WO2017126536A1

WO2017126536A1 - Resin composition, resin sheet with support, multilayered printed wiring board, and semiconductor device

Info

Publication number: WO2017126536A1
Application number: PCT/JP2017/001510
Authority: WO
Inventors: 鈴木　卓也; 慎也喜多村; 誠司四家
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2016-01-20
Filing date: 2017-01-18
Publication date: 2017-07-27
Also published as: JPWO2017126536A1; CN108495878B; TW201736963A; CN108495878A; KR20180103819A; TWI770001B; JP6858351B2

Abstract

Provided are: a resin composition which, when used to produce a multilayered printed wiring board, imparts excellent heat resistance and developability; a resin sheet having a support attached thereto; a multilayered printed wiring board including same; and a semiconductor device. The resin composition comprises a compound (A) represented by formula (1) and having an acid value of 30-120 mg-KOH/g, a photocuring initiator (B), and a maleimide compound (C) and/or a blocked isocyanate (D).

Description

Resin composition, resin sheet with support, multilayer printed wiring board, and semiconductor device

The present invention relates to a resin composition, a resin sheet with a support using the same, a multilayer printed wiring board, and a semiconductor device.

2. Description of the Related Art Studies are being actively made to reduce the thickness of laminated boards used in multilayer printed wiring boards by reducing the size and increasing the density of multilayer printed wiring boards. As the thickness is reduced, the insulating layer is also required to be reduced in thickness, and a resin sheet that does not include glass cloth is required. A thermosetting resin is mainly used as a resin composition as a material for the insulating layer, and a hole for obtaining conduction between insulating layers is generally performed by laser processing.
On the other hand, drilling by laser processing has a problem that the processing time becomes longer as the high-density substrate having a larger number of holes is obtained. Therefore, in recent years, there has been a demand for a resin sheet that can be collectively punched in a development process by using a resin composition that is cured by light or the like and dissolved by development.

In such a resin composition, an alkali development type is the mainstream, and an acrylate containing an acid anhydride group or a carboxyl group is used to enable development. For example, Patent Document 1 discloses a composition that can be developed into an aqueous alkaline solution using an acid-modified novolak epoxy acrylate. In patent document 2, the photosensitive resin composition which improved the mechanical characteristic by containing a specific hardening | curing agent is disclosed. Patent Document 3 discloses a photosensitive resin composition for use in an interlayer insulating layer of a multilayer printed wiring board.

Japanese Patent Laid-Open No. 61-243869 JP 2006-047501 A International Publication No. 2015/002071 Pamphlet

However, a cured product using a conventional acrylate cannot provide sufficient physical properties, and there is a limit to the formation of a protective film having high heat resistance and an interlayer insulating layer.
In the composition described in Patent Document 1, the use is limited to an etching resist or a solder resist for printed wiring boards, and the heat resistance is not sufficient for use as an interlayer insulating layer. In the photosensitive resin composition described in Patent Document 2, the glass transition temperature is 115 ° C., and the heat resistance is not sufficient. The photosensitive resin composition described in Patent Document 3 is developed using an organic solvent as a developing solution, and is an aqueous type that does not use an organic solvent such as an alkaline aqueous solution that is mainly used in developing solutions in the field of printed wiring boards. The developability with a developer is not sufficient.

Accordingly, the present invention has been made in view of the above problems, and when used in a multilayer printed wiring board, a resin composition having excellent heat resistance and developability, a resin sheet with a support, and the like To provide a multilayer printed wiring board and a semiconductor device using the above.

Means for Solving the Invention

The present inventors represent a compound (A) represented by the following formula (1) and having an acid value of 30 mgKOH / g or more and 120 mgKOH / g or less, a photocuring initiator (B), a maleimide compound (C) and / or The present inventors have found that the above problems can be solved by using a resin composition containing blocked isocyanate (D), and have completed the present invention.

(In Formula (1), each of the plurality of R ₁ independently represents a hydrogen atom or a methyl group, each of the plurality of R ₂ independently represents a hydrogen atom or a methyl group, and each of the plurality of R ₃ represents, Independently, it represents a substituent represented by the following formula (2), a substituent represented by the following formula (3), or a hydroxy group.

(In formula (3), R ₄ represents a hydrogen atom or a methyl group).

That is, the present invention includes the following contents.
[1] A compound (A) represented by the formula (1) having an acid value of 30 mgKOH / g or more and 120 mgKOH / g or less, a photocuring initiator (B), a maleimide compound (C) and / or a blocked isocyanate. (D) and a resin composition containing.
[2] The resin composition according to [1], further comprising an epoxy resin (E).
[3] The resin composition according to [1] or [2], further including a compound (F) having an ethylenically unsaturated group other than the compound (A).
[4] The resin composition according to any one of [1] to [3], further including an inorganic filler (G).
[5] A resin sheet with a support, comprising the resin composition according to any one of [1] to [4], which is applied to the support.
[6] A multilayer printed wiring board having the resin composition according to any one of [1] to [4].
[7] A semiconductor device comprising the resin composition according to any one of [1] to [4].

