TW201736963A - Resin composition, resin sheet with support body, multilayer printed wiring board, and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition and a resin sheet with a support body which exhibit excellent heat resistance and developability when used in a multilayer printed wiring board, and a multilayer printed wiring board and semiconductor device that use the resin composition and the resin sheet. The resin composition includes a compound (A) having an acid value of 30 mgKOH/g to 120 mgKOH/g, which is represented by formula (1) below, a photocuring initiator (B), a maleimide compound (C) and/or a blocked isocyanate (D).

Description

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

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

Due to the miniaturization and high density of multilayer printed circuit boards, research into thinning laminated boards used for multilayer printed circuit boards is flourishing. As the thickness thereof is reduced, a thinner film is also sought for the insulating layer, and a resin sheet containing no glass cloth is being sought. The resin composition which is a material of the insulating layer is mainly made of a thermosetting resin, and an opening for obtaining electrical conduction between the insulating layers is generally performed by laser processing. On the other hand, the opening of the hole by the laser processing has a problem that the processing time becomes longer as the high-density substrate having the larger number of holes is formed. Therefore, in recent years, a resin sheet which can be subjected to one-time opening processing in the development step by using a resin composition which is hardened by light or the like and which is dissolved by development is being sought.

In such a resin composition, an alkali development type is mainly used, and an acid anhydride group or a carboxyl group-containing acrylate is used in order to make development possible. For example, Patent Document 1 discloses a composition which can be developed in an aqueous alkali solution using an acid-modified novolak resin type epoxy acrylate. Patent Document 2 discloses a photosensitive resin composition containing a predetermined curing agent to improve mechanical properties. Patent Document 3 discloses a photosensitive resin composition used for an interlayer insulating layer of a multilayer printed wiring board. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2006-047501 (Patent Document 3) International Publication No. 2015/002071

[Problems to be Solved by the Invention] However, conventionally, a cured product of acrylate is used, and sufficient physical properties cannot be obtained, and the formation of a protective film and an interlayer insulating layer having high heat resistance is limited. Further, the use of the composition described in Patent Document 1 is limited to an etching resist for a printed circuit board or a solder resist, and the heat resistance is insufficient when used as an interlayer insulating layer. The photosensitive resin composition described in Patent Document 2 has a glass transition temperature of 115 ° C and is insufficient in heat resistance. In the photosensitive resin composition described in Patent Document 3, the developing solution is developed using an organic solvent, and developability in an aqueous developing solution which does not use an organic solvent, such as an aqueous alkali solution which is mainly used in a developing solution in the field of printed circuit boards. insufficient.

In view of the above, the present invention provides a resin composition excellent in heat resistance and developability for use in a multilayer printed wiring board, a resin sheet with a support, and a multilayer printed wiring board and a semiconductor device using the same. [Means for solving the problem]

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

[Chemical 1]

In the formula (1), a plurality of R ₁ each independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ each independently represent a hydrogen atom or a methyl group, and a plurality of R ₃ each independently represent a substitution represented by the following formula (2). A substituent or a hydroxyl group represented by the following formula (3).

[Chemical 2]

[Chemical 3]

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

In other words, the present invention includes the following: [1] A resin composition comprising: the compound (A) represented by the above formula (1) and having an acid value of 30 mgKOH/g or more and 120 mgKOH/g or less, and a photohardening initiator (B) ), maleic imine compound (C) and/or blocked isocyanate (D). [2] The resin composition as described in [1], further comprising an epoxy resin (E). [3] The resin composition according to [1] or [2], further comprising 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 comprising an inorganic filler (G). [5] A resin sheet provided with a support, which has a resin composition as described in any one of [1] to [4]. [6] A multilayer printed circuit board comprising 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]. [Effects of the Invention]

According to the present invention, it is possible to provide a resin composition which is excellent in coating property, heat resistance and developability, and which is suitable for physical properties of a protective film and an interlayer insulating layer of a multilayer printed circuit board, and which is provided with a support. The use of such multilayer printed circuit boards and semiconductor devices.

Hereinafter, the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The following examples are intended to illustrate the invention and are not intended to limit the invention. The present invention can be carried out with appropriate changes within the scope of the gist of the invention.

In addition, the term "(meth) acrylate" in the present specification means "acryloyl fluorenyl" and "methacryl fluorenyl group" corresponding to propylene fluorenyl group, and "(meth) acrylate" means "Acrylate" and "methacrylate" corresponding to acrylate, "(meth)acrylic" means both "acrylic" and "methacrylic acid" corresponding to acrylic acid. In the present embodiment, the term "resin solid content" or "resin solid content in the resin composition" is defined as a resin composition other than the solvent and the inorganic filler (G) unless otherwise specified. The component "100 parts by mass of the resin solid content" means that the total of the components other than the solvent and the inorganic filler (G) in the resin composition is 100 parts by mass.

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

<Compound (A)> The compound (A) used in the present embodiment is a compound represented by the above formula (1). The compound (A) may be used singly or in the form of an isomer such as a structural isomer or a stereoisomer, or a compound having two or more different structures may be used in combination as appropriate.

In the above formula (1), a plurality of R ₁ each independently represent a hydrogen atom or a methyl group. Among them, in view of improving the reactivity of the photo-curing reaction, it is preferred to contain a hydrogen atom, and it is more preferable that all of R ₁ is a hydrogen atom. A plurality of R ₂ each independently represent a hydrogen atom or a methyl group. Among them, in view of improving the heat resistance of the cured product, it is preferred to contain a methyl group, and it is more preferable that all of R ₂ is a methyl group.

A plurality of R ₃ each independently represent a substituent represented by the above formula (2), a substituent represented by the above formula (3) or a hydroxyl group. Among them, in view of improving heat resistance, it is preferred to contain a hydroxyl group. Further, in the present embodiment, it is preferable to use a compound (A) containing a substituent represented by the above formula (2) among a plurality of R ₃ from the viewpoint of improving the developability. In the present embodiment, it is preferable to use a compound (A) containing a substituent represented by the above formula (3) among a plurality of R ₃ from the viewpoint of improving heat resistance. In the above formula (3), R ₄ represents a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the reactivity of the photo-curing reaction, it is preferably a hydrogen atom.

With respect to a plurality of R ₃ , from the viewpoint of improving the developability, among all the R ₃ substituents, the ratio of the substituent represented by the above formula (2) is preferably 20% or more and 85% or less, and the above formula (3) represents The ratio of the substituent is preferably 5% or more and 70% or less, and the ratio of the hydroxyl group is preferably 10% or more and 75% or less.

