] [化8] [Chemistry 9] [化10] [11] [化12] [Chemistry 13]

In the general formulae (7) to (10), R ¹ , R ⁵ , R ¹⁶ and R ¹⁹ each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the formula (11), and R ²¹ And represents a hydroxyl group, a glycidoxy group, an acryloxy group or a methacryloxy group, R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ each represent a hydroxyl group, a glycidoxy group, an acryloxy group, a methacryloxy group, a group represented by the formula (12) or a pass. In the group represented by the formula (13), R ²² and R ²³ each represent a hydroxyl group, a glycidoxy group, an acryloxy group or a methacryloxy group, and n and m are each an integer of from 1 to 10.

Examples of the compound having a glycidoxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl glycol. Ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, dipentaerythritol hexahydroglyceryl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, Trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerol triglycidyl ether, glycerol propoxy triglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, 1,2-ring Diglycidyl hexanedicarboxylate and the like. These glycidyloxy group-containing compounds may be used alone or in combination of two or more.

Among the compounds having a glycidyloxy group, trishydroxymethylethane triglycidyl ether or trimethylolpropane triglycidyl ether may be used in terms of excellent sensitivity and resolution.

The glycidyloxy group-containing compound can be, for example, Epolight 40E, Epolight 100E, Epolight 70P, Epolight 200P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (above, manufactured by Kyoeisha Chemical Co., Ltd., product name), alkane Base type epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., product name), DENACOL EX-212L, DENACOL EX-214L, DENACOL EX-216L, DENACOL EX-321L and DENACOL EX-850L (above Nagase chemteX Co., Ltd. manufactures, product name) is commercially available.

Examples of the compound having a propylene fluorenyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and EO-modified di-trimethylolpropane tetraacrylate. PO modified di-trimethylolpropane tetraacrylate, di-trimethylolpropane tetraacrylate, EO modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO modified pentaerythritol Triacrylate, PO modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO modified trimethylolpropane acrylate, PO modified trimethylolpropane acrylate, trimethylolpropane acrylate, EO modification Triglyceride, PO modified glycerin triacrylate, glycerin triacrylate, and the like. These compounds having an acryloxy group may be used singly or in combination of two or more.

Examples of the compound having a methacryloxycarbonyl group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexa-methacrylate, and EO-modified bis-three. Hydroxymethylpropane tetramethacrylate, PO modified di-trimethylolpropane tetramethacrylate, di-trimethylolpropane tetramethacrylate, EO modified pentaerythritol tetramethacrylate, PO Modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO modified pentaerythritol trimethacrylate, PO modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO modified trimethylol Propane methacrylate, PO modified trimethylolpropane methacrylate, trimethylolpropane methacrylate, EO modified glycerol trimethacrylate, PO modified glycerol trimethacrylate, glycerin Trimethacrylate and the like. These compounds having a methacryloxy group may be used singly or in combination of two or more.

Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. These compounds having a hydroxyl group may be used singly or in combination of two or more.

The content of the component (C) may be 20 parts by mass to 70 parts by mass, 25 parts by mass to 65 parts by mass, or 35 parts by mass to 55 parts by mass per 100 parts by mass of the component (A). When the content of the component (C) is 20 parts by mass or more, the crosslinking in the exposed portion is sufficient, and the viscosity tends to be sufficient. When the content is 70 parts by mass or less, the photosensitive resin composition is easily formed. The film formation tends to be difficult to reduce the resolution on the desired support.

<Component (D)> The photo-sensitive acid generator as the component (D) is a compound which generates an acid by irradiation with actinic rays or the like. Further, when the component (B) is contained, not only the component (B) reacts with each other but also the component (B) reacts with the component (A) or (C) to form a photosensitive resin. The solubility of the developer to the developer is lowered, whereby a negative pattern can be formed. Further, when the component (C) is a compound having an acryloxy group or a methacryloxy group, a radical of an acryloxy group or a methacryloxy group is also carried out by irradiation with an actinic ray or the like. polymerization.

The component (D) is not particularly limited as long as it is a compound which generates an acid by irradiation with an actinic ray or the like, and examples thereof include an onium salt compound, a halogen-containing compound, a diazoketone compound, an anthraquinone compound, and a sulfonic acid compound. , sulfonium imine compounds, diazomethane compounds, and the like. Among them, an onium salt compound or a sulfonium imide compound can be used from the viewpoint of availability. In particular, when a solvent is used as the component (E), an onium salt compound can be used from the viewpoint of solubility of the solvent. Hereinafter, a specific example thereof will be described.

