TWI770001B - 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 support-attached resin sheet, a multilayer printed circuit board, and a semiconductor device using the resin composition.

Due to the miniaturization and high density of the multilayer printed circuit board, researches to reduce the thickness of the laminate used for the multilayer printed circuit board are being vigorously carried out. Along with the thinning, the insulating layer is also sought to be thinned, and a resin sheet without glass cloth is being sought. The resin composition used as the material of the insulating layer is mainly a thermosetting resin, and generally, laser processing is used to obtain conductive openings between the insulating layers.

On the other hand, there is a problem that the processing time of a high-density substrate with a larger number of holes becomes longer when the holes are opened by laser processing. Therefore, in recent years, by using a resin composition which is hardened by light or the like and dissolved by development, a resin sheet that can be subjected to a one-time drilling process in a development step has been sought.

Among such resin compositions, the alkali-developing type is the mainstream, and acrylates containing an acid anhydride group and a carboxyl group are used in order to enable image development. For example, Patent Document 1 discloses a composition that 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 in which mechanical properties are improved by containing a predetermined curing agent. Patent Document 3 discloses a photosensitive resin composition used for an interlayer insulating layer of a multilayer printed wiring board.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 61-243869

[Patent Document 2] Japanese Patent Laid-Open No. 2006-047501

[Patent Document 3] International Publication No. 2015/002071 Pamphlet

However, conventional cured products using acrylate cannot obtain sufficient physical properties, and there are limitations on the formation of protective films and interlayer insulating layers having high heat resistance.

In addition, the use of the composition described in Patent Document 1 is limited to etching resists or solder resists for printed wiring boards, and its heat resistance is insufficient for use 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. The photosensitive resin composition described in Patent Document 3 is developed using an organic solvent as a developing solution, and developability in an aqueous developing solution that does not use an organic solvent, such as an alkaline aqueous solution that has become the mainstream in the developing solution in the field of printed wiring boards. insufficient.

Then, in view of the above-mentioned problems, the present invention provides a resin composition excellent in heat resistance and developability when used in a multilayer printed wiring board, a resin sheet with a support, a multilayer printed wiring board and a semiconductor device using the same.

The present inventors found that by using a compound (A) represented by the following formula (1) and having an acid value of not less than 30 mgKOH/g and not more than 120 mgKOH/g, a photohardening initiator (B), a maleimide compound (C) ) and/or a resin composition of blocked isocyanate (D), the above-mentioned problems can be solved, and the present invention can be completed.

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

[hua 3]

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

That is, the present invention includes the following:

[1] A resin composition comprising: a compound (A) represented by the aforementioned formula (1) and having an acid value of not less than 30 mgKOH/g and not more than 120 mgKOH/g, a photohardening initiator (B), a maleimide compound ( C) and/or blocked isocyanates (D).

[2] The resin composition according to [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 aforementioned compound (A).

[4] The resin composition according to any one of [1] to [3], which further contains an inorganic filler (G).

[5] A resin sheet with a support, comprising the resin composition according to any one of [1] to [4] 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 having the resin composition according to any one of [1] to [4].

According to the present invention, it is possible to provide a resin composition cured by active energy rays and a resin sheet with a support, which are excellent in coating film properties, heat resistance and developability, and have physical properties suitable for protective films and interlayer insulating layers of multilayer printed circuit boards. , Use of these multilayer printed circuit boards and semiconductor devices.

Hereinafter, an embodiment for implementing the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and the present invention is not intended to be limited to the following contents. The present invention can be appropriately changed and implemented within the scope of its gist.

In addition, the "(meth)acryloyl group" in this specification means both the "acryloyl group" and the "methacryloyl group" corresponding to the acryl group, and the "(meth)acrylate" means Refers to both "acrylate" and "methacrylate" corresponding to acrylate, and "(meth)acrylic" means both "acrylic" and "methacrylic" corresponding to acrylic. In addition, in this embodiment, the following definitions are used: "resin solid content" or "resin solid content in the resin composition", unless otherwise specified, refers to the resin composition except for the solvent and the inorganic filler (G). As for the components, "100 parts by mass of 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 this embodiment contains the said compound (A), a photohardening 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 aforementioned formula (1). The compound (A) may be used alone, or may include isomers such as structural isomers and stereoisomers, and may be used in combination of two or more compounds having different structures as appropriate.

In the aforementioned formula (1), a plurality of R _1s each independently represent a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the reactivity of the photohardening reaction, it is preferable to contain hydrogen atoms, and it is more preferable that all R ₁ are hydrogen atoms.

A plurality of R ₂ each independently represents a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the heat resistance of the cured product, methyl groups are preferably contained, and all of R ₂ are preferably methyl groups.

A plurality of R ₃ 's each independently represent a substituent represented by the aforementioned formula (2), a substituent represented by the aforementioned formula (3), or a hydroxyl group. Among them, from the viewpoint of improving heat resistance, it is preferable to contain a hydroxyl group. Moreover, in this embodiment, it is also preferable to use the compound (A) which contains the substituent represented by said formula (2) among many R< ₃ > from the viewpoint of improving developability. In the present embodiment, from the viewpoint of improving heat resistance, it is also preferable to use a compound (A) containing a substituent represented by the aforementioned formula (3) among a plurality of R ₃ . In the aforementioned formula (3), R ₄ represents a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the reactivity of the photohardening reaction, a hydrogen atom is preferable.

For a large number of R ₃ , from the viewpoint of improving developability, among all R ₃ substituents, the ratio of the substituent represented by the aforementioned formula (2) is preferably 20% or more and 85% or less, and the aforementioned formula (3) represents The ratio of substituents is preferably 5% or more and 70% or less, and the ratio of hydroxyl groups is preferably 10% or more and 75% or less.

The compound (A) preferably contains any one or more of the following compounds (A1) to (A5), since the reactivity of the photohardening reaction, the heat resistance and the developability of the cured product can be improved, so at least More preferably, it contains compound (A1), more preferably contains any two or more of (A1) to (A5), and even more preferably contains any one or more of compound (A1) and compounds (A2) to (A5). It is also desirable for the compound (A) to contain at least the compounds (A2) and (A3).

Such a compound can also use a commercial item, for example, KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR-6007H ( The above are the trade names, 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 from the viewpoint of improving developability, and preferably 50 mgKOH/g or more from the viewpoint of further improving developability. In addition, from the viewpoint of preventing dissolution by a developer after curing with active energy rays, the acid value of the compound (A) is 120 mgKOH/g or less, and preferably 110 mgKOH/g or less in terms of preventing dissolution . In addition, the "acid value" in this embodiment shows the value measured by the method based on JISK0070:1992.