When the compound (A) contains at least one of the following compounds (A1) to (A5), it is preferable that the reactivity of the photocuring reaction and the heat resistance and developability of the cured product are improved. The compound (A1) is more preferably contained in any one or more of (A1) to (A5), and more preferably one or more of the compound (A1) and the compound (A2) to (A5). It is also preferable that the compound (A) contains at least the compounds (A2) and (A3).

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemistry 7]

[化8]

Commercially available products may be used as such a compound, and examples thereof include KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, and KAYARAD (registered trademark) ZCR-6007H ( The above is the trade name, Nippon Kayaku Co., Ltd., etc.

In the resin composition of the present embodiment, the acid value of the compound (A) is preferably 30 mgKOH/g or more in view of improving the developability, and is preferably 50 mgKOH/g or more in terms of improving the developability. In addition, it is considered that the acid value of the compound (A) is 120 mgKOH/g or less from the viewpoint of dissolution by the developer after the curing by the active energy ray, and it is preferable to prevent the dissolution, and it is preferably 110 mgKOH/g or less. . In addition, the "acid value" in this embodiment shows the value measured by the method of JISK 0070:1992.

In the resin composition of the present embodiment, the content of the compound (A) is not particularly limited. However, from the viewpoint of curing the resin composition by active energy rays, it is preferable to set 100 parts by mass of the resin solid content in the resin composition. It is more preferably 2 parts by mass or more, more preferably 3 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 25 parts by mass or more, and more preferably set to 30 parts by mass or more. More than the mass is better. In view of the fact that the active energy ray is sufficiently cured and the heat resistance and the developability are improved, it is preferably set to 98 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. More preferably, the amount is preferably 97 parts by mass or less, more preferably 90 parts by mass or less, more preferably 75 parts by mass or less, and more preferably 73 parts by mass or less.

<Photohardening initiator (B)> The photocuring initiator (B) used in the present embodiment is not particularly limited, and those generally used in the field of using a photocurable resin composition can be used.

Examples of the photohardening initiator (B) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; benzoin; An organic peroxide exemplified by benzamidine, oxidized laurel, acetoxy peroxide, p-chlorobenzothymidine, di(tertiary butyl) diperphthalic acid, etc.; acetophenone, 2, 2 -diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1 Acetophenones such as hydroxycyclohexyl phenyl ketone and 2-methyl-1-[4-(methylthio)phenyl]-2- morpholyl-propan-1-one; 2-ethyl Anthraquinones, 2-tertiary butyl hydrazine, 2-chloroindole, 2-pentyl hydrazine, etc.; 2,4-diethyl-9-oxosulfanyl, 2-isopropyl 9-oxosulfuric acid such as -9-oxosulfuric acid, 2-chloro-9-oxosulfuric acid, etc.; ketal such as acetophenone dimethyl ketal and benzoin dimethyl ketal a benzophenone such as benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide or 4,4'-bismethylaminobenzophenone; 2, 4, 6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethyl Phosphine oxides such as benzhydryl)-phenylphosphine oxide; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzamide)] (1 a radical photohardening initiator such as 2-Octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) or the like, or p-methoxybenzene fluorophosphonate a diazonium salt of Lewis acid such as a diazonium salt, a hexafluorophosphonic acid-N,N-diethylaminophenyl diazonium salt; a diphenylphosphonium hexafluorophosphonate; a diphenyl hexafluoroantimonate a barium salt of Lewis acid such as a salt; a triphenylsulfonium hexafluorophosphonate; a barium salt of Lewis acid such as a triphenylsulfonium hexafluoroantimonate; a triphenylsulfonium hexafluoroantimonate; A cationic photopolymerization initiator of Lewis acid, a halide, a trihalide initiator, a borate initiator, and other photoacid generators.

Among them, considering the reactivity which is suitable for the use of a multilayer printed circuit board, and the reliability of the metal conductor is high, 2-benzyl-2-dimethylamino-1-(4-cylinylphenyl)- An acetophenone-based radical photocuring initiator such as butanone-1 (manufactured by BASF JAPAN Co., Ltd., Irgacure (registered trademark) 369) is preferred.

These photohardening initiators (B) may be used singly or in combination of two or more kinds thereof, or a combination of a radical and a cationic initiator.

The content of the photo-curing initiator (B) in the resin composition of the present embodiment is not particularly limited, but the resin composition is sufficiently cured by the active energy ray to improve the heat resistance, and the resin composition is considered. The amount of the resin solid content is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 1 part by mass or more. In addition, it is preferable to set it to 30 mass parts or less, and it is set to 25 mass parts or less, and it is preferable to set it as the resin solid content in the resin composition, and it is preferable to set it as it is [ It is more preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

Any of the maleic imide compound (C) or the blocked isocyanate (D) may be used in the resin composition of the present embodiment, and these may be used in combination. In view of the improvement of the coating property, the heat resistance, and the developability, it is preferable to use the maleic imine compound (C), and to improve the heat resistance and developability, and to improve the coating property, and to use the horse. The imide compound (C) and the blocked isocyanate (D) are more preferred. The maleidinium compound (C) and the blocked isocyanate (D) are described in detail below.

<Malayimine compound (C)> The maleidide compound (C) used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimine groups in the molecule. Specific examples thereof include N-phenylmaleimide, phenylmethane maleimide, N-hydroxyphenylmaleimide, and bis(4-maleimide phenyl). Methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, bis(3,5- Dimethyl-4-maleimine phenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl- 4-maleimide phenyl)methane, polytetrahydrofuran-bis(4-maleimide benzoate), o-phenyl-p-maleimide, meta-phenyl phenylephrine Amine, p-phenylene bismaleimide, phenyl phenyl sulphate, phenyl bisphosphonium imine, phenyl phenyl sulphate, 2,2- Bis(4-(4-maleimide phenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane double mala Imine, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4 -diphenyl ether bismaleimide, 4,4-diphenylfluorene bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3- (4-maleimide phenoxy)benzene, 4,4-diphenylmethane bis citrate, 2,2-bis[4-(4- citrate iminophenoxy)benzene Propane, bis(3,5-dimethyl-4-limampamidine phenyl)methane, bis(3-ethyl-5-methyl-4-xanthene phenylene phenyl)methane, Bis(3,5-diethyl-4-scinoconazole phenyl)methane, polyphenylmethane maleimide, maleic imine compound represented by the following formula (4), the following formula (5) And a prepolymer of the maleic imine compound, and the prepolymer of the maleimide compound and the amine compound.