Onium salt compound: Examples of the onium salt compound include a phosphonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt, and a pyridinium salt. Specific examples of the onium salt compound include diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, and diphenylsulfonium hexafluorophosphate. a diarylsulfonium salt such as diphenylphosphonium tetrafluoroborate; a triarylsulfonium salt such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate or triphenylsulfonium hexafluoroantimonate; Salt; 4-tert-butylphenyl-diphenylfluorene trifluoromethanesulfonate; 4-tert-butylphenyl-diphenylphosphonium p-toluenesulfonate; 4,7-di-n-butoxy Naphthyltetrahydrothiophene trifluoromethanesulfonate and the like.

Sulfonimide compound: Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)butanediamine, N-(trifluoromethanesulfonyloxy)o-phenylene Mercaptoimine, N-(trifluoromethanesulfonyloxy)diphenylmethylene iodide, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene- 2,3-dimethylimine, N-(trifluoromethanesulfonyloxy)naphthoquinone imine, N-(p-toluenesulfonyloxy)-1,8-naphthyldimethylimine, N-(10-camphorsulfonyloxy)-1,8-naphthyldimethylimine and the like.

In the present embodiment, the component (D) may have a triflate group, a hexafluoroantimonate group, a hexafluorophosphate group or a tetrafluoro group in terms of more excellent sensitivity and resolution. Borate-based compound. Further, the component (D) may be used singly or in combination of two or more.

The content of the component (D) may be from 0.1 part by mass to 15 parts by mass, or from 0.3 part by mass to 10 parts per 100 parts by mass of the component (A), from the viewpoint of further improving the sensitivity, the analytical property, the pattern shape and the like. Parts by mass.

<(E) Component> In order to improve the handleability of the photosensitive resin composition, or to adjust the viscosity and storage stability, the photosensitive resin composition may further contain a solvent as the component (E). The component (E) may be an organic solvent. The organic solvent is not particularly limited as long as it exhibits the above properties, and examples thereof include ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. Alkyl ether acetates; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ethers; propylene glycol dimethyl ether, propylene glycol diethyl ether, Propylene glycol dialkyl ether such as propylene glycol dipropyl ether or propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl Propylene glycol monoalkyl ether acetate such as ether acetate; cellosolve such as ethyl cellosolve or butyl cellosolve: carbitol such as butyl carbitol; methyl lactate, ethyl lactate, n-propyl lactate , lactate such as isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, An aliphatic carboxylic acid ester such as n-butyl propionate or isobutyl propionate; methyl 3-methoxypropionate, 3-methyl Other esters such as ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; a ketone such as butanone, 2-heptanone, 3-heptanone, 4-heptanone or cyclohexanone; N,N-dimethylformamide, N-methylacetamide, N,N-dimethyl a decylamine such as acetamide or N-methylpyrrolidone; or a lactone such as γ-butyrolactone. These organic solvents may be used alone or in combination of two or more.

The content of the component (E) may be 30 parts by mass to 200 parts by mass, 50 parts by mass to 120 parts by mass, or 60 parts by mass to 100 parts by mass based on the total amount of the photosensitive resin composition other than the component (E). 120 parts by mass.

<(F) component> The photosensitive resin composition contains the inorganic filler as the component (F), and according to the content of the component (F), the thermal expansion coefficient of the cured product obtained by heating the photosensitive layer after the resin pattern formation can be reduced. . The component (F) may be used alone or in combination of two or more. The inorganic filler can be dispersed to a maximum particle diameter of 2 μm or less when dispersed in the resin composition.

Examples of the inorganic filler include aluminum compounds such as alumina and aluminum hydroxide; alkali metal compounds; alkaline earth metal compounds such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, and magnesium hydroxide; talc and mica; Mineral compounds derived from minerals; molten spherical cerium oxide, molten pulverized cerium oxide, aerosolized cerium oxide, cerium dioxide such as sol-gel cerium oxide. These may be pulverized by a pulverizer, classified according to the case, and dispersed at a maximum particle diameter of 2 μm or less.