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 by active energy rays, it is preferably set to 100 parts by mass of the resin solid content in the resin composition It is 1 part by mass or more, 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, still more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more Parts by mass or more are even more preferable. In addition, from the viewpoint of sufficiently hardening with active energy rays and improving heat resistance and developability, it is preferable to set it to 99 parts by mass or less, and 98 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. The following is more preferable, 97 parts by mass or less is still more preferable, 90 parts by mass or less is still more preferable, 75 parts by mass or less is still more preferable, and 73 parts by mass or less is most preferable.

<Photo-hardening initiator (B)>

The photocurable initiator (B) used in the present embodiment is not particularly limited, and those known in the field in which photocurable resin compositions are generally used can be used.

啉基-丙烷-1-酮等之苯乙酮類；2-乙基蒽醌、2-三級丁基蒽醌、2-氯蒽醌、2-戊基蒽醌等之蒽醌類；2,4-二乙基-9-氧硫

、2-異丙基-9-氧硫

、2-氯-9-氧硫

等之9-氧硫

類；苯乙酮二甲基縮酮、苯偶醯二甲基縮酮等之縮酮類；二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫醚、4,4’-雙甲基胺基二苯甲酮等之二苯甲酮類；2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等之氧化膦類；1,2-辛烷二酮，1-[4-(苯硫基)-,2-(O-苯甲醯肟)](1,2-Octanedione,1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime))等之肟酯類等之自由基型光硬化起始劑、或氟膦酸對甲氧基苯基重氮鹽、六氟膦酸-N,N-二乙基胺基苯基重氮鹽等之路易士酸的重氮鹽；六氟膦酸二苯基錪鹽、六氟銻酸二苯基錪鹽等之路易士酸之錪鹽；六氟膦酸三苯基鋶鹽、六氟銻酸三苯基鋶鹽等之路易士酸之鋶鹽；六氟銻酸三苯基鏻鹽等之路易士酸之鏻鹽；其他之鹵化物、三

系起始劑、硼酸鹽系起始劑、及其他之光酸產生劑等之陽離子系光聚合起始劑。 Examples of the photohardening initiator (B) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; peroxides Organic peroxides exemplified by benzyl, lauryl peroxide, acetyl peroxide, p-chlorobenzyl peroxide, di(tertiary butyl) diperphthalic acid, etc.; acetophenone, 2,2 -diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1 -Hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-

Acetophenones such as olinyl-propan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tertiary butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone, etc.; 2 ,4-Diethyl-9-oxothio

, 2-isopropyl-9-oxothio

, 2-chloro-9-oxosulfur

9-oxosulfur

ketals such as acetophenone dimethyl ketal, benzil dimethyl ketal, etc.; benzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 4, 4'-Dimethylaminobenzophenone and other benzophenones; 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethyl) Phosphine oxides such as benzyl)-phenylphosphine oxide; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzyl oxime)](1 , 2-Octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime)) and other oxime esters such as radical type photohardening initiators, or fluorophosphonic acid p-methoxybenzene diazonium salt of Lewis acid such as diazonium hexafluorophosphonate, N,N-diethylaminophenyl diazonium hexafluorophosphonate, etc.; diphenyl iodonium hexafluorophosphonate, diphenyl hexafluoroantimonate Iodonium salts of Lewis acids such as iodonium salts; strontium salts of Lewis acids such as triphenyl hexafluorophosphonate, triphenyl hexafluoroantimonate, etc.; triphenyl phosphonium hexafluoroantimonate, etc. phosphonium salts of Lewis acids; other halides, three

Cationic photopolymerization initiators such as initiators, borate initiators, and other photoacid generators.

啉基苯基)-丁酮-1(BASF JAPAN(股)製，Irgacure(註冊商標)369)等之苯乙酮類之自由基型光硬化起始劑係為理想。 Among them, 2-benzyl-2-dimethylamino-1-(4-benzyl-2-dimethylamino-1-(4-benzyl-2-dimethylamino-1-(4-

Radical type photohardening initiators such as acetophenones such as olinylphenyl)-butanone-1 (manufactured by BASF JAPAN Co., Ltd., Irgacure (registered trademark) 369) are preferable.

These photohardening initiators (B) can be used individually by 1 type, or in mixture of 2 or more types suitably, and can also use together the initiator of both a radical type and a cation type.

The content of the photohardening initiator (B) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently hardening the resin composition with active energy rays and improving heat resistance, it is relatively The resin solid content in 100 parts by mass is preferably 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, still more preferably 1 part by mass or more. In addition, from the viewpoint of preventing thermal hardening after photocuring and lowering heat resistance, it is preferable to set it to 30 parts by mass or less, more preferably 25 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is still more preferable that it is 20 parts by mass or less, and it is still more preferable that it is 10 parts by mass or less.

In the resin composition of the present embodiment, either the maleimide compound (C) or the blocked isocyanate (D) may be used, or these may be used in combination. Among them, the maleimide compound (C) is preferably used from the viewpoint of improving the coating film property, heat resistance, and developability. From the viewpoint of further improving the heat resistance and developing property, and also improving the coating film property, the maleimide compound (C) is preferably used. Lyimide compound (C) and blocked isocyanate (D) are more preferred. 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 N-phenylmalein Imine, phenylmethanemaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimide) Imidophenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polytetrahydrofuran-bis (4-maleimide benzoate), o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bismaleimide bis-citraconic imide, m-phenyl bis-citraconic imine, p-phenyl bis-citraconic imine, 2,2-bis(4-(4-maleimide phenoxy) -Phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bis Maleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenyl ether bismaleimide, 4,4- Diphenyl bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4 , 4-Diphenylmethane bis-citraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4 - Citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconiminophenyl) iminophenyl)methane, polyphenylmethane maleimide, maleimide compounds represented by the following formula (4), maleimide compounds represented by the following formula (5), and these maleimide A prepolymer of an imide compound, or a prepolymer of a maleimide compound and an amine compound.

Among them, the maleimide compound represented by the following formula (4) and the maleimide compound represented by the following formula (5) are preferable from the viewpoint of obtaining good coating film properties and excellent heat resistance, which are represented by the following formulae The maleimide compound represented by (4) is more preferable. A commercial item can also be used for the maleimide compound represented by the following formula (4), for example, BMI-2300 (manufactured by Yamato Chemical Industry Co., Ltd.) can be mentioned. A commercial item can also be used for the maleimide compound represented by the following formula (5), for example, MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.).