In view of the above, it is preferable that the maleic imine compound represented by the following formula (4) and the maleidin compound represented by the following formula (5) are preferable from the viewpoint of obtaining good coating property and being excellent in heat resistance. (4) The maleidin compound represented by the compound is more preferable. A commercially available product may be used as the maleic imine compound represented by the following formula (4), and for example, BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) may be mentioned. A commercially available product can also be used for the maleic imine compound represented by the following formula (5), and for example, MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. These maleimide compounds (C) may be used alone or in combination of two or more.

[Chemistry 9]

In the formula (4), a plurality of R ₅ each independently represent a hydrogen atom or a methyl group. n ₁ represents an integer of 1 or more, and an integer of 1 to 10 is more preferable.

[化10]

In the formula (5), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group. n ₂ represents an integer of 1 or more, and an integer of 1 to 5 is more preferable.

The content of the maleic imine compound (C) in the resin composition of the present embodiment is not particularly limited, but the resin solid in the resin composition is considered from the viewpoint of sufficiently curing the resin composition and improving heat resistance. The amount of the component is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, and still more preferably 0.5 parts by mass or more. In addition, it is preferable to set it to 50 mass parts or less, and it is set to 45 mass parts or less, and it is more preferable to set it as 40 mass parts or less, and it is more preferable to set it as the mass of the resin solids in the resin composition. It is more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and more preferably 7 parts by mass or less.

<The blocked isocyanate (D)> The blocked isocyanate (D) used in the present embodiment is inactive at normal temperature (25 ° C), but when heated, the blocking agent is reversely dissociated to regenerate the isocyanate. There is no special restriction on the base. Examples of the blocked skeleton of the blocked isocyanate (D) include an isocyanurate type, a biuret type, and an addition type. The isocyanurate type is considered from the viewpoint of heat resistance. ideal. These blocked isocyanates (D) may be used singly or in combination of two or more kinds as appropriate.

The blocking agent which is inactive at normal temperature (25 ° C), but dissociates in the reverse direction when heated, may be selected from the group consisting of diketones, anthraquinones, phenols, alkanols and caprolactams. At least one compound. Specific examples thereof include methyl ethyl ketone oxime and ε-caprolactam. The dissociation temperature of the blocking agent is not particularly limited, but it is preferably 120 ° C or more from the viewpoint of sufficiently curing the resin composition to improve heat resistance. Further, from the viewpoint of sufficiently dissociating the blocking agent to harden the resin composition, it is preferable to be 200 ° C or lower.

The above blocking agent is discharged as a gas after dissociation upon heating. Considering the reason for the decrease in volume, it is preferable to use a small molecular weight as the blocking agent. Specifically, it is desirable to use a methyl ethyl ketone oxime type.

Such a blocked isocyanate can be easily obtained in the form of a commercially available product, and examples thereof include SUMIDUR (registered trademark) BL-3175, BL-4265, BL-5375, BL-1100, and BL-1265 (above, trade name, Sumika) Covestro Urethane Co., Ltd.; CORONATE (registered trademark) 2507, CORONATE (registered trademark) 2554 (above is the trade name, manufactured by Tosoh Corporation); DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) 17B-60PX (the above is a trade name, manufactured by Asahi-Kasei Chemicals Co., Ltd.) and the like. Among these, the blocked skeleton is preferably one or more selected from the group consisting of SUMIDUR (registered trademark) BL-3175 and DURANATE (registered trademark) TPA-B80E of the isocyanurate type. By containing such a type of blocked isocyanate, there is a tendency to further improve the heat resistance of the obtained cured product.

The content of the blocked isocyanate (D) in the resin composition of the present embodiment is not particularly limited. However, from the viewpoint of sufficiently curing the resin composition and improving heat resistance, the resin solid content in the resin composition is considered. It is preferably set to 0.1 part by mass or more, more preferably 0.2 part by mass or more, more preferably 0.3 part by mass or more, even more preferably 0.5 part by mass or more. In addition, from the viewpoint of suppressing the decrease in the volume of the resin composition and the improvement of the developability, the amount of the resin solid content in the resin composition is preferably 5.0 parts by mass or less or less than 5.0 parts by mass, and is set to 4.0 mass. More preferably, it is less than 4.0 parts by mass, and it is more preferably 3.0 mass parts or less or less than 3.0 parts by mass.

When the maleic imine compound (C) and the blocked isocyanate (D) are used in combination, the content thereof is not particularly limited, but the resin composition is sufficiently hardened and the heat resistance is improved, and the resin composition is considered. The amount of the resin solid content in the resin is preferably 0.11 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more. In addition, it is preferable to set the amount of the resin composition to be less than 55 parts by mass, and to set the amount of the resin composition to be more excellent, and to improve the developability, and to obtain a more favorable coating film. It is more preferably 25 parts by mass or less, more preferably 15 parts by mass, more preferably 13 parts by mass or less, and even more preferably 10 parts by mass.

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

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 bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol A novolac resin type epoxy resin. Resin, biphenyl type epoxy resin, phenol novolac resin type epoxy resin, cresol novolac resin type epoxy resin, xylenol varnish resin type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy Resin, naphthalene skeleton modified novolac resin epoxy resin, naphthyl ether epoxy resin, phenol aralkyl epoxy resin, fluorene epoxy resin, trifunctional phenol epoxy resin, tetrafunctional phenol type Epoxy resin, triepoxypropyl isocyanurate, glycidyl ester epoxy resin, cycloaliphatic epoxy resin, dicyclopentadiene novolac resin epoxy resin, biphenolic aldehyde varnish resin ring Oxygen resin, phenol aralkyl novolac resin epoxy resin, naphthol aralkyl novolac resin epoxy resin, aralkyl novolac resin epoxy resin, biphenyl aralkyl epoxy resin, naphthalene Phenol aralkyl type epoxy resin, dicyclopentadiene type ring An oxygen resin, a polyol epoxy resin, a phosphorus-containing epoxy resin, a compound obtained by epoxidizing a double bond such as a glycidylamine or a butadiene, and a hydroxy group-containing fluorenone resin and an epichlorohydrin. The compound obtained by the reaction, and the halides thereof.

Among them, one or more selected from the group consisting of a biphenyl aralkyl type epoxy resin, a stretch naphthyl ether type epoxy resin, a polyfunctional phenol type epoxy resin, and a naphthalene type epoxy resin are preferable. It is more preferred to be a biphenyl aralkyl type epoxy resin. By containing such an epoxy resin, there is a tendency to further improve the heat resistance of the obtained cured product. These epoxy resins (E) may be used alone or in 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 it is preferably set in accordance with 100 parts by mass of the resin solid content in the resin composition from the viewpoint of improving the heat resistance of the cured product. It is more preferably set to 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. In view of the fact that the resin composition of the resin composition is preferably 100 parts by mass or less, it is preferably set to 70 parts by mass or less, and more preferably 50 parts by mass. The following is even better, and it is even better to set it to 25 parts by mass or less.