ADVANTAGE OF THE INVENTION According to this invention, the resin composition hardened | cured with the active energy ray which is excellent in coating-film property, heat resistance, and developability, and has a suitable property for the protective film of a multilayer printed wiring board, and an interlayer insulation layer, Resin with support Sheets, multilayer printed wiring boards using them, and semiconductor devices can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

In the present specification, “(meth) acryloyl group” means both “acryloyl group” and the corresponding “methacryloyl group”, and “(meth) acrylate” means “acrylate” and the corresponding “methacrylate”. "(Meth) acrylic acid" means both "acrylic acid" and the corresponding "methacrylic acid". Further, in the present embodiment, “resin solid content” or “resin solid content in the resin composition” means a component excluding the solvent and the inorganic filler (G) in the resin composition unless otherwise specified. The “resin solid content of 100 parts by mass” means that the total of the components excluding the solvent and the inorganic filler (G) in the resin composition is 100 parts by mass.

The resin composition of this embodiment contains the compound (A), a photocuring initiator (B), a maleimide compound (C) and / or a blocked isocyanate (D). Hereinafter, each component will be described.

<Compound (A)>
The compound (A) used in the present embodiment is a compound represented by the formula (1). Compound (A) may be used alone, may contain isomers such as structural isomers and stereoisomers, and may be used in appropriate combination of two or more compounds having different structures.

In said formula (1), several R < ₁ > represents a hydrogen atom or a methyl group each independently. Among them, it is preferable to include a viewpoint from hydrogen atoms to improve the reactivity of the photocuring reaction, more preferably all of R ₁ is a hydrogen atom.
Several R < ₂ > represents a hydrogen atom or a methyl group each independently. Among them, preferably comprises a methyl group from the viewpoint of improving the heat resistance of the cured product, and more preferably all of R ₂ is a methyl group.

Several R < ₃ > represents the substituent represented by the said Formula (2), the substituent represented by the said Formula (3), or a hydroxy group each independently. Among these, it is preferable that a hydroxyl group is included from a viewpoint of improving heat resistance. Moreover, in this embodiment, it is also preferable from a viewpoint of improving developability to use the compound (A) containing the substituent represented by said Formula (2) among several R < ₃ >. In the present embodiment, it is also preferable to use the compound (A) containing a substituent represented by the formula (3) among the plurality of R ₃ from the viewpoint of improving heat resistance. In the formula (3), R ₄ represents a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable from the viewpoint of improving the reactivity of the photocuring reaction.

From the viewpoint of improving developability, the plurality of R ₃ have a ratio of the substituent represented by the formula (2) of 20% or more and 85% or less of all the substituents of R ₃ , and the formula (3). Is preferably 5% to 70%, and the hydroxy group is preferably 10% to 75%.

The compound (A) preferably contains at least one of the following compounds (A1) to (A5) because the reactivity of the photocuring reaction, the heat resistance of the cured product and the developability can be improved. More preferably, at least compound (A1) is included, more preferably any two or more of (A1) to (A5) are included, and any one of compound (A1) and compounds (A2) to (A5) is included. More preferably, it contains more than one species. As the compound (A), it is also preferable that at least the compounds (A2) and (A3) are included.

Such compounds may be commercially available, for example, KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR- 6007H (above, trade name, manufactured by Nippon Kayaku Co., Ltd.).

In the resin composition of the present embodiment, the acid value of the compound (A) is 30 mgKOH / g or more from the viewpoint of improving developability, and the developability is further improved, so that it is 50 mgKOH / g or more. preferable. In addition, from the viewpoint of preventing dissolution by the developer after curing with active energy rays, the acid value of the compound (A) is 120 mgKOH / g or less, and since dissolution can be further prevented, it is 110 mgKOH / g or less. Is preferred. The “acid value” in the present embodiment indicates a value measured by a method according to JISK 0070: 1992.

In the resin composition of the present embodiment, the content of the compound (A) is not particularly limited, but from the viewpoint of curing the resin composition with active energy rays, the resin solid content in the resin composition is 100 parts by mass. 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, still more preferably 10 parts by mass or more, even more preferably 25 parts by mass or more. It is still more preferable, and it is still more preferable to set it as 30 mass parts or more. Further, from the viewpoint of sufficiently curing with active energy rays and improving heat resistance and developability, it is preferably 99 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition, and 98 parts by mass. More preferably, it is more preferably 97 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 75 parts by mass or less, and even more preferably 73 parts by mass or less. Most preferred.

<Photocuring initiator (B)>
Although the photocuring initiator (B) used for this embodiment is not specifically limited, A well-known thing can be used in the field | area generally used for a photocurable resin composition.

Examples of the photocuring initiator (B) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, and parachlorobenzoyl peroxide. Organic peroxides exemplified by oxides, di-tert-butyl-di-perphthalate, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- Dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- -Acetophenones such as morpholino-propan-1-one, anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone Thioxanthones such as 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2, Radical photocuring initiators such as oxime esters such as octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylamino Lewis acid diazonium salts such as phenyldiazonium hexafluorophosphonate, Lewis acid iodonium salts such as diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, Lewis such as triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate Sulfonium salts of acids, phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate, other halides, triazine initiators, borate Examples thereof include cationic photopolymerization initiators such as system initiators and other photoacid generators.

Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (from the viewpoint of reactivity suitable for multilayer printed wiring board applications and high reliability for metal conductors) A radical photocuring initiator of acetophenones such as ISFacure (registered trademark) 369 manufactured by BASF Japan Ltd. is preferable.

These photocuring initiators (B) can be used alone or in combination of two or more, and both radical and cationic initiators may be used in combination.