These maleimide compounds (C) may be used alone or in an appropriate mixture of two or more.

[Chemical 9]

In formula (4), a plurality of R ₅ each 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 formula (5), a plurality of R ₆ each 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 hardening the resin composition and improving heat resistance, the content of the maleimide compound in the resin composition is relatively 100 parts by mass of the component is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, still more preferably 0.03 part by mass or more, still more preferably 0.5 part by mass or more. In addition, from the viewpoint of optimizing the developability, the resin solid content in the resin composition is preferably set to 50 parts by mass or less, more preferably 45 parts by mass or less, more preferably 40 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. It is more preferable to set it to 20 mass parts or less, it is more preferable to set it to 10 mass parts or less, and it is more preferable to set it to 7 mass parts or less.

<Blocked Isocyanate (D)>

The blocked isocyanate (D) used in this embodiment is not particularly limited as long as it is inactive at normal temperature (25°C), but when heated, the blocking agent dissociates in reverse to regenerate isocyanate groups.

Examples of the blocked skeleton of the blocked isocyanate (D) include isocyanurate type, biuret type, and adduct type, and from the viewpoint of heat resistance, the isocyanurate type is ideal.

These blocked isocyanates (D) may be used alone or in a suitable mixture of two or more.

As an end-capping agent which is inactive at normal temperature (25°C) but dissociates in a reverse direction when heated, one selected from the group consisting of diketones, oximes, phenols, alkanols, and caprolactams is exemplified. at least one compound. Specifically, methyl ethyl ketoxime, ε-caprolactam, etc. are mentioned.

The dissociation temperature of the blocking agent is not particularly limited, but from the viewpoint of sufficiently hardening the resin composition and improving heat resistance, it is preferably 120° C. or higher. In addition, from the viewpoint of sufficiently dissociating the terminal blocking agent and curing the resin composition, a temperature of 200° C. or lower is preferable.

The above-mentioned end-capping agent is dissociated during heating and is discharged as a gas. Considering the situation that causes the volume reduction, it is preferable to use a terminal blocker having a smaller molecular weight. Specifically, it is desirable to use a methyl ethyl ketoxime type.

Such blocked isocyanates can be easily obtained in the form of commercial products, for example, SUMIDUR (registered trademark) BL-3175, BL-4265, BL-5375, BL-1100, BL-1265 (the above are trade names, Sumika). Covestro Urethane Co., Ltd.); CORONATE (registered trademark) 2507, CORONATE (registered trademark) 2554 (the above are trade names, manufactured by Tosoh Corporation); DURANATE (Note registered trademark) TPA-B80E, DURANATE (registered trademark) 17B-60PX (the above are trade names, manufactured by Asahi-Kasei Chemicals Co., Ltd.), and the like.

Among these, the blocked skeleton is preferably at least one selected from the group consisting of isocyanurate-type SUMIDUR (registered trademark) BL-3175 and DURANATE (registered trademark) TPA-B80E. By containing such a type of blocked isocyanate, the heat resistance of the obtained 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 hardening the resin composition and improving heat resistance, the content of the blocked isocyanate in the resin composition is relative to the resin solid content in the resin composition. 100 parts by mass, preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, still more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more. In addition, from the viewpoint of suppressing the volume reduction of the resin composition and improving the developability, it is preferable to set it as 5.0 parts by mass or less or less than 5.0 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition, and set it as 4.0 parts by mass part or less than 4.0 parts by mass is more preferably set to 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, the content of these is not particularly limited, but from the viewpoint of sufficiently hardening the resin composition and improving the heat resistance, relative to the resin composition The resin solid content in the medium 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, still more preferably 3 parts by mass or more. In addition, from the viewpoint of suppressing the volume reduction of the resin composition, improving the developability, and obtaining a more favorable coating film, it is preferable to set the resin composition to 55 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. 25 mass parts or less is more preferable, 15 mass parts is more preferable, 13 mass parts or less is still more preferable, and 10 mass parts is still more preferable.

<Epoxy resin (E)>

In the resin composition of the present embodiment, in order to improve the developability and the heat resistance of the cured product, an epoxy resin (E) may be used in combination.

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 novolak resin type epoxy resin. Resin, biphenyl type epoxy resin, phenol novolak resin type epoxy resin, cresol novolak resin type epoxy resin, xylenol novolak resin type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin Resin, naphthalene skeleton modified novolak resin type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin Epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, cycloaliphatic epoxy resin, dicyclopentadiene novolak resin type epoxy resin, biphenyl novolak resin type epoxy resin Oxygen resin, phenol aralkyl novolak resin type epoxy resin, naphthol aralkyl novolak resin type epoxy resin, aralkyl novolak resin type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene Phenol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, compounds obtained by epoxidizing double bonds such as glycidylamine and butadiene , Compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and their halides.

Among them, more than one kind selected from the group consisting of biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, multifunctional phenol type epoxy resin, and naphthalene type epoxy resin is ideal, More preferably, it is a biphenyl aralkyl type epoxy resin. By containing such a kind of epoxy resin, there exists a tendency for the heat resistance of the hardened|cured material obtained to be improved more.

These epoxy resins (E) can be used individually by 1 type, or in mixture of 2 or more types suitably.

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, it is preferably set to 100 parts by mass of the resin solid content in the resin composition It is 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, still more preferably 2.0 parts by mass or more, and still more preferably 8 parts by mass or more. In addition, from the viewpoint of optimizing the developability of the resin composition, the content of the resin solid content in the resin composition is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. It is still more preferable below, and it is still more preferable to set it to 25 mass parts or less.

<Compound (F) having an ethylenically unsaturated group>

In the resin composition of the present embodiment, the compound (F) having an ethylenically unsaturated group may be used in combination in order to increase the reactivity to active energy rays (eg, ultraviolet rays) and to improve developability and heat resistance. The compound (F) having an ethylenically unsaturated group used in the present embodiment is other than the compound (A) whose acid value represented by the aforementioned formula (1) is 30 mgKOH/g or more and 120 mgKOH/g or less, and has 1 in 1 molecule. The compound having one or more ethylenically unsaturated groups is not particularly limited, and examples thereof include compounds having a (meth)acryloyl group, a vinyl group, and the like. The compound (F) which has these ethylenically unsaturated groups can be used individually by 1 type or in a suitable mixture of 2 or more types.