<Compound (F) having an ethylenically unsaturated group> The resin composition of the present embodiment can also be used in combination in order to improve reactivity with an active energy ray (for example, ultraviolet ray) and to improve developability and heat resistance. Unsaturated group of compound (F). The compound (F) having an ethylenically unsaturated group used in the present embodiment is a compound (A) having an acid value of 30 mgKOH/g or more and 120 mgKOH/g or less represented by the above formula (1), and has 1 in one molecule. The compound having at least one of the ethylenically unsaturated groups is not particularly limited, and examples thereof include compounds having a (meth)acryl fluorenyl group and a vinyl group. These compounds (F) having an ethylenically unsaturated group may be used singly or in combination of two or more kinds as appropriate.

Examples of the compound having a (meth)acryl fluorenyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, and poly(methyl). Ethylene glycol acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenyl ethyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Benzyl methacrylate, tetrahydrofurfuryl (meth) acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate , bis(meth)acrylate decyl glycol ester, di(meth)acrylic acid glycolate, di(ethyl) methacrylate, ethylene glycol di(meth)acrylate, isocyanuric acid (Meth) propylene oxime ethyl ester, poly(meth)acrylic acid propylene glycol ester, di(meth)acrylic acid adipate epoxy ester, di(meth)acrylic acid bisphenol ethylene oxide ester, (methyl Acrylic acid hydrogenated bisphenol ethylene oxide ester, bis(meth)acrylic acid bisphenol ester, ε-caprolactone modified di(meth)acrylic acid hydroxytrimethylacetate neopentyl glycol ester, ε-caprolactone Modified hexa(methyl) propylene Dipentaerythritol ester, ε-caprolactone modified poly(m-pentaerythritol) (meth) acrylate, neopentyl glycol (meth) acrylate, trimethylol tris(meth)acrylate Propane ester, trishydroxyethyl tris(meth)acrylate, and its ethylene oxide adduct; pentaerythritol tris(meth)acrylate, and its ethylene oxide adduct; Methyl) neopentyl glycol acrylate, dipentaerythritol hexa(meth)acrylate, an ethylene oxide adduct thereof, and the like.

Further, a urethane (meth) acrylate having a (meth) acrylonitrile group bonded to a urethane in the same molecule; and also having (meth) propylene in the same molecule a thiol-ester-bonded polyester (meth) acrylate; an epoxy (meth) acrylate derived from an epoxy resin and having a (meth) acrylonitrile group; compositely utilizing the bonding Reactive oligomers and the like.

The above urethane (meth) acrylate refers to a reactant containing a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as needed. For example, hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or hydroxybutyl (meth)acrylate; glycerol mono(meth)acrylate; (meth)acrylic acid glycerides such as (meth)acrylic acid glyceride; neopentyl glycol di(meth)acrylate, neopentyl glycol tri(meth)acrylate, and bis(methyl)acrylic acid (meth)acrylic acid sugar alcohol esters such as pentaerythritol ester, and toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate Vulverone ester, decylene diisocyanate, dylyl diisocyanate, xylyl diisocyanate, dicyclohexyl methylene diisocyanate, and the isocyanuric acid A polyisocyanate such as an acid ester or a biuret reactant is reacted to form a urethane (meth) acrylate.

The above epoxy (meth) acrylate means a compound having an epoxy group and a carboxylic acid ester compound of (meth)acrylic acid. For example, a phenol novolak resin type epoxy (meth) acrylate, a cresol novolak resin type epoxy (meth) acrylate, a hydroxy phenyl methane type epoxy (meth) acrylate, a dicyclopentyl Diene phenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate , bisphenol A novolac resin epoxy (meth) acrylate, naphthalene skeleton epoxy (meth) acrylate, glyoxal epoxy (meth) acrylate, heterocyclic epoxy (a An acrylate or the like, and an acid anhydride-modified epoxy (meth) acrylate or 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 the styrenes include styrene, methylstyrene, ethylstyrene, divinylbenzene, α-methylstyrene, and the like. Examples of the other vinyl compound include triallyl isocyanurate, trimethylallyl isocyanurate, bisallylnadiimide, and the like.

Among these, it is preferably selected from neopentyl tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, cresol novolac resin epoxy (meth) acrylate, One or more of the group consisting of bisphenol A epoxy (meth) acrylate, epoxy (meth) acrylate containing naphthalene skeleton, and bisallyl nadic ylidene amide ) Dipentaerythritol acrylate is preferred. By containing such a compound having an ethylenically unsaturated group, there is a tendency to further improve the heat resistance of the obtained cured product.

In the resin composition of the present embodiment, the content of the compound (F) having an ethylenically unsaturated group is not particularly limited. However, from the viewpoint of good developability, 100 parts by mass of the resin solid content in the resin composition is used. It is preferably set to 0.5 parts by mass or more, more preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, even more preferably 5 parts by mass or more, and more preferably 15 parts by mass or more. In addition, it is preferable to set it to 90 mass parts or less, and it is set to 70 mass parts or less, and it is set to 50 mass parts or less, and it is set to 50 mass parts or less with respect to 100 mass parts of resin solids in the resin composition from the viewpoint of the heat resistance optimization of a hardening|curing material. More preferably, it is more preferably set to 25 parts by mass or more.

<Inorganic filler (G)> In the resin composition of the present embodiment, the inorganic filler (G) can be used in combination in order to improve various properties such as coating property, developability, and heat resistance. The inorganic filler (G) used in the present embodiment is not particularly limited as long as it has insulating properties, and examples thereof include cerium oxide (for example, natural cerium oxide, molten cerium oxide, amorphous cerium oxide, and hollow). Cerium oxide, etc.), aluminum compounds (such as soft boehmite, aluminum hydroxide, aluminum oxide, etc.), magnesium compounds (such as magnesium oxide, magnesium hydroxide, etc.), calcium compounds (such as calcium carbonate, etc.), molybdenum compounds (such as oxidation) Molybdenum, zinc molybdate, etc.), antimony compounds (such as barium sulfate, barium strontium citrate, etc.), talc (such as natural talc, calcined talc, etc.), mica (mica), glass (for example, short fibrous glass, spherical glass, powder) Glass (for example, E glass, T glass, D glass, etc.), etc., anthrone powder, and the like.