As the kind of the inorganic filler, any kind may be used, but it may be cerium oxide. Further, the thermal expansion coefficient of the cerium oxide may be 5.0 × 10 ^-6 /° C or less, and from the viewpoint of the particle diameter, it may be a molten spherical cerium oxide, an aerosolized cerium oxide, or a sol-gel cerium oxide. Cerium oxide can also be fumed cerium oxide or sol-gel cerium oxide. As the cerium oxide, cerium oxide (nano-cerium oxide) having an average primary particle diameter of 5 nm to 100 nm can be used. These photosensitive resin compositions can be dispersed with a maximum particle diameter of 2 μm or less. In this case, a decane coupling agent can be used in order to disperse in a resin in a state which does not aggregate.

When measuring the particle diameter of each inorganic filler, a well-known particle size distribution meter can be used. For example, the maximum particle diameter of the inorganic filler is the maximum particle diameter of the inorganic filler in a state of being dispersed in the photosensitive resin composition, and is a value measured as follows. First, after the photosensitive resin composition was diluted (or dissolved) to 1000 times (volume ratio) by methyl ethyl ketone, a submicron particle analyzer (manufactured by Beckman Coulter Co., Ltd., The product name and model number: N5), the particles dispersed in the solvent were measured at a refractive index of 1.38 according to the international standard specification ISO 13321, and the particle diameter when the cumulative value in the particle size distribution was 99.9% (volume basis) was defined as the maximum particle diameter. Further, even if the photosensitive layer or the cured product of the photosensitive resin composition provided on the support is diluted (or dissolved) to 1000 times (volume ratio) using a solvent as described above, the secondary microparticles are used. The analyzer performs the measurement.

The content of the component (F) may be 1% by mass or more and 70% by mass or less, or may be 3% by mass or more and 65% by mass or less based on the total amount of the photosensitive resin composition other than the component (E).

The inorganic filler used in the present embodiment may have an average primary particle diameter of 100 nm or less or 80 nm or less, and particularly preferably 50 nm or less from the viewpoint of sensitivity. When the average primary particle diameter is 100 nm or less, there is a tendency that the photosensitive resin composition is less likely to be cloudy, and light such as exposure actinic rays is easily transmitted through the resin composition, and the unexposed portion is easily removed, and the resolution is hardly lowered.

The average primary particle diameter is a value obtained by converting a specific surface area according to a Brunauer-Emmett-Teller (BET).

<(G) Component> The photosensitive resin composition may contain a decane coupling agent as the component (G). By containing the component (G), the adhesion strength between the photosensitive layer and the substrate after the resin pattern formation can be improved.

As the component (G), those which are generally available can be used, and for example, alkyl decane, alkoxy decane, vinyl decane, epoxy decane, amino decane, acryl decyl decane, methacryl decyl decane can be used. Mercaptodecane, thioether decane, isocyanate decane, thiodecane, styryl decane, alkyl chlorodecane, and the like.

Specific examples of the component (G) include methyltrimethoxydecane, dimethyldimethoxydecane, trimethylmethoxydecane, methyltriethoxydecane, and methyltriphenoxydecane. Ethyltrimethoxydecane, n-propyltrimethoxydecane, diisopropyldimethoxydecane, isobutyltrimethoxydecane, diisobutyldimethoxydecane, isobutyltriethoxy Decane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, cyclohexylmethyldimethoxydecane, n-octyltriethoxydecane, n-dodecylmethoxydecane, phenyltrimethoxy Baseline, diphenyldimethoxydecane, triphenylstanol, methyltrichlorodecane, dimethyldichlorodecane, trimethylchlorodecane, n-octyldimethylchlorodecane, tetraethoxy Decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-amine Ethylethyl)aminopropylmethyldimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxy Methyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, bis(3-(triethoxydecyl)alkyl )propyl)disulfide, bis(3-(triethoxydecyl)propyl)tetrasulfide, vinyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane , vinyl triisopropoxy decane, allyl trimethoxy decane, diallyldimethyl decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene decyloxy Propylmethyldimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3 - mercaptopropyltriethoxydecane, N-(1,3-dimethylbutylidene)-3-aminopropyltriethoxydecane, aminodecane, and the like.

The component (G) may be an epoxy decane having one or more glycidoxy groups, or an epoxy decane having a trimethoxydecyl group or a triethoxydecyl group. Further, propylene decyl decane or methacryl decyl decane can be used.

The content of the component (G) may be from 1 part by mass to 20 parts by mass, or from 3 parts by mass to 10 parts by mass, per 100 parts by mass of the component (A).