Examples of the compound having a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, poly(meth)acrylate ) ethylene glycol acrylate, poly(ethylene glycol) (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Benzyl meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate , Nonanediol di(meth)acrylate, Glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, ginseng isocyanurate (Meth)Acrylooxyethyl ester, Polypropylene glycol di(meth)acrylate Esters, epoxy adipate di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bis(meth)acrylate Phenolic ester, ε-caprolactone modified hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, ε-caprolactone modified hexa(meth)acrylate dipivoerythritol, ε-hexane Lactone-modified poly(meth)acrylate dipeutaerythritol, poly(meth)acrylate dipeptaerythritol, trimethylolpropane tri(meth)acrylate, trimethylolpropanetri(meth)acrylate Hydroxyethyl propane, and its ethylene oxide adducts; tri(meth)acrylate neotaerythritol, and its ethylene oxide adducts; tetra(meth)acrylate neotaerythritol, Dipivalerythritol hexa(meth)acrylate, and its ethylene oxide adducts, etc.

In addition, urethane (meth)acrylates having both a (meth)acryloyl group and a urethane bond in the same molecule can also be mentioned; Polyester (meth)acrylates bound by acyl groups and esters; epoxy (meth)acrylates derived from epoxy resins and having (meth)acryloyl groups at the same time; reactive oligomers, etc.

The above-mentioned urethane (meth)acrylates refer to the reactants of hydroxyl-containing (meth)acrylates, polyisocyanates, and other alcohols used as required. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; Glyceryl (meth)acrylates such as glycerol (meth)acrylate; neopentaerythritol di(meth)acrylate, neotaerythritol tri(meth)acrylate, and two new penta(meth)acrylates (Meth) acrylic acid sugar alcohol esters such as pentaerythritol ester, and tolyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isocyanato diisocyanate Phorone esters, norbornyl diisocyanate, xylyl diisocyanate, hydroxylylene diisocyanate, dicyclohexanemethylene diisocyanate, and isocyanurates of these Polyisocyanates such as acid esters and biuret reactants react to form urethane (meth)acrylates.

The above-mentioned epoxy (meth)acrylates refer to a compound having an epoxy group and a carboxylate compound of (meth)acrylic acid. For example, a phenol novolak resin type epoxy (meth)acrylate, a cresol novolak resin type epoxy (meth)acrylate, a parahydroxyphenylmethane type epoxy (meth)acrylate, a dicyclopenta 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 type epoxy (meth)acrylate, epoxy (meth)acrylate containing naphthalene skeleton, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate base) acrylates, etc., and these acid anhydride-modified epoxy (meth)acrylates 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. The styrenes include styrene, methylstyrene, ethylstyrene, divinylbenzene, α-methylstyrene, and oligomers thereof. As another vinyl compound, triallyl isocyanurate, trimethallyl isocyanurate, bisallylnadiimide, etc. are mentioned.

Among these, it is preferably selected from neotaerythritol tetra(meth)acrylate, dipaerythritol hexa(meth)acrylate, cresol novolac epoxy (meth)acrylate, One or more selected from the group consisting of bisphenol A epoxy (meth)acrylate, epoxy (meth)acrylate containing naphthalene skeleton, and bisallyl nadic imide, and hexa(methyl) ) dipivaloerythritol acrylate is more preferred. By containing such a compound having an ethylenically unsaturated group, the heat resistance of the obtained 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 good developability, it is 100 parts by mass of the resin solid content in the resin composition. It is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, still more preferably 5 parts by mass or more, and most preferably 15 parts by mass or more. again, From the viewpoint of optimizing the heat resistance of the rigid material, it is preferable to set it as 90 parts by mass or less, more preferably 70 parts by mass or less, more preferably 50 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. , it is still more preferable to set it to 25 parts by mass or less.

<Inorganic filler (G)>

In the resin composition of this embodiment, in order to improve various characteristics, such as coating film property, developability, or heat resistance, an inorganic filler (G) can also be used together. The inorganic filler (G) used in this embodiment is not particularly limited as long as it has insulating properties, for example, silica (such as natural silica, fused silica, amorphous silica, hollow silica, etc.) Silicon dioxide, etc.), aluminum compounds (such as boehmite, aluminum hydroxide, alumina, etc.), magnesium compounds (such as magnesium oxide, magnesium hydroxide, etc.), calcium compounds (such as calcium carbonate, etc.), molybdenum compounds (such as oxide Molybdenum, zinc molybdate, etc.), barium compounds (such as barium sulfate, barium silicate, etc.), talc (such as natural talc, calcined talc, etc.), mica (mica), glass (such as short-fiber glass, spherical glass, powder Glass (such as E-glass, T-glass, D-glass, etc.), silicone powder, etc.

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

These inorganic fillers (G) can also be surface-treated with a silane coupling agent or the like described later.

In particular, from the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties, silica is suitable, and fused silica is particularly preferred. Specific examples of silica include: SFP-130MC manufactured by Denka Corporation, SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Corporation, and the like.

These inorganic fillers (G) can be used individually by 1 type or in a suitable mixture of 2 or more types.

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, it is preferably set to 100 parts by mass of the resin solid content in the resin composition It is 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. Furthermore, from the viewpoint of optimizing the developability of the resin composition, the resin solid content in the resin composition is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, and 300 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. It is still more preferable below, and it is still more preferable to set it to 100 mass parts or less.

<Silane coupling agent and wetting and dispersing agent>

In the resin composition of the present embodiment, in order to improve the dispersibility of the inorganic filler and the adhesive strength of the polymer and/or the resin and the inorganic filler, a silane coupling agent and/or a wetting and dispersing agent may be used in combination.

These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; γ- Epoxysilanes such as glycidoxypropyltrimethoxysilane; acrylic silanes such as γ-acryloyloxypropyltrimethoxysilane; N-β-(N-vinylbenzylamino) Ethyl)-γ-aminopropyl trimethoxysilane hydrochloride and other cationic silanes; phenylsilane-based silane coupling agents. These silane coupling agents may be used alone or in an appropriate 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 relative 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 and stabilizer used in coating applications. Specific examples include wetting and dispersing agents such as DISPERBYK (registered trademark)-110, 111, 118, 180, and 161 manufactured by BYK Japan Co., Ltd.; BYK (registered trademark)-W996, W9010, and W903. These wetting and dispersing agents may be used alone or in a suitable mixture 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 relative to 100 parts by mass of the resin composition.

<Thermal hardening accelerator>

In the resin composition of the present embodiment, a thermosetting accelerator may be used in combination within a range that does not impair the characteristics of the present embodiment.