The content of the photocuring initiator (B) in the resin composition of the present embodiment is not particularly limited. From the viewpoint of sufficiently curing the resin composition with active energy rays and improving heat resistance, the resin composition. It is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the resin solid content therein. It is still more preferable to set it as 1 mass part or more. Further, from the viewpoint of preventing the heat curing after photocuring and preventing the heat resistance from being lowered, the content is preferably 30 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

In the resin composition of the present embodiment, either the maleimide compound (C) or the blocked isocyanate (D) can be used, and these can be used in combination. Among them, from the viewpoint of improving the coating properties, heat resistance and developability, it is preferable to use the maleimide compound (C), further improving the heat resistance and developability, and further improving the coating properties. More preferably, the maleimide compound (C) and the blocked isocyanate (D) are used in combination. The maleimide compound (C) and the blocked isocyanate (D) are described in detail below.

<Maleimide compound (C)>
The maleimide compound (C) used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include, for example, N-phenylmaleimide, phenylmethanemaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane. 4,4-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4 -Maleimidophenyl) methane, polytetramethylene oxide-bis (4-maleimidobenzoate), o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide , P-fe Renbiscitraconimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenyl sulfone bismaleimide, 1,3-bis (3-maleimide) Phenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] propane, bis (3,5 -Dimethyl-4-citraconimidophenyl) methane, bis (3-ethyl-5- Til-4-citraconimidophenyl) methane, bis (3,5-diethyl-4-citraconimidophenyl) methane, polyphenylmethanemaleimide, a maleimide compound represented by the following formula (4), represented by the following formula (5) Maleimide compounds, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

Among these, from the viewpoint of obtaining good coating properties and excellent heat resistance, a maleimide compound represented by the following formula (4) and a maleimide compound represented by the following formula (5) are preferable, and the following formula (4) ) Is more preferred. A commercially available product can be used as the maleimide compound represented by the following formula (4), and examples thereof include BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.). As the maleimide compound represented by the following formula (5), a commercially available product can be used, and examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.).
These maleimide compounds (C) can be used singly or in appropriate combination of two or more.

(In the formula (4), each of the plurality of R ₅ independently represents a hydrogen atom or a methyl group. N ₁ represents an integer of 1 or more, preferably an integer of 1 to 10).

(In the formula (5), each of the plurality of R ₆ independently represents a hydrogen atom or a methyl group. N ₂ represents an integer of 1 or more, preferably an integer of 1 to 5).

The content of the maleimide compound (C) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, the resin solid content 100 in the resin composition is 100%. It is preferable to set it as 0.01 mass part or more with respect to a mass part, It is more preferable to set it as 0.02 mass part or more, It is still more preferable to set it as 0.03 mass part or more, 0.5 mass part or more Even more preferably. Moreover, from a viewpoint of making developability favorable, it is preferable to set it as 50 mass parts or less with respect to 100 mass parts of resin solid content in a resin composition, It is more preferable to set it as 45 mass parts or less, 40 masses More preferably, it is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and most preferably 7 parts by mass or less.

<Blocked isocyanate (D)>
The blocked isocyanate (D) used in the present embodiment is not particularly limited as long as it is inactive at room temperature (25 ° C.), but the blocking agent is reversibly dissociated to regenerate isocyanate groups when heated.
Examples of the blocked skeleton of the blocked isocyanate (D) include isocyanurate type, biuret type, and adduct type, and isocyanurate type is preferable from the viewpoint of heat resistance.
These blocked isocyanates (D) can be used singly or in appropriate combination of two or more.

Examples of the blocking agent that is inactive at room temperature (25 ° C.) but reversibly dissociates when heated include at least one compound selected from diketones, oximes, phenols, alkanols, and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam.
The dissociation temperature of the blocking agent is not particularly limited, but is preferably 120 ° C. or higher from the viewpoint of sufficiently curing the resin composition and improving heat resistance. Moreover, the thing below 200 degreeC is preferable from a viewpoint of making a block agent fully dissociate and hardening a resin composition.

The above blocking agent is dissociated during heating and discharged as a gas. Therefore, it is preferable to use a blocking agent having a small molecular weight because it causes a volume reduction. Specifically, it is preferable to use a methyl ethyl ketone oxime type.

Such blocked isocyanates are readily available as commercial products, for example, Sumidur (registered trademark) BL-3175, BL-4265, BL-5375, BL-1100, BL-1265, , Sumika Covestrourethane Co., Ltd.), Coronate (registered trademark) 2507, Coronate (registered trademark) 2554 (trade name, manufactured by Tosoh Corporation), Duranate (registered trademark) TPA-B80E, Duranate (Registered Trademark) 17B-60PX (above, trade name, manufactured by Asahi Kasei Chemicals Corporation) and the like.
Among these, it is preferable that the blocked skeleton is at least one selected from the group of isocyanurate type, selected from Sumidur (registered trademark) BL-3175 and Duranate (registered trademark) TPA-B80E. By including such kind of blocked isocyanate, the heat resistance of the resulting cured product tends to be further improved.

The content of the blocked isocyanate (D) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, the resin solid content in the resin composition It is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.3 parts by mass or more, and 0.5 parts by mass with respect to 100 parts by mass. It is even more preferable to use the above. Further, from the viewpoint of suppressing the volume reduction of the resin composition and being excellent in developability, it is 5.0 parts by mass or less or less than 5.0 parts by mass with respect to 100 parts by mass of resin solid content in the resin composition. It is preferably 4.0 parts by mass or less or less than 4.0 parts by mass, more preferably 3.0 parts by mass or less or less than 3.0 parts by mass.