<(H) component> The photosensitive resin composition can contain a sensitizer as (H) component. Examples of the sensitizer include 9,10-dibutoxyfluorene. Further, the component (H) may be used singly or in combination of two or more. By containing the (H) component, the sensitivity of the photosensitive resin composition can be improved.

The content of the component (H) may be from 0.01 part by mass to 1.5 parts by mass, or from 0.05 part by mass to 0.5 part by mass, per 100 parts by mass of the component (A).

Further, the photosensitive resin composition may contain a phenolic low molecular compound having a molecular weight of less than 1,000 (hereinafter referred to as "phenol compound (a)") in addition to the component (A). For example, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl) 1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-double [ 1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, 1,1,2,2 - Tetrakis(4-hydroxyphenyl)ethane and the like. The phenol compound (a) can be contained in the range of 0% by mass to 40% by mass, particularly preferably 0% by mass to 30% by mass based on the component (A).

Further, the photosensitive resin composition may contain other components than the above components. Examples of the other component include an inhibitor accompanying the reaction of irradiation with actinic rays, an adhesion aid, and the like.

<Support> As the support, for example, a polyester such as polyethylene terephthalate or a polymer film having heat resistance and solvent resistance such as polypropylene or polyethylene can be used. Further, the polymer film may be used by using one as a support and the other as a protective layer, which is laminated on both sides of the photosensitive layer so as to sandwich the photosensitive layer.

<Anthrone resin layer or alkyd resin layer> The dry film of the present embodiment is provided with an fluorenone resin layer or an alkyd resin layer on the support. Thereby, when the photosensitive layer is laminated on the substrate, the photosensitive layer is easily transferred to the substrate, and in particular, the resolution can be improved. In the dry film 10, an fluorenone resin layer or an alkyd resin layer 3 is formed on the support 1. Further, when the support 1 and the photosensitive layer 5 are peeled off, the oxime resin layer or the alkyd resin layer 3 may be provided on the support 1 . That is, it can be said that the support 1 and the fluorenone resin layer or the alkyd resin layer 3 may or may not be integrated. At least one surface of the support may be treated by an fluorenone resin or an alkyd resin. Here, the treatment by an fluorenone resin or an alkyd resin means a chemical treatment in which an fluorenone resin or an alkyd resin is thinly coated on the surface of a support. Examples of the anthrone resin include an anthrone modified resin, polydimethylsiloxane, and the like.

When the fluorenone resin or the alkyd resin is applied onto the support, it can be applied thinly to the extent that the effect of demolding can be obtained. After coating, the fluorenone resin or alkyd resin can be fixed to the support by heat or ultraviolet (UV) treatment. The undercoat layer may be applied to the support before the coating of the fluorenone resin or the alkyd resin.

Further, from the viewpoint of the releasability (release property) of the photosensitive layer, the 180° C peel strength at 23° C. of the fluorenone resin-treated surface or the alkyd-treated surface of the support may be 5 gf/inch to 300 gf. /inch (1.97 gf/cm to 118 gf/cm or 19.3×10 ^-3 N/cm to 1156.4×10 ^-3 N/cm), 5 gf/inch to 200 gf/inch (1.97 gf/cm to 78.7 gf/ Cm or 19.3 × 10 ^-3 N / cm ~ 771.3 × 10 ^-3 N / cm), or 100 gf / inch ~ 200 gf / inch (39.4 gf / cm ~ 78.7 gf / cm or 386.1 × 10 ^-3 N / cm ~771.3×10 ^-3 N/cm). The 180° peel strength can be measured by a usual method (for example, according to the method of JIS K6854-2, etc.) using a tape (manufactured by Nitto Denko Corporation, product name: "NITTO31B").

The thickness of the fluorenone resin layer or the alkyd resin layer may be from about 0.005 μm to 1 μm, and particularly from 0.01 μm to 0.1 μm. When the thickness of the fluorenone resin layer or the alkyd resin layer is in the above range, the adhesion between the support and the fluorenone resin layer or the alkyd resin layer is good. Further, the dry film may have both an anthrone resin layer and an alkyd resin layer.