啉、三乙醇胺、三乙二胺、四甲基丁二胺、N-甲基哌啶等之三級胺類；苯酚、二甲酚、甲酚、間苯二酚、鄰苯二酚等之苯酚類；環烷酸鉛、硬脂酸鉛、環烷酸鋅、辛基酸鋅、油酸錫、馬來酸二丁基錫、環烷酸錳、環烷酸鈷、乙醯基丙酮鐵等之有機金屬鹽；將該等有機金屬鹽溶解於苯酚、雙酚等含羥基之化合物而成者；氯化錫、氯化鋅、氯化鋁等之無機金屬鹽；氧化二辛基錫、其他烷基錫、氧化烷基錫等之有機錫化合物；1,2-二甲基咪唑、1-苄基-2-苯基咪唑、三苯基咪唑(TPIZ)等之咪唑化合物等。 The thermosetting accelerator is not particularly limited, and examples thereof include benzyl peroxide, lauryl peroxide, acetyl peroxide, p-chlorobenzyl peroxide, and di(tertiary butyl) diperphthalate. Organic peroxides exemplified by etc.; azo compounds such as azobisnitriles; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2- N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methyl

tertiary amines such as phenol, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, etc.; phenol, xylenol, cresol, resorcinol, catechol, etc. Phenols; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, etc. Organic metal salts; those obtained by dissolving these organic metal salts in phenol, bisphenol and other hydroxyl-containing compounds; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride, etc.; dioctyl tin oxide, other alkanes Organic tin compounds such as tin, alkyl tin oxide, etc.; imidazole compounds such as 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, triphenylimidazole (TPIZ), etc.

These thermosetting accelerators may be used alone or in a suitable mixture 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 relative to 100 parts by mass of the resin composition.

<Organic solvent>

The resin composition of this 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 cellulose; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol Monomethyl ether and its acetate.

These organic solvents may be used alone or in an appropriate mixture of two or more.

<Other ingredients>

環之化合物、及磷系化合物之磷酸鹽化合物、芳香族縮合磷酸酯、含鹵素縮合磷酸酯等。添加劑可列舉：紫外線吸收劑、抗氧化劑、螢光增白劑、光敏劑、染料、顏料、增黏劑、潤滑劑、消泡劑、表面調整劑、光澤劑、聚合抑制劑等。 In the resin composition of the present embodiment, thermosetting resins, thermoplastic resins, oligomers, elastomers, etc., which have not been listed so far, can be used in combination within the range that does not impair the characteristics of the present embodiment. Various polymer compounds; flame retardant compounds that have not been listed so far; additives, etc. These are not particularly limited as long as they are commonly used by users. For example, the flame-retardant compound includes nitrogen-containing compounds such as melamine and benzoguanamine,

Ring compounds, phosphate compounds of phosphorus-based compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, and the like. The additives include ultraviolet absorbers, antioxidants, optical brighteners, photosensitizers, dyes, pigments, tackifiers, lubricants, antifoaming agents, surface conditioners, glossing agents, polymerization inhibitors, and the like.

These components can be used individually by 1 type or in mixture of 2 or more types suitably.

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, respectively, with respect to 100 parts by mass of the resin composition.

The resin composition of the present embodiment is prepared by combining the compound (A), the photohardening initiator (B), the maleimide compound (C) and/or the blocked isocyanate (D), and according to need, Epoxy resin (E), compound with ethylenically unsaturated group (F), inorganic filler (G), silane coupling agent, wetting and dispersing agent, thermosetting accelerator, organic solvent, or other ingredients are mixed appropriately. have to. The resin composition of the present embodiment is preferably used as a varnish for producing the resin sheet with a support of the present embodiment to be described later.

<Manufacturing method of resin composition>

The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mixing the above-mentioned each component in a solvent in order and stirring well is mentioned.

The resin composition may be subjected to known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component as necessary. Specifically, the dispersibility of the inorganic filler (G) with respect to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirring tank having a suitable stirring ability. The above-mentioned stirring, mixing, and kneading treatment can be appropriately carried out using the following well-known apparatuses: stirring apparatuses for the purpose of dispersion such as ultrasonic homogenizers; three-roll mills, ball mills, bead mills, sand mills, etc. A device for the purpose of mixing; or a mixing device for revolution or autotransformation, etc. 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.

<Use>

The resin composition of this embodiment can be used in applications that require an insulating resin composition without particular limitation, and can be used in the following applications: photosensitive films, photosensitive films with supports, resin sheets with supports, prepregs Insulating resin sheets, circuit boards (for laminated boards, for multilayer printed circuit boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealing materials, filling resins, parts embedded resins, etc. Among them, a resin composition for an insulating layer of a multilayer printed wiring board, or a solder resist is preferably used.

<Resin sheet with support>

The resin sheet with a 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. Resin sheet with support on one or both sides. The resin sheet with a support can be obtained by coating the resin composition on the support and drying.

The support used in the resin sheet with a support of the present embodiment is not particularly limited, and a well-known one can be used, and a resin film is suitable. 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, polyvinyl alcohol film, triacetate film and other resin films. Among them, PET film is suitable.

In order to easily peel the resin film from the resin composition layer, it is preferable to use one coated with a release agent on the surface. The thickness of the resin film is preferably in the range of 5 μm to 100 μm, 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 damaged when the support is peeled off before development, and when the thickness exceeds 100 μm, the resolution tends to decrease when exposed from above the support.

Moreover, in order to reduce the scattering of exposure light by active energy rays, such as an ultraviolet-ray, it is preferable that a resin film is excellent in transparency.

In addition, in the resin sheet with a support in this embodiment, the resin composition layer may be protected with a protective film.

By protecting the resin composition layer with the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer or to be scratched. As the protective film, a film made of the same material as the above-mentioned 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, 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 decrease, and when the thickness exceeds 50 μm, there is a tendency for low cost performance to be poor. In addition, the protective film is preferably the one with 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 manufacturing method of the resin sheet with a support of the present embodiment is not particularly limited, for example, by applying the resin composition of the present embodiment to a support such as a PET film, drying and removing the organic solvent can be used to manufacture the resin sheet with a support. The method of the resin sheet of the support, etc.

The above-mentioned coating can be implemented by a known method using, for example, a roll coater, a gravure coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, an extrusion coater, and the like. The above drying can be implemented by, for example, 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 mass % or less with respect to the total mass of the resin composition layer from the viewpoint of preventing the diffusion of the organic solvent in the subsequent steps. Resin composition layer For the thickness of the support, the resin set of the resin sheet with the support is considered from the viewpoint of improving the workability. The thickness of the resulting layer is preferably set to be 1.0 μm or more. Moreover, considering the viewpoint of improving the transmittance and making developability favorable, it is preferable to set it as 300 micrometers or less.