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

These inorganic fillers (G) may be surface-treated by a decane coupling agent or the like which will be described later.

In particular, from the viewpoint of improving the heat resistance of the cured product and obtaining good coating film properties, it is preferably cerium oxide, which is particularly preferred as molten cerium oxide. Specific examples of the cerium oxide include SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Co., Ltd., and the like. These inorganic fillers (G) may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the inorganic filler (G) is not particularly limited. However, from the viewpoint of improving the heat resistance of the cured product, it is preferable to set 100 parts by mass of the resin solid content in the resin composition. It is more preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. In view of the fact that the resin composition of the resin composition is preferably 100 parts by mass or less, it is preferably set to 350 parts by mass or less, and more preferably 300 parts by mass. More preferably, it is better to set it to 100 parts by mass or less.

<Centane coupling agent and wetting dispersing agent> The resin composition of the present embodiment can also be used in combination with a decane coupling agent and/or wet in order to improve the dispersibility of the inorganic filler, the adhesion strength of the polymer and/or the resin and the inorganic filler. Dispersant.

The decane coupling agent is not particularly limited as long as it is a decane coupling agent which is usually used for the surface treatment of an inorganic substance. Specific examples include, for example, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, and the like; γ- An epoxy decane system such as glycidoxypropyltrimethoxydecane; an acrylic decane system such as γ-acryloxypropyltrimethoxydecane; and N-β-(N-vinylbenzylamino group) a cationic decane system such as ethyl)-γ-aminopropyltrimethoxydecane hydrochloride; a phenyl decane-based decane coupling agent. These decane coupling agents may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the decane coupling agent is not particularly limited, and is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition.

In the case of the wetting dispersant, there is no particular limitation if it is a dispersion stabilizer used for coating purposes. Specific examples thereof include DISPERBYK (registered trademark)-110, 111, 118, 180, 161 manufactured by BYK Japan Co., Ltd.; BYK (registered trademark)-W996, W9010, W903 and the like. These wetting dispersing agents may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the wet dispersant is not particularly limited, and is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition.

<Thermal Curing Accelerator> The resin composition of the present embodiment can also be used in combination with the thermosetting accelerator in the range which does not impair the characteristics of the embodiment.

The thermosetting accelerator is not particularly limited, and examples thereof include benzammonium peroxide, lauric acid peroxide, ethidium peroxide, p-chlorobenzothyron peroxide, and di(tertiary butyl diperoxide). Ordinary exemplified organic peroxide; azo compound such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2- Three grades of N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methyl porphyrin, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, etc. Amines; phenols such as phenol, xylenol, cresol, resorcinol, catechol; lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, An organic metal salt such as dibutyltin maleate, manganese naphthenate, cobalt naphthenate or iron acetoxyacetate; the organic metal salt is dissolved in a hydroxyl group-containing compound such as phenol or bisphenol; An inorganic metal salt such as tin, zinc chloride or aluminum chloride; an organotin compound such as dioctyltin oxide, other alkyl tin or alkyl tin oxide; 1,2-dimethylimidazole, 1-benzyl- 2-phenylimidazole An imidazole compound such as triphenylimidazole (TPIZ).

These thermosetting accelerators may be used alone or in combination of two or more.

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

<Organic solvent> The resin composition of the present embodiment may contain a solvent as needed. For example, when an organic solvent is used, the viscosity at the time of preparation of the resin composition can be adjusted. The type of the solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition. Specific examples thereof are not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl siatone; aromatic hydrocarbons such as toluene and xylene; and guanamines such as dimethylformamide; and propylene glycol; Monomethyl ether and its acetate.

These organic solvents may be used alone or in combination of two or more.

<Other components> In the resin composition of the present embodiment, the thermosetting resin, the thermoplastic resin and the oligomer thereof, and the elasticity which have not been enumerated so far can be used in combination within the range which does not impair the characteristics of the embodiment. Various polymer compounds such as bulks; flame retardant compounds not yet listed; additives, and the like. These are generally not subject to any particular restrictions by the user. For example, the flame retardant compound may, for example, be a nitrogen-containing compound such as melamine or benzoguanamine, a compound containing a □ ring, a phosphate compound of a phosphorus compound, an aromatic condensed phosphate, or a halogen-containing condensed phosphate. . Examples of the additives include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, lubricants, antifoaming agents, surface conditioners, glossing agents, polymerization inhibitors, and the like. These components may be used alone or in combination of two or more.

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

The resin composition of the present embodiment is obtained by using the compound (A), the photocuring initiator (B), the maleimide compound (C) and/or the blocked isocyanate (D), and if necessary The epoxy resin (E), the compound (F) having an ethylenically unsaturated group, the inorganic filler (G), the decane coupling agent, the wetting dispersing agent, the thermosetting accelerator, the organic solvent, or other components are appropriately mixed. Got it. In the resin composition of the present embodiment, it is preferable to use a varnish as a resin sheet to which the support of the present embodiment described later is produced.

<Method for Producing Resin Composition> The method for producing the resin composition of the present embodiment is not particularly limited, and for example, a method in which the above components are blended into a solvent in order and sufficiently stirred is mentioned.

The resin composition may be subjected to a known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing the components at the time of production. Specifically, the dispersibility of the inorganic filler (G) to the resin composition can be improved by performing the agitation dispersion treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The stirring, mixing, and kneading treatment can be suitably carried out by using a known apparatus such as a stirring device for dispersing, such as an ultrasonic homogenizer; a three-roll mill, a ball mill, a bead mill, a sand mill, or the like. a device for mixing purposes; or a mixing device for revolution or self-transition. Further, when the resin composition of the present embodiment is prepared, 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 in an application requiring an insulating resin composition, and is not particularly limited, and can be used in the following applications: a photosensitive film, a photosensitive film with a support, and a resin sheet with a support attached thereto. Insulating resin sheet such as prepreg, circuit board (for laminated board, for multilayer printed circuit board, etc.), solder resist, underfill material, chip solder material, semiconductor sealing material, landfill resin, part embedded resin Wait. Among them, a resin composition or a solder resist for use as an insulating layer of a multilayer printed circuit board is preferably used.

<Resin sheet to which the support is attached> The resin sheet with the support of the present embodiment includes a support and a resin composition layer containing the resin composition of the present embodiment formed on the surface of the support, and the resin composition is The resin sheet coated with the support is applied to one side or both sides of the support. The resin sheet to which the support is attached can be obtained by applying a resin composition onto a support and drying it.