When the maleimide compound (C) and the blocked isocyanate (D) are used in combination, their content is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, It is preferable to set it as 0.11 mass part or more with respect to 100 mass parts of resin solid content of this, It is more preferable to set it as 0.5 mass part or more, It is still more preferable to set it as 1 mass part or more, 3 mass parts It is even more preferable to use the above. Moreover, from a viewpoint that the volume reduction of a resin composition is suppressed, it is excellent in developability, and a more favorable coating film is obtained, it shall be 55 mass parts or less with respect to 100 mass parts of resin solid content in a resin composition. It is preferably 25 parts by mass or less, more preferably 15 parts by mass, still more preferably 13 parts by mass or less, and still more preferably 10 parts by mass.

<Epoxy resin (E)>
In order to improve the developability and the heat resistance of the cured product, the epoxy resin (E) can be used in combination with the resin composition of the present embodiment.

The epoxy resin (E) used in the present embodiment is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolak type epoxy resin, xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, Trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, triglycidyl isocyanurate, glycidyl ester epoxy resin, alicyclic Poxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, di Cyclopentadiene-type epoxy resins, polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, epoxidized compounds such as butadiene, compounds obtained by reaction of hydroxyl-containing silicone resins with epichlorohydrin, and halogens thereof A compound.

Among them, it is preferably at least one selected from the group consisting of biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins, and biphenyl aralkyl type epoxy resins are more preferable. . By including such kind of epoxy resin, the heat resistance of the obtained cured product tends to be further improved.
These epoxy resins (E) can be used singly or in appropriate combination of two or more.

In the resin composition of the present embodiment, the content of the epoxy resin (E) is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, the resin solid content in the resin composition is 100 parts by mass. 1.0 part by mass or more, preferably 1.5 parts by mass or more, more preferably 2.0 parts by mass or more, and even more preferably 8 parts by mass or more. . Further, from the viewpoint of improving the developability of the resin composition, it is preferably 90 parts by mass or less and more preferably 70 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, it is 50 mass parts or less, More preferably, it is 25 mass parts or less.

<Compound (F) having an ethylenically unsaturated group>
The resin composition of the present embodiment is used in combination with a compound (F) having an ethylenically unsaturated group in order to increase the reactivity to active energy rays (for example, ultraviolet rays) and improve the developability and heat resistance. Is also possible. The compound (F) having an ethylenically unsaturated group used in the present embodiment is other than the compound (A) represented by the formula (1) and having an acid value of 30 mgKOH / g or more and 120 mgKOH / g or less. Although it will not specifically limit if it is a compound which has 1 or more ethylenically unsaturated groups, For example, the compound which has a (meth) acryloyl group, a vinyl group, etc. is mentioned. These compounds (F) having an ethylenically unsaturated group can be used singly or in appropriate combination of two or more.

As a compound having a (meth) acryloyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether , Phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylenedi (meth) a Relate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (Meth) acrylate, bisphenol di (meth) acrylate, ε-caprolactone modified hydroxypivalic acid neopent glycol di (meth) acrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified dipentaerythritol poly ( (Meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) a Relate, triethylolpropane tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, And ethylene oxide adducts thereof.

In addition, urethane (meth) acrylates that have (meth) acryloyl groups and urethane bonds in the same molecule, polyester (meth) acrylates that have (meth) acryloyl groups and ester bonds in the same molecule, and epoxy resins Epoxy (meth) acrylates derived from the above and having a (meth) acryloyl group, and reactive oligomers in which these bonds are used in combination.

The urethane (meth) acrylate is a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as necessary. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin (meta) such as glycerin mono (meth) acrylate, glycerin di (meth) acrylate, etc. ) Sugar alcohol (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , Isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate Dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.

The above epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolak type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy ( And (meth) acrylate and the like, and acid anhydride-modified epoxy (meth) acrylate and the like.

Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, ethyl styrene, divinyl benzene, α-methyl styrene, and oligomers thereof. Other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, bisallyl nadiimide and the like.

Among these, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cresol novolac type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, bisary One or more selected from the group consisting of lunadiimide is preferred, and dipentaerythritol hexa (meth) acrylate is more preferred. By including the compound having such an ethylenically unsaturated group, the heat resistance of the resulting cured product tends to be further improved.

In the resin composition of the present embodiment, the content of the compound (F) having an ethylenically unsaturated group is not particularly limited, but from the viewpoint of improving developability, the resin solid content in the resin composition is 100 mass. 0.5 parts by mass or more with respect to parts, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, and more preferably 5 parts by mass or more. Is more preferable, and it is most preferable to set it to 15 parts by mass or more. Further, from the viewpoint of improving the heat resistance of the cured product, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. 50 parts by mass or less, more preferably 25 parts by mass or more.

<Inorganic filler (G)>
In the resin composition of the present embodiment, an inorganic filler (G) can be used in combination in order to improve various properties such as coating properties, developability and heat resistance. The inorganic filler (G) used in the present embodiment is not particularly limited as long as it has insulating properties. For example, silica (for example, natural silica, fused silica, amorphous silica, hollow silica, etc.), an aluminum compound (for example, Boehmite, aluminum hydroxide, alumina, etc.), magnesium compounds (eg, magnesium oxide, magnesium hydroxide, etc.), calcium compounds (eg, calcium carbonate, etc.), molybdenum compounds (eg, molybdenum oxide, zinc molybdate, etc.), barium compounds (eg, sulfuric acid) Barium, barium silicate, etc.), talc (eg, natural talc, calcined talc, etc.), mica (mica), glass (eg, short fiber glass, spherical glass, fine powder glass (eg, E glass, T glass, D glass, etc.)) Etc.) and silicone powder.