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

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

<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 can be specifically produced by the following method.

(lamination step)

The resin composition layer of the resin sheet with a support of the present embodiment is laminated on one side or both sides of the circuit board using a vacuum laminator. Examples of the circuit substrate include glass epoxy resin substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. In addition, a circuit board here means the board|substrate which formed the conductor layer (circuit) obtained by pattern processing on the single side|surface or both sides of the above-mentioned board|substrate. Also, in a multilayer printed circuit board in which conductor layers and insulating layers are alternately laminated, a substrate in which conductor layers (circuits) are formed by patterning one or both sides of the outermost layer of the multilayer printed circuit board is also applicable. Include the circuit boards referred to herein. In addition, the surface of the conductor layer may be subjected to roughening treatment in advance by blackening treatment, copper etching, or the like. In the lamination step, if the resin sheet with the support has a protective film, after peeling off the protective film, the resin sheet with the support and the circuit board are preheated according to the need, and the resin composition layer is added after the protective film is removed. In the case of pressing and heating, it is crimped to the circuit board. In the resin sheet with a support of the present embodiment, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

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

(exposure step)

After the resin sheet with the support is placed on the circuit board by the lamination step, the predetermined part of the resin composition layer is irradiated with active energy rays, and the exposure step of curing the resin composition layer in the irradiated part is performed. The irradiation of the active energy rays may be performed through a mask pattern, or a direct drawing method of directly irradiating the active energy rays may be used.

Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation dose of ultraviolet rays is approximately 10mJ/cm ² ~1000mJ/cm ² . The exposure method through the mask pattern includes a contact exposure method in which the mask pattern is adhered to a printed circuit board, and a non-contact exposure method in which the mask pattern is not adhered and exposed using parallel light, whichever one may be used. Moreover, when a support exists in a resin composition layer, exposure may be performed from the upper direction of a support, and exposure may be performed after peeling a support.

(Development step)

After the exposure step, if there is a support on the resin composition layer, after removing the support, the part that is not photohardened (unexposed part) is removed and developed by wet development, whereby an insulating layer pattern can be formed. .

In the case of the above-mentioned wet development, the developer is not particularly limited as long as the unexposed portion can be selectively eluted, and a developer such as an alkaline aqueous solution, an aqueous developer, and an organic solvent can be used. In the present embodiment, the development step using an alkaline aqueous solution is particularly preferable. These developers may be used alone or in combination of two or more. Moreover, as a developing method, a well-known method, such as spraying, shaking dipping, brushing, scraping, etc. can be used.

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

The concentration of the above-mentioned alkaline aqueous solution is preferably 0.1% by mass to 60% by mass relative to the total amount of the developer. In addition, the temperature of the alkaline aqueous solution can be adjusted according to the developability. Moreover, these alkaline aqueous solutions can be used individually by 1 type or in combination of 2 or more types.

In the pattern formation of this embodiment, you may use together the said 2 or more types of developing methods as needed. The developing methods include: dipping, dipping, spraying, high-pressure spraying, brushing, scraping, etc. High-pressure spraying can improve resolution, so it is ideal. The spray pressure should be 0.02MPa~0.5MPa when using the spray type.

(post bake step)

After the above-mentioned developing step is completed, a post-baking step is performed to form an insulating layer (hardened product). As a post-baking process, the ultraviolet irradiation process by a high pressure mercury lamp, the heating process using a dust-free oven, etc. are mentioned. When irradiating ultraviolet rays, the irradiation amount can be adjusted according to the needs, for example, the irradiation can be performed with an irradiation amount of about 0.05J/cm ² ~10J/cm ² . In addition, the heating conditions can be appropriately selected according to the type and content of the resin components in the resin composition, but should be selected in 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 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, the support body is placed in a vacuum container and the metal is heated and evaporated to form a metal film on the insulating layer. For example, in the sputtering method, a support body can be placed in a vacuum container, a passive gas such as argon can be introduced, and a DC voltage can be applied to cause the ionized passive gas to collide with the target metal and knock out the metal, whereby the metal is ejected. A metal film is formed on the insulating layer.

In the case of wet plating, the surface of the formed insulating layer is sequentially subjected to: swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid, whereby the insulating layer is formed. Surface roughening. The swelling treatment by the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50° C. to 80° C. for 1 minute to 20 minutes. An alkaline solution is mentioned as a swelling liquid, and a sodium hydroxide solution, a potassium hydroxide solution, etc. are mentioned as this alkaline solution. As a commercially available swelling liquid, APPDES (registered trademark) MDS-37 manufactured by Uemura Kogyo Co., Ltd., etc. can be mentioned, for example.

The roughening treatment by the oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution of 60° C. to 80° C. for 5 minutes to 30 minutes. Examples of the oxidizing agent include potassium permanganate or sodium permanganate. Alkaline permanganic acid solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, etc. dissolved in an aqueous solution of sodium hydroxide. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably set to 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as APPDES (registered trademark) MDE-40 and APPDES (registered trademark) ELC-SH manufactured by Uemura Kogyo Co., Ltd. The neutralization treatment by the neutralization liquid is performed by immersing in the neutralization liquid at 30° C. to 50° C. for 1 minute to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and as a commercial product, APPDES (registered trademark) MDN-62 manufactured by Uemura Industrial Co., Ltd. may be mentioned.

Then, a conductor layer is formed by combining electroless plating and electrolytic plating. In addition, it is also possible to form a plating resist in which the conductor layer is a reverse pattern, and to form the conductor layer only by electroless plating. As a method of pattern formation thereafter, 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 can be specifically manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive position of the multilayer printed circuit board of this embodiment. Here, the conductive position refers to the position where the electrical signal can be transmitted in the multilayer printed circuit board, and the position can be on the surface or embedded in any position. In addition, the semiconductor wafer is not particularly limited as long as it is a circuit element using a semiconductor as a material.

The mounting method of the semiconductor chip in the manufacture of the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip can effectively function. Specifically, the mounting method by wire bonding, the flip chip mounting method, the bumpless mounting method can be mentioned. A mounting method by layer (BBUL), a mounting method by anisotropic conductive film (ACF), a mounting method by non-conductive film (NCF), etc.

Moreover, a semiconductor device can also be manufactured by laminating|stacking the resin sheet with a support of this embodiment on a semiconductor wafer. After lamination, it can be produced by the same method as the aforementioned multilayer printed circuit board.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples at all.