A polyethylene terephthalate (PET) film which is treated with at least one surface by an fluorenone resin or an alkyd resin can be obtained, for example, from a commercial product by the company Teijin Dupont Films Co., Ltd. The product names are "Purex A53", "Purex A70", "Purex A31-25", "Purex A51-25" and "Purex A53-38" ("Purex" is a registered trademark). From the viewpoint of availability, the support in the dry film of the present embodiment may be provided with an fluorenone resin layer on the support.

The support of at least one surface treated with an oxime resin or an alkyd resin may have a thickness of 15 μm to 50 μm, or 25 μm to 40 μm. When the thickness of the support is 15 μm or more, strain at the time of treatment with an oxime resin or an alkyd resin is hard to remain, and the occurrence of curl is suppressed when the dry film is wound into a roll. When the thickness of the support is 50 μm or less, there is a tendency that bubbles are less likely to be caught between the substrate and the photosensitive layer when the pressure-sensitive adhesive layer is laminated on the substrate.

<Protective layer> As the protective layer 7, for example, a polymer film such as polyester such as polyethylene, polypropylene or polyethylene terephthalate can be used. Further, as with the support, a polymer film treated by an fluorenone resin or an alkyd resin can be used. From the viewpoint of the flexibility when the dry film is wound into a roll, the protective layer may be a polyethylene film. Further, in order to reduce the depression of the surface of the photosensitive layer, the protective layer may be a film of a low fisheye.

The protective layer 7 may have a thickness of 10 μm to 100 μm or 15 μm to 80 μm.

The photosensitive layer may be coated on the fluorenone resin-treated surface or the alkyd-treated surface of the support, the fluorenone resin layer or the alkyd resin layer, or the protective layer on the support. Formed on the top. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method. The thickness of the photosensitive layer varies depending on the application, and it is particularly preferable to dry the photosensitive layer to 1 μm in terms of the film forming property of the photosensitive layer of the dry film on the support and the resolution of the photosensitive layer. ~100 μm, 3 μm to 60 μm, 5 μm to 50 μm, 5 μm or more and less than 50 μm, or 5 μm to 25 μm.

[Method of Forming Resist Pattern] Next, a method of forming the resist pattern of the present embodiment will be described.

First, a photosensitive layer is formed using the dry film on a substrate on which a resist pattern is to be formed (a copper foil with a resin, a copper foil laminate, a tantalum wafer with a metal sputter film, an alumina substrate, or the like). .

Then, the photosensitive layer is exposed to a predetermined pattern via a predetermined mask pattern. Examples of the actinic ray used for the exposure include visible light rays from a g-ray stepper or the like; ultraviolet rays from a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an i-ray stepper, etc.; an electron beam; a laser Light, etc. The exposure amount is appropriately selected depending on the light source used and the thickness of the photosensitive layer, for example, when irradiating ultraviolet rays from a high pressure mercury lamp, when the thickness of the photosensitive layer is from 10 μm to 50 μm, the exposure amount is from 100 mJ/cm ² to 5000 mJ. /cm ² or so. Further, when the photosensitive layer is exposed, the photosensitive layer may be exposed through the support, or the support may be peeled off and the photosensitive layer may be exposed.

Then, heat treatment (post-exposure baking) is performed after the exposure. By performing post-exposure baking, the hardening reaction of the (A) component and (B) component by the acid by the photo-sensitive acid generator can be accelerated. The conditions for post-exposure baking vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, and can be usually heated at 70 to 150 ° C for 1 minute to 60 minutes, or at 80 ° C. Heat at 120 ° C for 1 minute to 60 minutes.

Then, the photosensitive layer subjected to the post-exposure baking is developed by an alkaline developing solution, and the region of the unexposed portion is dissolved and removed, whereby a desired resin pattern can be obtained. Examples of the development method at this time include a shower development method, a spray development method, a immersion development method, and a liquid coating development method. The development conditions are usually from 1 minute to 10 minutes at 20 to 40 °C.

The alkaline developing solution is, for example, a basic compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or choline dissolved in water at a concentration of about 1% by mass to 10% by mass. An alkaline aqueous solution or an alkaline aqueous solution such as ammonia water is obtained. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution. Further, after development by the alkaline developing solution, it is washed with water and dried. In terms of excellent analytical properties, the alkaline developing solution may be an aqueous solution of tetramethylammonium hydroxide.

Then, the obtained resin pattern is heat-treated in order to exhibit the properties of the insulating film, whereby a cured product (resist pattern) of the photosensitive resin composition is obtained. The curing condition is not particularly limited, and the resin pattern can be cured by heating at 50 ° C to 250 ° C for 30 minutes to 10 hours depending on the use of the cured product.