Among them, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, magnesium hydroxide, and barium sulfate is preferable.

These inorganic fillers (G) may be surface-treated with a silane coupling agent described later.

In particular, silica is preferable and fused silica is particularly preferable from the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties. Specific examples of silica include SFP-130MC manufactured by Denka Corporation, SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Corporation.
These inorganic fillers (G) can be used singly or in appropriate combination of two or more.

In the resin composition of the present embodiment, the content of the inorganic filler (G) is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, the resin solid content in the resin composition is 100 parts by mass. It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. Further, from the viewpoint of improving the developability of the resin composition, it is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, the amount is 300 parts by mass or less, and more preferably 100 parts by mass or less.

<Silane coupling agent and wetting and dispersing agent>
In the resin composition of this embodiment, in order to improve the dispersibility of the inorganic filler, the adhesion strength between the polymer and / or resin and the inorganic filler, a silane coupling agent and / or a wet dispersant is used in combination. It is also possible.

These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for inorganic surface treatment. Specific examples include, for example, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane Acrylic silanes such as γ-acryloxypropyltrimethoxysilane; cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane silane cups A ring agent is mentioned. These silane coupling agents can be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include wet dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, and W903 manufactured by Big Chemie Japan Co., Ltd. . These wetting and dispersing agents can be used singly or in appropriate combination of two or more.

In the resin composition of the present embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

<Thermosetting accelerator>
In the resin composition of the present embodiment, a thermosetting accelerator can be used in combination as long as the characteristics of the present embodiment are not impaired.

The thermosetting accelerator is not particularly limited, and examples thereof include organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, and the like. Azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline , N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, tertiary amines such as N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, stearic acid lead, Organic metal salts such as zinc phthalate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and acetylacetone iron; these organic metal salts are dissolved in hydroxyl-containing compounds such as phenol and bisphenol Inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; Dioctyl tin oxide, other organic tin compounds such as alkyl tin and alkyl tin oxide; 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, Examples thereof include imidazole compounds such as triphenylimidazole (TPIZ).

These thermosetting accelerators can be used singly or in appropriate combination of two or more.

In the resin composition of the present embodiment, the content of the thermosetting accelerator is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

<Organic solvent>
The resin composition of the present embodiment may contain a solvent as necessary. For example, when an organic solvent is used, the viscosity at the time of preparing the resin composition can be adjusted. The kind of solvent will not be specifically limited if it can melt | dissolve part or all of resin in a resin composition. Specific examples thereof include, but are not particularly limited to, for example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and acetate thereof Is mentioned.

These organic solvents can be used singly or in appropriate combination of two or more.

<Other ingredients>
In the resin composition of the present embodiment, various polymer compounds such as thermosetting resins, thermoplastic resins and oligomers thereof, elastomers, etc., which have not been mentioned so far, as long as the characteristics of the present embodiment are not impaired. Flame retardant compound not mentioned so far; combined use of additives and the like is also possible. These are not particularly limited as long as they are generally used. Examples of flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. Additives include UV absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface conditioners, brighteners, polymerization inhibitors, etc. It is done.
These components can be used alone or in appropriate combination of two or more.

In the resin composition of the present embodiment, the content of other components is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

The resin composition of the present embodiment comprises a compound (A), a photocuring initiator (B), a maleimide compound (C) and / or a blocked isocyanate (D), and, if desired, an epoxy resin (E), ethylenic It is prepared by appropriately mixing a compound (F) having an unsaturated group, an inorganic filler (G), a silane coupling agent, a wetting and dispersing agent, a thermosetting accelerator, an organic solvent and other components. The resin composition of this embodiment can be used suitably as a varnish at the time of producing the resin sheet with a support body of this embodiment mentioned later.

<Method for producing resin composition>
The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix | blending each component mentioned above in a solvent sequentially and fully stirring is mentioned.

In the production of the resin composition, a known process (such as stirring, mixing, and kneading process) for uniformly dissolving or dispersing each component can be performed as necessary. Specifically, the dispersibility of the inorganic filler (G) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The stirring, mixing, and kneading processes described above are, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll, ball mill, bead mill, and sand mill, or a revolving or rotating type. It can carry out suitably using well-known apparatuses, such as a mixing apparatus. Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as needed. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

<Application>
The resin composition of the present embodiment can be used for applications where an insulating resin composition is required, and is not particularly limited, but a photosensitive film, a photosensitive film with a support, a resin sheet with a support, Used for insulating resin sheets such as prepreg, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-filling resins, etc. be able to. Especially, it can be conveniently used as a resin composition for insulating layers of a multilayer printed wiring board or a solder resist.

<Resin sheet with support>
The resin sheet with a support of the present embodiment comprises the support and a resin composition layer that is formed on the surface of the support and includes the resin composition of the present embodiment. It is the resin sheet with a support body apply | coated to the single side | surface or both surfaces. The resin sheet with a support can be produced by applying the resin composition onto a support and drying.

The support used in the resin sheet with a support of the present embodiment is not particularly limited, but a known one can be used, and a resin film is preferable. Examples of the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, and polyvinyl alcohol. Examples thereof include resin films such as films and triacetyl acetate films. Among these, a PET film is preferable.

The resin film having a release agent coated on the surface thereof can be suitably used in order to facilitate peeling from the resin composition layer. The thickness of the resin film is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm. If the thickness is less than 5 μm, the support tends to be broken when the support is peeled off before development, and if the thickness exceeds 100 μm, the resolution when exposed from the support tends to decrease. is there.