[Example 1]

(Production of resin composition and resin sheet with support)

啉基苯基)-丁酮-1(Irgacure(註冊商標)369，BASF JAPAN(股)製)5質量份、作為馬來醯亞胺化合物(C)之馬來醯亞胺化合物(BMI-2300，大和化成工業(股)製)3.5質量份、作為環氧樹脂(E)之聯苯芳烷基型環氧樹脂(NC3000H，日本化藥(股)製)19.8質量份、作為具有乙烯性不飽和基之化合物(F)之六丙烯酸二新戊四醇酯(KAYARAD(註冊商標)DPHA，日本化藥(股)製)18.9質量份、作為無機填充材(G)之經環氧矽烷處理之二氧化矽之甲乙酮(以下有時會簡稱為MEK)漿狀物(SC2050MB，平均粒徑0.5μm，非揮發成分70質量%，Admatechs(股)製)71.4質量份(按非揮發成分換算為50質量份)，以超音波均質機攪拌獲得清漆(樹脂組成物之溶液)。將該等清漆塗佈於厚度38μm之PET膜(UNIPEEL(註冊商標)TR1-38，尤尼吉可(股)製，商品名)上，於80℃加熱乾燥7分鐘，獲得以PET膜作為支持體且樹脂組成物層之厚度為30μm之附設支持體之樹脂片。 Propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA) solution (KAYARAD (registered trademark) ZCR-6002H, which is a TrisP-PA epoxy acrylate compound blended as compound (A), non-volatile content 65% by 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 non-volatile components), 2-benzyl-2-dimethyl as a photohardening initiator (B) Amino-1-(4-

Linophenyl)-butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF JAPAN Co., Ltd.) 5 parts by mass, maleimide compound (BMI-2300) as maleimide compound (C) , Yamato Chemical Industry Co., Ltd.) 3.5 parts by mass, biphenyl aralkyl type epoxy resin (NC3000H, Nippon Kayaku Co., Ltd.) 19.8 parts by mass as epoxy resin (E), 19.8 parts by mass as epoxy resin (E) 18.9 parts by mass of dipivoerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.), which is a saturated compound (F), treated with epoxysilane as an inorganic filler (G) Silica methyl ethyl ketone (hereinafter sometimes abbreviated as MEK) slurry (SC2050MB, average particle size 0.5 μm, non-volatile content 70% by mass, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (50 parts by non-volatile content parts by mass), and stirred with an ultrasonic homogenizer to obtain a varnish (solution of resin composition). These varnishes were coated on a PET film with a thickness of 38 μm (UNIPEEL (registered trademark) TR1-38, manufactured by Unijico Co., Ltd., trade name), and heated and dried at 80° C. for 7 minutes to obtain a PET film as a support. A resin sheet with a support body and the thickness of the resin composition layer is 30 μm.

In addition, the said KAYARAD (registered trademark) ZCR-6002H is a mixture containing any one or more of the said compound (A1) and the said compound (A2)-(A5).

(Fabrication of inner layer circuit board)

Double-sided copper-clad laminate with glass cloth base material BT resin formed with inner layer circuit (copper foil thickness 18μm, laminate thickness 0.2mm, Mitsubishi Gas Chemical Co., Ltd. CCL (registered trademark)-HL832NS) double The surface was roughened with CZ8100 manufactured by MEC (stock) to obtain an inner layer circuit board.

(Fabrication of laminated body for evaluation)

The resin surface of the above-mentioned resin sheet with a support was placed on the inner layer circuit board, and vacuum suction (5.0 MPa or less) was performed for 30 seconds using a vacuum laminator (manufactured by Nikko-Materials), followed by a pressure of 10 kgf. /cm ² , lamination molding at a temperature of 70°C for 30 seconds. Further, by performing lamination molding under the conditions of a pressure of 10 kgf/cm ² and a temperature of 70° C. for 60 seconds, a laminate including an inner-layer circuit board, a resin composition layer, and a support layered was obtained. An exposure step of irradiating the obtained laminate with ultraviolet rays of 200 mJ/cm ² was performed, and the support was peeled off and developed in a 1 mass % sodium carbonate aqueous solution to prepare a laminate for evaluation.

(Production of hardened product for evaluation)

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

[Example 2]

啉基苯基)-丁酮-1(Irgacure(註冊商標)369，BASF JAPAN(股)製)5質量份、作為封端化異氰酸酯化合物(D)之SUMIDUR(註冊商標)BL-3175(溶劑石腦油溶液，非揮發成分75質量%(惟包含封端劑)，Sumika Covestro Urethane(股)製，商品名)3.3質量份(按非揮發成分換算為2.5質量份(惟包含封端劑))、聯苯芳烷基型環氧樹脂(NC3000H，日本化藥(股)製)19.9質量份、六丙烯酸二新戊四醇酯(KAYARAD(註冊商標)DPHA，日本化藥(股)製)19.2質量份、經環氧矽烷處理之二氧化矽之MEK漿狀物(SC2050MB，平均粒徑0.5μm，非揮發成分70質量%，Admatechs(股)製)71.4質量份(按非揮發成分換算為50質量份)，以超音波均質機攪拌獲得清漆(樹脂組成物之溶液)。之後與實施例1同樣地進行而獲得附設支持體之樹脂片、評價用疊層體、評價用硬化物。 PGMEA solution (KAYARAD (registered trademark) ZCR-6002H, 65% by mass of nonvolatile content, acid value: 60 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd. ) 82.1 parts by mass (53.4 parts by mass in terms of non-volatile components), 2-benzyl-2-dimethylamino-1-(4-

Linophenyl)-butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF JAPAN Co., Ltd.) 5 parts by mass, SUMIDUR (registered trademark) BL-3175 (solvite) as the blocked isocyanate compound (D) Naphtha solution, 75% by mass of non-volatile content (including end-capping agent), Sumika Covestro Urethane Co., Ltd., trade name) 3.3 parts by mass (converted to 2.5 parts by mass in terms of non-volatile content (including end-capping agent)) , Biphenyl aralkyl epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 19.9 parts by mass, Dipivalerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 19.2 Parts by mass, 71.4 parts by mass of epoxy silane-treated silica MEK slurry (SC2050MB, average particle size 0.5 μm, non-volatile content 70% by mass, manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of non-volatile content parts by mass), and stirred with an ultrasonic homogenizer to obtain a varnish (solution of resin composition). Then, it carried out similarly to Example 1, and obtained the resin sheet with a support body, the laminated body for evaluation, and the cured product for evaluation.