Further, in order to sufficiently perform hardening or to prevent deformation of the obtained resin pattern, heating may be performed in two stages. For example, it may be heated in the first stage at 50 ° C to 120 ° C for 5 minutes to 2 hours, and then in the second stage, heated at 80 ° C to 200 ° C for 10 minutes to 10 hours to be hardened.

In the case of the hardening conditions, the heating device is not particularly limited, and a general oven, an infrared oven, or the like can be used.

[Multilayer Printed Wiring Board] The cured product containing the photosensitive resin composition can be preferably used, for example, as a solder resist and/or an interlayer insulating film in a multilayer printed wiring board. 2(a) to 2(f) are views showing a method of manufacturing a multilayer printed wiring board including the cured product of the present embodiment as a solder resist and/or an interlayer insulating film. The multilayer printed wiring board 100A shown in FIG. 2(f) has a wiring pattern on the front surface and inside. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A according to the embodiment of the present disclosure will be briefly described with reference to FIGS. 2(a) to 2(f).

First, an interlayer insulating film 103 is formed on both surfaces of a substrate 101 having a wiring pattern 102 on its surface (see FIG. 2(a)). The interlayer insulating film 103 is formed by preparing the dry film in advance and attaching the photosensitive layer of the dry film to the surface of the substrate 101 using a bonding machine. Then, the opening portion 104 is formed using a Yttrium Aluminum Garnet (YAG) laser or a carbon dioxide laser at a portion that is required to be electrically connected to the outside (see FIG. 2(b)). The slag (residue) around the opening 104 is removed by the desmear treatment. Then, the seed layer 105 is formed by electroless plating (see FIG. 2(c)). A photosensitive layer containing a semi-additive photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a resin pattern 106 (see FIG. 2(d)). An adhesion layer, for example, a titanium layer having a thickness of about 30 nm is formed on the seed layer, and then a Cu layer having a thickness of about 100 nm is formed. The adhesion layers can be formed by sputtering. Then, the wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by the plating method, and after removing the resin pattern 106 by the stripping liquid, the seed layer 105 is removed by etching (refer to FIG. 2(e) ). By repeating the above operation, the solder resist 108 containing the cured product of the photosensitive resin composition is formed on the outermost surface, whereby the multilayer printed wiring board 100A can be produced (see FIG. 2(f)).

The thus obtained multilayer printed wiring board 100A can mount semiconductor elements at corresponding portions and ensure electrical connection. [Examples]

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited by the examples. In addition, the parts in the following examples and comparative examples are used in the meaning of a mass part unless otherwise indicated.

<Preparation of photosensitive resin composition> With respect to 100 parts by mass of the novolac resin (A-1 to A-2), it is prepared in a predetermined amount as shown in Tables 1 and 2: having two or more methylol groups or alkoxy groups a compound (B-1 to B-3) of an alkyl group, or a compound having two or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group (C-1) -C-8, C'-9 to C'-10), photo-sensitive acid generator (D-1), solvent (E-1), and inorganic filler (F-1) to obtain a photosensitive resin composition .

<Preparation of Dry Film> As the support, those in which the fluorenone resin layer or the alkyd resin layer is formed on the support are not formed. The photosensitive resin composition is applied to the support or the fluorenone resin layer or the alkyd resin layer so that the thickness of the photosensitive resin composition becomes uniform, and dried by a hot air convection dryer at 90 ° C After 10 minutes, a photosensitive layer having a thickness after drying as shown in Tables 1 and 2 was formed. A polyethylene film (manufactured by Tamapoly Co., Ltd., product name: NF-15) is attached as a protective layer on the photosensitive layer, or an anthrone resin layer or an alkyd resin on the support layer. On the layer, a dry film obtained by sequentially laminating the photosensitive layer and the protective layer is obtained.

<Release Evaluation> The dry film was laminated on a 6-inch tantalum wafer so that the photosensitive layer of the dry film was brought into contact with the surface of the tantalum while the protective layer was peeled off. After the support is peeled off, the surface of the support and the surface of the germanium wafer are observed, and the film formed on the germanium wafer is set to "A", which will be on the support (or an anthrone resin layer or an alkyd resin). On the layer, even if a part of the photosensitive layer is left as "B", the release property is evaluated. Further, lamination was carried out using a heating roll at 120 ° C at a roll speed of 1.0 m/min under a pressure of 0.4 MPa.