Also, in order to reduce light scattering during exposure by active energy rays such as ultraviolet rays, it is preferable that the resin film has excellent transparency.

Furthermore, in the resin sheet with a support in the present embodiment, the resin composition layer may be protected with a protective film.
By protecting the resin composition layer side with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer. As the protective film, a film made of the same material as the above resin film can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 50 μm, and more preferably in the range of 5 μm to 40 μm. When the thickness is less than 1 μm, the handleability of the protective film tends to be lowered, and when it exceeds 50 μm, the inexpensiveness tends to be inferior. The protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support.

The production method of the resin sheet with a support of the present embodiment is not particularly limited. For example, the resin sheet of the present embodiment is applied to a support such as a PET film and the organic solvent is removed by drying. Examples thereof include a method for producing a body-attached resin sheet.

The coating can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, squeeze coater or the like. The drying can be performed, for example, by a method of heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes.

The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less with respect to the total mass of the resin composition layer from the viewpoint of preventing diffusion of the organic solvent in the subsequent step. The thickness of the resin composition layer with respect to the support is preferably 1.0 μm or more in terms of the resin composition layer thickness of the resin sheet with the support, from the viewpoint of improving the handleability. Further, from the viewpoint of improving the transmittance and improving the developability, the thickness is preferably 300 μm or less.

The resin sheet with a support of the present embodiment can be used as an interlayer insulating layer of a multilayer printed wiring board.

The multilayer printed wiring board of the present embodiment can be obtained by, for example, stacking and curing one or more of the above-described resin sheets with a support.

<Multilayer printed wiring board>
The multilayer printed wiring board of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and can be specifically manufactured by the following method.

(Lamination process)
The resin composition layer side of the resin sheet with a support of the present embodiment is laminated on one or both sides of a circuit board using a vacuum laminator. Examples of the circuit board include a glass epoxy board, a metal board, a ceramic board, a silicon board, a semiconductor sealing resin board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. Here, the circuit board refers to a board on which a conductor layer (circuit) patterned on one or both sides of the board is formed. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate that is a conductor layer (circuit) in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned, It is included in the circuit board here. The surface of the conductor layer may be previously roughened by blackening treatment, copper etching, or the like. In the laminating step, when the resin sheet with a support has a protective film, the protective film is peeled and removed, and then the resin sheet with the support and the circuit board are preheated as necessary, and the resin composition layer is removed. Crimp to circuit board while pressing and heating. In the resin sheet with a support of this embodiment, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used.

The conditions for the laminating step are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 50 ° C. to 140 ° C., the pressure bonding pressure is preferably 1 kgf / cm ² to 15 kgf / cm ² , and the pressure bonding time. Is preferably 5 seconds to 300 seconds, and lamination is performed under reduced pressure so that the air pressure is 20 mmHg or less. The laminating step may be a batch type or a continuous type using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a 2-stage build-up laminator manufactured by Nikko Materials Co., Ltd. can be exemplified.

(Exposure process)
After the resin sheet with a support is provided on the circuit board by the laminating process, an exposure process is performed in which a predetermined portion of the resin composition layer is irradiated with active energy rays to cure the resin composition layer of the irradiated portion. The active energy ray may be irradiated through a mask pattern or a direct drawing method in which an active energy ray is directly irradiated.

Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is about 10 mJ / cm ² to 1000 mJ / cm ² . There are two methods for exposing the mask pattern: a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board, and a non-contact exposure method in which exposure is carried out using parallel light rays without being brought into close contact. It doesn't matter. Moreover, when the support body exists on a resin composition layer, you may expose from a support body and may expose after a support body peels.

(Development process)
After the exposure step, if a support is present on the resin composition layer, the support is removed, and then development is performed by removing the uncured portion (unexposed portion) by wet development. Thus, the pattern of the insulating layer can be formed.

In the case of the above-described wet development, the developer is not particularly limited as long as it selectively elutes an unexposed portion, but a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. . In the present embodiment, a development step using an alkaline aqueous solution is particularly preferable. These developers can be used singly or in combination of two or more. Moreover, as a developing method, it can carry out by well-known methods, such as spraying, rocking immersion, brushing, and scraping, for example.

The alkaline aqueous solution used as the developer is not particularly limited. For example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, 4-sodium borate, ammonia And amines.

The concentration of the alkaline aqueous solution is preferably 0.1% by mass to 60% by mass with respect to the total amount of the developer. Moreover, the temperature of aqueous alkali solution can be adjusted according to developability. Furthermore, these aqueous alkali solutions can be used singly or in combination of two or more.

In the pattern formation of this embodiment, two or more kinds of development methods described above may be used in combination as necessary. Development methods include a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is suitable for improving the resolution. The spray pressure when the spray method is employed is preferably 0.02 MPa to 0.5 MPa.

(Post bake process)
After the development step, a post-bake step is performed to form an insulating layer (cured product). Examples of the post-bake process include an ultraviolet irradiation process using a high-pressure mercury lamp and a heating process using a clean oven. Case of ultraviolet irradiation can adjust its dose optionally, the irradiation can be carried out, for example ^{0.05J / cm 2 ~ 10J / cm} 2 of about dose. The heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. It is selected in the range of 30 minutes to 150 minutes at ˜200 ° C.

(Plating process)
Next, a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on the insulating layer by placing the support in a vacuum vessel and evaporating the metal by heating. In the sputtering method, for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, the ionized inert gas is made to collide with the target metal, and the struck metal is used. A metal film can be formed on the insulating layer.