[Example 3]

啉基苯基)-丁酮-1(Irgacure(註冊商標)369，BASF JAPAN(股)製)5質量份、作為馬來醯亞胺化合物(C)之馬來醯亞胺化合物(BMI-2300，大和化成工業(股)製)3.5質量份、作為封端化異氰酸酯化合物(D)之SUMIDUR(註冊商標)BL-3175(溶劑石腦油溶液，非揮發成分75質量%(惟包含封端劑)，Sumika Covestro Urethane(股)製商品名)3.3質量份(按非揮發成分換算為2.5質量份(惟包含封端劑))、聯苯芳烷基型環氧樹脂(NC3000H，日本化藥(股)製)18質量份、六丙烯酸二新戊四醇酯(KAYARAD(註冊商標)DPHA，日本化藥(股)製)18.7質量份、經環氧矽烷處理之二氧化矽之MEK漿狀物(SC2050MB，平均粒徑0.5μm，非 揮發成分70質量%，Admatechs(股)製)71.4質量份(按非揮發成分換算為50質量份)，以超音波均質機攪拌獲得清漆(樹脂組成物之溶液)。之後與實施例1同樣地進行而獲得附設支持體之樹脂片、評價用疊層體、評價用硬化物。 PGMEA solution (KAYARAD (registered trademark) ZCR-6002H, 65% by mass of nonvolatile content, acid value: 60 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd. ) 80.5 parts by mass (52.3 parts by mass in terms of non-volatile components), 2-benzyl-2-dimethylamino-1-(4-

Linophenyl)-butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF JAPAN Co., Ltd.) 5 parts by mass, maleimide compound (BMI-2300) as maleimide compound (C) , Yamato Chemical Industry Co., Ltd.) 3.5 parts by mass, SUMIDUR (registered trademark) BL-3175 (solvent naphtha solution) as the blocked isocyanate compound (D), 75% by mass of non-volatile content (including blocking agent only) ), Sumika Covestro Urethane Co., Ltd. trade name) 3.3 parts by mass (converted to 2.5 parts by mass in terms of non-volatile components (only including end-capping agent)), biphenyl aralkyl type epoxy resin (NC3000H, Nippon Kayaku ( Co., Ltd.) 18 parts by mass, dipivoerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 18.7 parts by mass, MEK slurry of epoxysilane-treated silica (SC2050MB, average particle size 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 non-volatile content), stirred with an ultrasonic homogenizer to obtain a varnish (part of the resin composition) solution). Then, it carried out similarly to Example 1, and obtained the resin sheet with a support body, the laminated body for evaluation, and the cured product for evaluation.

[Comparative Example 1]

Bisphenol F type epoxy acrylate (KAYARAD (registered trademark) ZFR-1553H, 68% by mass of non-volatile content, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.6 parts by mass (converted to non-volatile content) Except having replaced the compound (A) with 52.8 mass parts), it carried out similarly to Example 1, and produced the varnish, and obtained the resin sheet with a support, the laminated body for evaluation, and the hardened|cured material for evaluation.

[Comparative Example 2]

72.3 parts by mass of cresol novolak resin type epoxy acrylate (EA-7140, non-volatile content: 73% by mass, acid value: 70 mgKOH/g, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (52.8 parts by non-volatile content) A varnish was produced in the same manner as in Example 1, except that the compound (A) was replaced with 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]

72.3 parts by mass of cresol novolak resin type epoxy acrylate (EA-7420, non-volatile content: 73% by mass, acid value: 1 mgKOH/g, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (52.8 parts by non-volatile content) A varnish was produced in the same manner as in Example 1, except that the compound (A) was replaced with 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]

Biphenyl aralkyl type epoxy acrylate (KAYARAD (registered trademark) ZCR-1642H, non-volatile content 60 mass %, acid value: 99 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 88 mass parts (as non-volatile A varnish was prepared in the same manner as in Example 1, except that the components were converted to 52.8 parts by mass) in place of the compound (A), and a resin sheet with a support, a laminate for evaluation, and a cured product for evaluation were obtained.

[Comparative Example 5]

Dicyclopentadiene type epoxy acrylate (KAYARAD (registered trademark) ZXR-1807H, non-volatile content 66 mass %, acid value: 103 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 80 mass parts (by non-volatile content) 52.8 parts by mass in conversion) were replaced with compound (A), except that it carried out similarly to Example 1, and produced the varnish, and obtained the resin sheet with a support, the laminated body for evaluation, and the hardened|cured material for evaluation.

[Evaluation of physical properties]

Each support-attached resin sheet, each laminated body for evaluation, and each hardened product for evaluation obtained using the varnishes obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were measured and evaluated by the following method. These results are summarized in Table 1.

<Filmability>

The edge of the resin surface of each A4 size resin sheet with a support was lightly pressed with a finger, and the degree of adhesion to the finger was evaluated according to the following criteria.

⊚: Sticking to fingers was not observed. The end of the resin sheet with the support is not lifted.

○: Sticking to fingers was hardly observed. Although the end of the resin sheet with the support was attached to the finger, it was peeled off from the finger and dropped when the height was less than 30 mm.

×: Sticking to fingers was observed. The end of the resin sheet with the support is attached to the finger, and the height is raised by more than 30mm.

<Heat resistance (glass transition temperature)>

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

<Developability>

After the developed surface of each laminated body for evaluation was visually observed, it was observed by SEM (magnification of 1000 times), and the presence or absence of residues was evaluated according to the following criteria.

○: There is no developing residue within the range of 30 mm square, and the developability is excellent.

×: Development residues are present within a 30 mm square range, and developability is poor.

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

Claims (7)

A resin composition comprising: a compound (A) with an acid value of 30 mgKOH/g or more and 120 mgKOH/g or less, a photohardening initiator (B), a maleimide compound (C) and/or a blocked isocyanate ( D); the compound (A) comprises: the compound represented by the following formula (A1), and any one of the compound represented by the following formula (A2) to the compound represented by the following formula (A5);

For example, the resin composition of claim 1 of the scope of the application further contains epoxy resin (E). The resin composition of claim 1 further contains a compound (F) having an ethylenically unsaturated group other than the aforementioned compound (A). For example, the resin composition of claim 1 of the scope of the application further contains an inorganic filler (G). A resin sheet with a support body is provided, which has the resin composition as claimed in item 1 of the patented scope coated on the support body. A multilayer printed circuit board having the resin composition according to any one of items 1 to 4 of the scope of the patent application. A semiconductor device having the resin composition according to any one of items 1 to 4 of the patent application scope.