<Evaluation of Analytical Property> The dry film was laminated on a 6-inch tantalum wafer so that the protective layer of the dry film was peeled off while the photosensitive layer was in contact with the surface of the crucible. After the support was peeled off, the photosensitive layer was subjected to reduction projection exposure by an i-ray (365 nm) through a mask using an i-ray stepper (manufactured by Canon Co., Ltd., product name: FPA-3000iW). As the mask, a pattern having a width of 1:1 between the exposed portion and the unexposed portion in a range of 2 μm: 2 μm to 30 μm: 30 μm on a scale of 1 μm is used. Further, in the exposure amount is ^{100 mJ / cm 2 ~ 3000 mJ} / cm ² within the range, while each change of 100 mJ / cm ^2, while for reduced projection exposure.

Then, the exposed photosensitive layer was heated at 65 ° C for 1 minute, followed by heating at 95 ° C for 4 minutes (baked after exposure), using a 2.38 mass % aqueous solution of tetramethylammonium hydroxide to correspond to the shortest development time (removal) The immersion was performed twice as long as the shortest time of the unexposed portion, whereby development was performed, and the unexposed portion was removed to carry out development processing. After the development treatment, the formed resin pattern was observed using a metal microscope. In a pattern formed by completely removing the gap portion (unexposed portion) and the line portion (exposure portion) is not formed with defects or defects, the exposure amount is in the range of 100 mJ/cm ² to 3000 mJ/cm ² . The value of the minimum gap width was evaluated as the minimum resolution.

<Evaluation of heat resistance> A dry film having a thickness of 40 μm in the photosensitive layer was produced by the method described above. The protective layer of the dry film was peeled off, and then an exposure machine having a high-pressure mercury lamp (manufactured by ORC MANUFACTURING Co., Ltd., product name: EXM-1201) was used, and the amount of irradiation energy was 3000 mJ/cm ² . Expose the photosensitive layer. The exposed photosensitive layer was heated on a hot plate at 65 ° C for 2 minutes, then at 95 ° C for 8 minutes, and heated by a hot air convection dryer at 180 ° C for 60 minutes to peel off the support. Hardened film. Using a thermomechanical analyzer (manufactured by Seiko Instruments Co., Ltd., product name: TMA/SS6000), the amount of thermal expansion of the cured film when the temperature was raised at a temperature increase rate of 5 ° C/min was measured, and the curve was determined based on the curve. The resulting inflection point is taken as the glass transition temperature Tg. When Tg is 145 ° C or more, heat resistance is excellent, and when Tg is 170 ° C or more, heat resistance is more excellent.

[Table 1] *1: Since the photosensitive layer remains on the support, the pattern cannot be formed. *2: Since the exposed portion of the photosensitive layer was also removed by development, the pattern could not be formed.

[Table 2]

PET-1: polyethylene terephthalate film (manufactured by DuPont Teijin Film Co., Ltd., product name: Purex A53, thickness: 25 μm): a film having an anthrone resin layer formed using an anthrone-modified resin PET-2: polyethylene terephthalate film (manufactured by DuPont Teijin Film Co., Ltd., product name: Purex A70, thickness: 25 μm): an anthrone resin layer formed using polydimethyl siloxane Film PET-3: polyethylene terephthalate film (manufactured by Toray Co., Ltd., product name "FB-40", thickness: 16 μm): no ketone resin layer or alkyd resin Film A-1 of the layer: cresol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., product name: TR4020G, weight average molecular weight: 15300) A-2: cresol novolac resin (Xu Organic Material Industry Co., Ltd.) Manufacturing, product name: TR4080G, weight average molecular weight: 4800) B-1:1, 3,4,6-tetrakis(methoxymethyl) glycoluril (Sanwa Chemical Co., Ltd., product name :MX-270) B-2: Methylated urea resin (Sanhe Chemicals Co., Ltd. Co., Ltd. Manufactured, product name: MX-280) B-3: 4,4'-(1,1,1,3,3,3-hexafluoroisopropylidene) bis[2,6-bis(hydroxyl) Phenol] (Manufactured by Honshu Chemical Industry Co., Ltd., product name: TML-BPAF) C-1: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., product name: ZX-1542 , refer to the following formula (14)) [Chemistry 14] C-2: Trimethylolethane triglycidyl ether (manufactured by Aldrich) C-3: Pentaerythritol polyglycidyl ether (manufactured by Nagase Chemical Co., Ltd., product name: EX-411) C-4: three Hydroxymethylpropane (manufactured by Wako Pure Chemical Industries, Ltd.) C-5: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., product name: TMPTA) C-6: Pentaerythritol triacrylate (Japan) Manufactured by Chemical Pharmaceutical Co., Ltd., product name: PET-30) C-7: Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate DPE-6A) C-8: EO modified three Hydroxymethylpropane trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name: FA-137M) C'-9: 2,2-bis(4-(methylpropenyloxydiethoxy)benzene Propane (manufactured by Hitachi Chemical Co., Ltd., product name: FA-324M, aromatic compound) C'-10: 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (Manufactured by Hitachi Chemical Co., Ltd., product name: FA-320M, aromatic compound) D-1: Triarylsulfonium salt (Sanya Manufactured by San-Apro Co., Ltd., product name: CPI-310B) E-1: methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) F-1: by 3-methyl propylene oxime The propylidene trimethoxydecane was subjected to coupling treatment with an average primary particle size of 15 nm of cerium oxide.