In the case of wet plating, the surface of the insulating layer is roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. . The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 1 to 20 minutes. Examples of the swelling liquid include an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Updes (registered trademark) MDS-37 manufactured by Uemura Kogyo Co., Ltd.

The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 5 to 30 minutes. Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Updes (registered trademark) MDE-40 and Updes (registered trademark) ELC-SH manufactured by Uemura Kogyo Co., Ltd. The neutralization treatment with the neutralizing solution is performed by immersing in the neutralizing solution at 30 to 50 ° C. for 1 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is Updes (registered trademark) MDN-62 manufactured by Uemura Kogyo Co., Ltd.

Next, a conductor layer is formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a pattern formation method thereafter, for example, a subtractive method, a semi-additive method, or the like can be used.

<Semiconductor device>
The semiconductor device of this embodiment includes an interlayer insulating layer containing the resin composition of this embodiment, and can be specifically manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present embodiment. Here, the conduction location is a location for transmitting an electrical signal in the multilayer printed wiring board, and the location may be the surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, a bump Examples include a mounting method using a none buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Also, a semiconductor device can be manufactured by laminating the resin sheet with a support of this embodiment on a semiconductor chip. After lamination, it can be produced by using the same method as the above multilayer printed wiring board.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
(Production of resin composition and resin sheet with support)
As the compound (A), a TrisP-PA epoxy acrylate compound in propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA) solution (KAYARAD (registered trademark) ZCR-6002H, nonvolatile content 65 mass%, acid value: 60 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) 81.2 parts by mass (52.8 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.) 5 parts by mass, maleimide compound (C), maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3 .5 parts by mass, as epoxy resin (E), biphenyl aralkyl type epoxy resin (NC300 H, manufactured by Nippon Kayaku Co., Ltd.) 19.8 parts by mass, as compound (F) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 18.9 parts by mass, as inorganic filler (G), methyl ethyl ketone (hereinafter sometimes abbreviated as MEK) slurry of epoxysilane-treated silica (SC2050MB, average particle size 0.5 μm, nonvolatile content 70% by mass, AD Co., Ltd.) 71.4 parts by mass (manufactured by Mattex) (50 parts by mass in terms of non-volatile content) was blended and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). These varnishes were coated on a 38 μm thick PET film (Unipeel® TR1-38, trade name, manufactured by Unitika Co., Ltd.) and dried by heating at 80 ° C. for 7 minutes to use the PET film as a support. A resin sheet with a support having a resin composition layer thickness of 30 μm was obtained.

The KAYARAD (registered trademark) ZCR-6002H is a mixture containing at least one of the compound (A1) and the compounds (A2) to (A5).

(Creation of inner layer circuit board)
Both sides of glass cloth base material BT resin double-sided copper-clad laminate (copper foil thickness 18μm, thickness 0.2mm, Mitsubishi Gas Chemical Co., Ltd. CCL (registered trademark) -HL832NS) on which inner layer circuit is formed MEC A copper surface was roughened with CZ8100 manufactured to obtain an inner layer circuit board.

(Preparation of evaluation laminate)
The resin surface of the resin sheet with the support is placed on an inner layer circuit board, and after vacuuming (5.0 MPa or less) for 30 seconds using a vacuum laminator (Nikko Materials Co., Ltd.), pressure Lamination molding was performed at 10 kgf / cm ² and a temperature of 70 ° C. for 30 seconds. Furthermore, the laminated body by which the inner-layer circuit board, the resin composition layer, and the support body were laminated | stacked by performing lamination molding for 60 seconds at a pressure of 10 kgf / cm < ² > and temperature of 70 degreeC was obtained. The obtained laminate was subjected to an exposure step of irradiating ultraviolet rays of 200 mJ / cm ² , the support was peeled off, and developed with a 1% by mass aqueous sodium carbonate solution to obtain a laminate for evaluation.

(Production of cured product for evaluation)
The resin sheet with the support was irradiated with 200 mJ / cm ² of ultraviolet rays, and further subjected to a post-baking step of heat treatment at 180 ° C. for 120 minutes, and then the support was peeled off to obtain a cured product for evaluation.

[Example 2]
As the compound (A), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6002H, non-volatile content 65% by mass, acid value: 60 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) 82.1 mass Parts (53.4 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.) 5 parts by mass, as blocked isocyanate compound (D), Sumidur (registered trademark) BL-3175 (solvent naphtha solution, non-volatile content: 75% by mass (including blocking agent), manufactured by Sumika Covestro Urethane Co., Ltd. , Product name) 3.3 parts by mass (2.5 parts by mass in terms of non-volatile content (however, the blocking agent is included)), biphenyla Rukyle type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 19.9 parts by mass, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 19.2 parts by mass, epoxy silane MEK slurry of treated silica (SC2050MB, average particle size 0.5 μm, non-volatile content 70% by mass, manufactured by Admatex Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of non-volatile content) was blended, and an ultrasonic homogenizer was used. Stirring gave a varnish (resin composition solution). Thereafter, in the same manner as in Example 1, a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation were obtained.