The support used in the resin sheet with the support of the present embodiment is not particularly limited, and a known one may be used, and a resin film is preferable. Examples of the resin film include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, and a polypropylene. A resin film such as a (PP) film, a polyethylene (PE) film, a polyethylene naphthalate film, a polyvinyl alcohol film, or a triethylene acetate film. Among them, it is preferably a PET film.

In order to easily peel off the resin composition layer, it is preferable to use a surface-coated release agent. 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. When the thickness is less than 5 μm, the support tends to be easily broken when the support is peeled off before development. When the thickness exceeds 100 μm, the resolution tends to decrease when exposed from above the support.

Further, in order to reduce scattering of light during exposure by active energy rays such as ultraviolet rays, the resin film is preferably excellent in transparency.

Further, in the resin sheet with the support attached in the embodiment, the resin composition layer may be protected by a protective film. By protecting the resin composition layer with a protective film, it is possible to prevent dust or the like from adhering to the surface of the resin composition layer or scratching. As the protective film, a film composed of the same material as the above resin film can be used. The thickness of the protective film is not particularly limited, and 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 workability of the protective film tends to be lowered. When the thickness exceeds 50 μm, the low-cost property tends to be poor. Further, the protective film is preferably one in which the adhesion between the resin composition layer and the support is small, and the adhesion between the resin composition layer and the protective film is small.

The method of producing the resin sheet with the support of the present embodiment is not particularly limited. For example, the resin composition of the present embodiment is applied to a support such as a PET film, and then the organic solvent is dried and removed to produce an attached product. A method of supporting a resin sheet of a body, and the like.

The above coating can be carried out by a known method using, for example, a roll coater, a coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, or an extrusion coater. The drying can be carried out, for example, by heating in a dryer at 60 to 200 ° C for 1 to 60 minutes.

The amount of the organic solvent remaining in the resin composition layer is preferably 5% by mass or less based on the total mass of the resin composition layer from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. In the resin composition layer, the thickness of the resin composition of the resin sheet to which the support is attached is preferably 1.0 μm or more from the viewpoint of improving the workability. Moreover, in view of improving the transmittance and improving the developability, it is preferably 300 μm or less.

The resin sheet to which the support is attached in 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, laminating one or more resin sheets with the support described above.

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

(Laminating step) The resin composition layer of the resin sheet with the support of the present embodiment is laminated on one side or both sides of the circuit board by a vacuum laminator. Examples of the circuit board include a glass epoxy resin substrate, a metal substrate, a ceramic substrate, a tantalum substrate, a semiconductor sealing resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit substrate herein refers to a substrate on which a conductor layer (circuit) obtained by patterning is formed on one surface or both surfaces of the substrate as described above. Further, in a multilayer printed wiring board in which a conductor layer and an insulating layer are alternately laminated, a single-sided or double-sided layer of the outermost layer of the multilayer printed wiring board is patterned to form a substrate of a conductor layer (circuit). Included in the circuit substrate referred to herein. Further, the surface of the conductor layer may be subjected to a roughening treatment by a blackening treatment or a copper etching. In the laminating step, when the resin sheet with the support has a protective film, the protective film is peeled off, and the resin sheet and the circuit board with the support are required to be preheated, and the resin composition layer is pressurized. It is crimped to the circuit board under heating. In the resin sheet with the support attached to the present embodiment, a method of laminating the circuit board under reduced pressure by vacuum lamination is preferably used.

The conditions of the laminating step are not particularly limited. For example, the crimping temperature (laminating temperature) should be set to 50 ° C to 140 ° C, and the crimping pressure should be set to 1 kgf / cm ² to 15 kgf / cm ² , and the crimping time should be set to It is preferable to carry out lamination under a reduced pressure of the air pressure of 20 mmHg or less for 5 seconds to 300 seconds. Further, the laminating step may be a batch type or a continuous type using a roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a two-stage build-up laminator manufactured by Nikko-Materials Co., Ltd., or the like can be mentioned.

(Exposure Step) After the resin sheet with the support is placed on the circuit board by the lamination step, the active energy ray is irradiated to a predetermined portion of the resin composition layer, and an exposure step of curing the resin composition layer of the irradiation portion is performed. The irradiation of the active energy ray may be by a mask pattern or a direct delineation method of directly illuminating the active energy ray.

Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, and X-rays, and are particularly excellent for ultraviolet rays. The amount of ultraviolet rays irradiated is approximately 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method by the mask pattern has a contact exposure method in which a mask pattern is adhered to a printed circuit board, and a non-contact exposure method in which parallel light is not used for exposure without being bonded, and any one of them may be used. Further, when a support is present on the resin composition layer, exposure may be performed from above the support, or the support may be peeled off and exposed.

(Developing Step) When the support is present on the resin composition layer after the exposure step, the support is removed, and the portion (unexposed portion) that has not been photo-cured is removed by wet development for development. An insulating layer pattern is formed.

In the case of the wet development, the developing solution is not particularly limited as long as it can selectively elute the unexposed portion, and a developing solution such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent can be used. In the present embodiment, the development step using an alkaline aqueous solution is particularly preferable. These developing solutions may be used alone or in combination of two or more. Further, the development method can be carried out by a known method such as spraying, shaking immersion, brushing, or scraping.

The aqueous alkali solution used as the developer is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, sodium tetraborate, ammonia, and amines.

The concentration of the aqueous alkali solution is preferably from 0.1% by mass to 60% by mass based on the total amount of the developing solution. Further, the temperature of the aqueous alkali solution can be adjusted in accordance with the developability. In addition, these alkali aqueous solutions may be used alone or in combination of two or more.

In the pattern formation of the present embodiment, the above two or more development methods may be used in combination as needed. The development methods include: dipping type, dipping type, spray type, high pressure spray type, brushing, slapping, etc., and high pressure spray type can improve the resolution. The spray pressure when using a spray type is preferably 0.02 MPa to 0.5 MPa.

(Post bake step) After the above development step is completed, a post-baking step is performed and an insulating layer (cured material) is formed. The post-baking step may be an ultraviolet irradiation step using a high-pressure mercury lamp or a heating step using a dust-free oven. When the ultraviolet ray is irradiated, the irradiation amount may be adjusted as needed, and for example, irradiation may be performed with an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² . Further, the heating condition may be appropriately selected depending on the type and content of the resin component in the resin composition, but it is preferably selected from the range of 150 ° C to 220 ° C for 20 minutes to 180 minutes, and 160 ° C to 200 ° C for 30 minutes. The range of ~150 minutes is better.