According to Tables 1 and 2, the dry film (Examples 1 to 25) in which the photosensitive layer was formed on the fluorenone resin layer of the support treated with the fluorenone resin, the laminated photosensitive layer and the support were The mold release property is good, the minimum resolution is 10 μm or less, and the Tg is good to 145 ° C or higher. When the photosensitive layer was formed on the support which was not subjected to the fluorenone resin treatment or the alkyd resin treatment, the release properties of the photosensitive layer and the support were deteriorated as in Comparative Example 1 and Comparative Example 2. [Industrial availability]

The dry film of the present invention can be preferably used in forming a solder resist or an interlayer insulating film of a printed wiring board, or a surface protective film (protective film) such as a semiconductor element or an interlayer insulating film (passivation film). In particular, since the photosensitive layer of the dry film of the present invention is excellent in both the resolution and the heat resistance after curing, the dry film of the present invention can be preferably used for a high-density package substrate which is thinned and densified.

1‧‧‧Support
3‧‧‧anthone resin layer or alkyd layer
5‧‧‧Photosensitive layer
7‧‧‧Protective layer
10‧‧‧ dry film
100A‧‧‧Multilayer printed wiring board
101‧‧‧Substrate
102, 107‧‧‧ wiring pattern
103‧‧‧Interlayer insulating film
104‧‧‧ openings
105‧‧‧ seed layer
106‧‧‧ resin pattern
108‧‧‧Soldering agent

1 is a schematic cross-sectional view of a dry film according to an embodiment of the present disclosure. 2(a) to 2(f) are schematic views showing a method of manufacturing a multilayer printed wiring board according to an embodiment of the present disclosure.

1‧‧‧Support

3‧‧‧anthone resin layer or alkyd layer

5‧‧‧Photosensitive layer

7‧‧‧Protective layer

10‧‧‧ dry film

Claims (7)

A dry film comprising a support, an oxime resin layer or an alkyd resin layer, and a photosensitive layer, wherein the photosensitive layer comprises: (A) component: a resin having a phenolic hydroxyl group; (B) a component and (C) Or one or both of the components, wherein the component (B) is at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and has a methylol group or an alkoxyalkyl group. a compound; and the component (C) is an aliphatic compound having two or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group; and a component (D): Photosensitive acid generator. The dry film of claim 1, wherein the photosensitive layer has a thickness of less than 50 μm. The dry film according to the first or second aspect of the invention, wherein the photosensitive layer contains 20 parts by mass to 70 parts by mass of the component (C) with respect to 100 parts by mass of the component (A). The dry film according to any one of claims 1 to 3, wherein the component (C) has three or more of the functional groups. A cured product obtained by using a photosensitive layer in a dry film according to any one of claims 1 to 4. A semiconductor device comprising the cured product according to claim 5, as a surface protective film or an interlayer insulating film. A method of forming a resist pattern, comprising: forming a photosensitive layer on a substrate using a dry film according to any one of claims 1 to 4; exposing the photosensitive layer a step of forming a predetermined pattern and performing heat treatment after exposure; and developing the photosensitive layer after the heat treatment and subjecting the obtained resin pattern to heat treatment.