Example 3
As compound (A), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6002H, nonvolatile content 65 mass%, acid value: 60 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 80.5 mass Parts (52.3 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.) 5 parts by mass, maleimide compound (C) as maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.5 parts by mass, and blocked isocyanate compound (D) as Sumidur (registered trademark) BL-3175 (Solvent naphtha solution, non-volatile content 75% by mass (including blocking agent), Sumika Cobest wax letter (Product name) 3.3 parts by mass (2.5 parts by mass in terms of non-volatile content (including block agent)), biphenyl aralkyl epoxy resin (NC3000H, Nippon Kayaku Co., Ltd.) 18 parts by mass Part, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Kayaku Co., Ltd.) 18.7 parts by mass, epoxysilane-treated silica MEK slurry (SC2050MB, average particle size 0.5 μm, nonvolatile content 70 mass) %, 71.4 parts by mass (manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of non-volatile content), and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). Thereafter, in the same manner as in Example 1, a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation were obtained.

[Comparative Example 1]
77.6 parts by mass (non-volatile) of bisphenol F type epoxy acrylate (KAYARAD (registered trademark) ZFR-1553H, non-volatile content 68% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) instead of compound (A) A varnish was prepared in the same manner as in Example 1 except that 52.8 parts by mass in terms of minutes was used, and a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation were obtained.

[Comparative Example 2]
Instead of the compound (A), cresol novolak type epoxy acrylate (EA-7140, non-volatile content 73 mass%, acid value: 70 mg KOH / g, manufactured by Shin-Nakamura Chemical Co., Ltd.) 72.3 parts by mass (non-volatile conversion 52 .8 parts by mass) was used in the same manner as in Example 1 to obtain a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation.

[Comparative Example 3]
Instead of the compound (A), cresol novolac epoxy acrylate (EA-7420, nonvolatile content 73 mass%, acid value: 1 mg KOH / g, manufactured by Shin-Nakamura Chemical Co., Ltd.) 72.3 parts by mass (52 in terms of nonvolatile content) .8 parts by mass) was used in the same manner as in Example 1 to obtain a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation.

[Comparative Example 4]
Instead of compound (A), biphenyl aralkyl type epoxy acrylate (KAYARAD (registered trademark) ZCR-1642H, non-volatile content 60 mass%, acid value: 99 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 88 mass parts (non-volatile conversion) A varnish was prepared in the same manner as in Example 1 except that 52.8 parts by mass) was used, and a resin sheet with a support, an evaluation laminate, and an evaluation cured product were obtained.

[Comparative Example 5]
80 parts by mass (nonvolatile content) of dicyclopentadiene type epoxy acrylate (KAYARAD (registered trademark) ZXR-1807H, non-volatile content 66% by mass, acid value: 103 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) instead of compound (A) A varnish was prepared in the same manner as in Example 1 except that 52.8 parts by mass in terms of conversion was used, and a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation were obtained.

(Measurement of physical properties)
Each resin sheet with a support, each evaluation laminate, and each evaluation cured product prepared using the varnishes obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were measured and evaluated by the following methods. . The results are summarized in Table 1.

<Coating properties>
A finger was lightly pressed against the resin surface edge of each A4-sized resin sheet with a support, and the degree of sticking to the finger was evaluated according to the following criteria.
A: Sticking to the finger is not recognized. The end of the resin sheet with the support does not float up.
○: Sticking to the finger is hardly recognized. Although the edge part of the resin sheet with a support body sticks to a finger | toe, it peels off from a finger | toe and falls by less than 30 mm in height.
X: Sticking to the finger is recognized. The edge part of the resin sheet with a support body sticks to a finger | toe, and 30 mm or more in height rises.

<Heat resistance (glass transition temperature)>
The cured product for evaluation was heated at 10 ° C./min using a DMA device (dynamic viscoelasticity measuring device DMAQ800 manufactured by TA Instruments), and the peak position of Loss Modulus was defined as the glass transition temperature (Tg, ° C.). .

<Developability>
After visually observing the development surface of each evaluation laminate, it was observed with a SEM (magnification 1000 times), and the presence or absence of a residue was evaluated according to the following criteria.
○: There is no development residue in the range of 30 mm square, and the developability is excellent.
X: There is a development residue in the range of 30 mm square, and the developability is inferior.

As is clear from Table 1, Examples 1 to 3 have high heat resistance (Tg) and excellent developability. Among them, Example 3 has particularly good coating properties. On the other hand, Comparative Examples 1 to 5 are insufficient in either heat resistance (Tg) or developability. Therefore, according to this invention, the resin composition excellent in heat resistance and developability, the resin sheet with a support body, a multilayer printed wiring board, and a semiconductor device are obtained.

Claims

A compound (A) represented by the following formula (1) and having an acid value of 30 mgKOH / g to 120 mgKOH / g, a photocuring initiator (B), a maleimide compound (C) and / or a blocked isocyanate (D) And a resin composition containing.

(In Formula (1), each of the plurality of R 1 independently represents a hydrogen atom or a methyl group, each of the plurality of R 2 independently represents a hydrogen atom or a methyl group, and each of the plurality of R 3 represents, Independently, it represents a substituent represented by the following formula (2), a substituent represented by the following formula (3), or a hydroxy group.

(In formula (3), R 4 represents a hydrogen atom or a methyl group.)
The resin composition according to claim 1, further comprising an epoxy resin (E).
The resin composition according to claim 1 or 2, further comprising a compound (F) having an ethylenically unsaturated group other than the compound (A).
The resin composition according to any one of claims 1 to 3, further comprising an inorganic filler (G).
A resin sheet with a support, comprising the resin composition according to any one of claims 1 to 4, which is applied to the support.
A multilayer printed wiring board comprising the resin composition according to any one of claims 1 to 4.
A semiconductor device comprising the resin composition according to any one of claims 1 to 4.