(Plating Step) Then, a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating. As the dry plating, a known method such as a vapor deposition method, a sputtering method, or an ion plating method can be used. The vapor deposition method (vacuum vapor deposition method) can form a metal film on the insulating layer by, for example, placing a support in a vacuum container and heating and evaporating the metal. The sputtering method can be carried out, for example, by placing a support in a vacuum container and introducing a passive gas such as argon, and applying a direct current voltage to cause the ionized passive gas to collide with the target metal and strike the metal. The formation of a metal film is performed on the insulating layer.

In the case of wet plating, the surface of the formed insulating layer is sequentially applied: a swelling treatment by a swelling liquid, a roughening treatment by an oxidizing agent, and a neutralization treatment using a neutralizing liquid, thereby insulating the layer The surface is roughened. The swelling treatment by the swelling liquid is carried out by immersing the insulating layer in a swelling liquid at 50 ° C to 80 ° C for 1 minute to 20 minutes. The swelling solution may be an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. As a commercially available swelling liquid, for example, APPDES (registered trademark) MDS-37 manufactured by Uemura Industrial Co., Ltd., and the like can be mentioned.

The roughening treatment by the oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 ° C to 80 ° C for 5 minutes to 30 minutes. The oxidizing agent may, for example, be an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably set to 5 mass% to 10 mass%. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as APPDES (registered trademark) MDE-40 manufactured by Uemura Industrial Co., Ltd., APPDES (registered trademark) ELC-SH. It is carried out by using a neutralization liquid as a neutralization treatment system and immersing it in 30 ° C - 50 ° C for 1 minute - 10 minutes. In the case of the neutralization liquid, an acidic aqueous solution is preferred, and as a commercial product, APPDES (registered trademark) MDN-62 manufactured by Uemura Industrial Co., Ltd. is exemplified.

Then, electroless plating and electrolytic plating are combined to form a conductor layer. Further, it is also possible to form a plating resist which is a reverse resist pattern with the conductor layer and to form the conductor layer only by electroless plating. As a method of forming the subsequent pattern, for example, a subtractive method, a semi-additive method, or the like can be used.

<Semiconductor device> The semiconductor device of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and specifically, it can be produced by the following method. A semiconductor wafer can be mounted by mounting a semiconductor wafer at a conductive position of the multilayer printed circuit board of the present embodiment. Here, the conductive position refers to a position in the multilayer printed circuit board where the electrical signal can be transmitted, and the place can be any position where the surface can be embedded or not. Further, the semiconductor wafer is not particularly limited as long as it is a circuit element made of a semiconductor.

The method of mounting the semiconductor wafer in the case of manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor wafer can function effectively, and specific examples thereof include a wire bonding method, a flip chip mounting method, and a bump-free method. The mounting method of the layer (BBUL), the mounting method by the anisotropic conductive film (ACF), the mounting method by the non-conductive film (NCF), and the like.

Further, a semiconductor device can be manufactured by laminating a resin sheet with a support according to the present embodiment on a semiconductor wafer. After lamination, it can be manufactured by the same method as the above-mentioned multilayer printed wiring board. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples.

[Example 1] (Preparation of a resin composition and a resin sheet with a support attached thereto) Propylene glycol monomethyl ether acetate of a TrisP-PA epoxy acrylate compound compounded as the compound (A) (hereinafter sometimes referred to simply as PGMEA) solution (KAYARAD (registered trademark) ZCR-6002H, non-volatile content: 65 mass%, acid value: 60 mg KOH/g, manufactured by Nippon Chemical Co., Ltd.), 81.2 parts by mass (52.8 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1-(4-cylinylphenyl)-butanone-1 as photohardening initiator (B) (Irgacure (registered trademark) 369, BASF JAPAN ( 5 parts by mass of 3.5 parts by mass of a maleic imine compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) as a maleic imine compound (C), as an epoxy resin (E) Pentaphenyl aralkyl type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 19.8 parts by mass of dipentaerythritol hexaacrylate as a compound (F) having an ethylenically unsaturated group (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd., 18.9 parts by mass, methyl ethyl ketone (hereinafter sometimes referred to as MEK) slurry of antimony oxide treated cerium oxide as inorganic filler (G) (SC2050MB, flat) Particle diameter of 0.5 m, a non-volatile content of 70 mass%, Admatechs (shares), Ltd.) 71.4 parts by weight (in terms of non-volatile component of 50 parts by mass), an ultrasonic homogenizer with stirring to obtain a varnish (resin solution of the composition). The varnish was applied to a PET film (UNIPEEL (registered trademark) TR1-38, manufactured by Uniji Co., Ltd., trade name) having a thickness of 38 μm, and dried by heating at 80 ° C for 7 minutes to obtain a PET film as a support. A resin sheet with a support having a thickness of 30 μm and a thickness of the resin composition layer.

In addition, KAYARAD (registered trademark) ZCR-6002H contains a mixture of any one or more of the above compound (A1) and the above compounds (A2) to (A5).

(Production of inner layer circuit board) A glass cloth substrate BT resin double-sided copper-clad laminate in which an inner layer circuit is formed (copper foil thickness: 18 μm, laminated plate thickness: 0.2 mm, Mitsubishi Gas Chemical Co., Ltd.) The double-sided surface of the registered trademark)-HL832NS was roughened by the surface of the CZ8100 manufactured by MEC (share) to obtain an inner layer circuit board.

(Production of the laminate for evaluation) The resin surface of the resin sheet with the support was placed on the inner layer circuit board, and vacuum suction was performed for 30 seconds using a vacuum laminator (manufactured by Nikko-Materials Co., Ltd.). After MPa or less, it was laminated and formed at a pressure of 10 kgf/cm ² and a temperature of 70 ° C for 30 seconds. Further, by laminating the laminate under the conditions of a pressure of 10 kgf/cm ² and a temperature of 70 ° C for 60 seconds, a laminate obtained by laminating an inner layer circuit board, a resin composition layer, and a support was obtained. An exposure step of irradiating the obtained laminate with ultraviolet rays of 200 mJ/cm ² was carried out, and the support was peeled off and developed in a 1% by mass aqueous sodium carbonate solution to prepare a laminate for evaluation.

(Preparation of cured product for evaluation) The resin sheet with the support was irradiated with ultraviolet rays of 200 mJ/cm ² , and then subjected to a heat treatment at 180 ° C for 120 minutes, followed by a baking step, and then the support was peeled off to obtain an evaluation. Use hardened materials.

[Example 2] A PGMEA solution (KAYARAD (registered trademark) ZCR-6002H, which is a compound of the compound (A), was added as a non-volatile component, and the acid value was 60 mgKOH/g, Nipponization. 82.1 parts by mass (53.4 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1-(4-cylinylphenyl)-butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF JAPAN Co., Ltd.) 5 parts by mass of SUMIDUR (registered trademark) BL-3175 (solvent naphtha solution, nonvolatile matter 75 mass%) as the blocked isocyanate compound (D) (including the capping agent), Sumika Covestro Urethane (stock), trade name) 3.3 parts by mass (2.5 parts by mass in terms of non-volatile content (including blocking agent)), biphenyl aralkyl type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 19.9 parts by mass of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 19.2 parts by mass, treated with epoxy decane MEK slurry of cerium oxide (SC2050MB, average particle diameter 0.5 μm, non-volatile content 70% by mass, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of nonvolatile content), supersonic Homogenizer with stirring to obtain a varnish (resin solution of the composition). 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] A PGMEA solution (KAYARAD (registered trademark) ZCR-6002H, which is a compound of the compound (A), was added as a non-volatile component, 65 mass%, acid value: 60 mgKOH/g, Nipponization 80.5 parts by mass (52.3 parts by mass in terms of nonvolatile content), 2-benzyl-2-dimethylamino-1-(4-cylinylphenyl)-butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF JAPAN Co., Ltd.) 5 parts by mass of a maleic imine compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) as a maleic imine compound (C) SUMIDUR (registered trademark) BL-3175 (solvent naphtha solution, nonvolatile matter 75 mass% (including terminal blocking agent), and Sumika Covestro Urethane (manufactured by the company) as a blocked isocyanate compound (D) Name) 3.3 parts by mass (2.5 parts by mass in terms of non-volatile content (including blocking agent)), biphenyl aralkyl type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.), 18 parts by mass, hexaacrylic acid Dimethyl pentaerythritol ester (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 18.7 parts by mass of MEK slurry of ceria-treated cerium oxide (SC2050MB, average particle diameter 0.5 μm, Volatile content 70 mass%, Admatechs (shares), Ltd.) 71.4 parts by weight (in terms of non-volatile component 50 parts by mass), an ultrasonic homogenizer with stirring to obtain a varnish (resin solution of the composition). 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 of bisphenol F type epoxy acrylate (KAYARAD (registered trademark) ZFR-1553H, nonvolatile matter 68% by mass, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) A varnish was obtained in the same manner as in Example 1 except that the compound (A) was replaced by a non-volatile component (52.8 parts by mass), and a resin sheet with a support, a laminate for evaluation, and hardening for evaluation were obtained. Things.

[Comparative Example 2] Using cresol novolak resin type epoxy acrylate (EA-7140, nonvolatile matter 73% by mass, acid value: 70 mgKOH/g, manufactured by Shin-Nakamura Chemical Co., Ltd.) 72.3 parts by mass (by non- A varnish was obtained in the same manner as in Example 1 except that the compound (A) was replaced with the volatile component (52.8 parts by mass), and a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation were obtained.

[Comparative Example 3] Using cresol novolak resin type epoxy acrylate (EA-7420, nonvolatile matter 73% by mass, acid value: 1 mgKOH/g, manufactured by Shin-Nakamura Chemical Co., Ltd.) 72.3 parts by mass A varnish was obtained in the same manner as in Example 1 except that the compound (A) was replaced with the volatile component (52.8 parts by mass), and a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation were obtained.

[Comparative Example 4] Using a biphenyl aralkyl type epoxy acrylate (KAYARAD (registered trademark) ZCR-1642H, nonvolatile matter 60% by mass, acid value: 99 mg KOH/g, manufactured by Nippon Chemical Co., Ltd.) 88 mass A varnish was obtained in the same manner as in Example 1 except that the compound (A) was replaced by a non-volatile component (52.8 parts by mass), and a resin sheet with a support and a laminate for evaluation were evaluated. Use hardened materials.

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

[Evaluation of physical property measurement] Each of the resin sheets with the support obtained by using the varnish obtained in Examples 1 to 3 and Comparative Examples 1 to 5, each of the evaluation laminates, and each of the cured products for evaluation were measured and subjected to the following methods. Evaluation. The results are summarized in Table 1.

<Coating property> The resin surface end portion of the resin sheet with the support of the A4 size was gently pressed with a finger, and the degree of adhesion to the finger was evaluated according to the following criteria. ◎: No attachment to the finger was observed. The end of the resin sheet to which the support is attached is not lifted. ○: Almost no attachment to the finger was observed. The end portion of the resin sheet with the support attached is attached to the finger, but is peeled off from the finger and dropped at a height of less than 30 mm. ×: The attachment to the finger was observed. The end of the resin sheet with the support is attached to the finger and raised to a height of 30 mm or more.

<Heat resistance (glass transition temperature)> Each of the cured products for evaluation was heated at 10 ° C/min using a DMA apparatus (dynamic viscoelasticity measuring apparatus DMAQ800 manufactured by TA Instruments), and the peak position of the LossModulus was set as the glass transition temperature ( Tg, °C).

<Developability> The development surface of each of the evaluation laminates was visually observed, and then observed by SEM (magnification: 1,000 times), and whether or not there was a residue was evaluated by the following criteria. ○: There is no development residue in the range of 30 mm square, and the developability is excellent. ×: There is a development residue in the range of 30 mm square, and the developability is poor.

[Table 1]

As is apparent from Table 1, Examples 1 to 3 have high heat resistance (Tg) and excellent developability. Among them, the coating property of Example 3 was particularly excellent. On the other hand, in Comparative Examples 1 to 5, either one of heat resistance (Tg) and developability was insufficient. Therefore, according to the present invention, a resin composition excellent in heat resistance and developability, a resin sheet with a support, a multilayer printed wiring board, and a semiconductor device can be obtained.

no

no

Claims (7)

A resin composition comprising: 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), and a maleimide compound (C); / or blocked isocyanate (D); [Chemical 1] In the formula (1), a plurality of R ₁ each independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ each independently represent a hydrogen atom or a methyl group, and a plurality of R ₃ each independently represent a substitution represented by the following formula (2). a substituent or a hydroxyl group represented by the following formula (3); [Chemical 2] [Chemical 3] In the formula (3), R ₄ represents a hydrogen atom or a methyl group. For example, the resin composition of claim 1 of the patent scope further contains an epoxy resin (E). The resin composition of claim 1 further contains a compound (F) having an ethylenically unsaturated group other than the above compound (A). The resin composition of the first aspect of the patent application further contains an inorganic filler (G). A resin sheet to which a support is attached, which has a resin composition coated on a support as in the first aspect of the patent application. A multilayer printed circuit board having the resin composition according to any one of claims 1 to 4. A semiconductor device having the resin composition according to any one of claims 1 to 4.