TW202122492A - Resin composition - Google Patents

Abstract

To provide: a resin composition that can suppress a curing shrinkage rate, and gives a cured product with an excellent dielectric constant; a resin sheet containing the resin composition; and a printed wiring board, a multilayer flexible substrate and a semiconductor device having an insulating layer formed using the resin composition. A resin composition contains (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a polyimide resin. The (B) component content is 10 mass% or more and 50 mass% or less when a nonvolatile content in the resin composition is 100 mass%.

Description

Resin composition

The present invention relates to a resin composition. Furthermore, the present invention relates to a resin sheet, a printed wiring board, a multilayer flexible substrate, and a semiconductor device obtained by using the resin composition.

In terms of the manufacturing technology of printed wiring boards, there is known a manufacturing method in which an insulating layer and a conductor layer are alternately stacked and assembled.

As for the insulating material of the printed wiring board used for such an insulating layer, the resin composition of patent document 1, for example, has been disclosed. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2019-6869

[Discovery of Invention] [The problem to be solved by the invention]

In recent years, the dielectric constant of the insulating layer has been required to further increase. In addition, with the spread of smartphones, etc., the demand for thinning has been intensified, and therefore, thinning of the insulating layer has been required. If the insulating layer becomes thinner, there is a tendency for warping to occur, so it is required to suppress the curing shrinkage rate of the insulating layer.

The subject of the present invention is to obtain a resin composition capable of suppressing curing shrinkage and having an excellent dielectric constant, a resin sheet containing the resin composition, and a printed wiring provided with an insulating layer formed using the resin composition Board and semiconductor device. [Means to solve the problem]

The inventors of the present invention have devoted themselves to the research and review of the above-mentioned problems, and found that the requested resin composition contains (A) an aromatic ester skeleton and unsaturated bond-containing compound and a predetermined amount of (B) polyimide resin, namely The above-mentioned problems can be solved.

(一般式(A-1)中，Ar¹¹ 各自獨立地表示可具有取代基之1價的芳香族烴基，Ar¹² 各自獨立地表示可具有取代基之2價的芳香族烴基，Ar¹³ 各自獨立地表示可具有取代基之2價的芳香族烴基、可具有取代基之2價的脂肪族烴基、氧原子、硫原子或由此等之組合所成的2價的基。n表示0~10之整數。)

(一般式(A-2)中，Ar²¹ 表示可具有取代基之m價的芳香族烴基，Ar²² 各自獨立地表示可具有取代基之1價的芳香族烴基。m表示2或3之整數。) [3] 如[1]或[2]之樹脂組成物，其中，令樹脂組成物中的不揮發成分為100質量%時，(A)成分的含量為0.1質量%以上30質量%以下。 [4] 如[1]~[3]中任一項之樹脂組成物，其中，進一步含有(C)無機填充材。 [5] 如[4]之樹脂組成物，其中，令樹脂組成物中的不揮發成分為100質量%時，(C)成分的含量為30質量%以上。 [6] 如[1]~[5]中任一項之樹脂組成物，其中，進一步含有(D)熱硬化性樹脂。 [7] 如[1]~[6]中任一項之樹脂組成物，其係絕緣層形成用。 [8] 如[1]~[7]中任一項之樹脂組成物，其係為了形成導體層之絕緣層形成用。 [9] 一種樹脂薄片，其係包含支持體，與設置於該支持體上含有[1]~[8]中任一項之樹脂組成物的樹脂組成物層。 [10] 一種印刷配線板，其係包含藉由[1]~[8]中任一項之樹脂組成物的硬化物所形成之絕緣層。 [11] 一種多層可撓性基板，其係包含藉由[1]~[8]中任一項之樹脂組成物的硬化物所形成之絕緣層。 [12] 一種半導體裝置，其係包含[10]之印刷配線板。 [13] 一種半導體裝置，其係包含[11]之多層可撓性基板。 [發明之效果]That is, the present invention includes the following contents. [1] A resin composition containing (A) a compound containing an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin, wherein the non-volatile content in the resin composition is 100% by mass , The content of (B) component is 10% by mass or more and 50% by mass or less. [2] The resin composition according to [1], wherein the component (A) is any one of the compound represented by the following general formula (A-1) and the compound represented by the following general formula (A-2) .

(In the general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group ^{that may have a substituent, Ar 12} each independently represents a divalent aromatic hydrocarbon group that may have a substituent, and Ar ¹³ each independently Ground means a divalent aromatic hydrocarbon group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination of these. n represents 0-10 Integer.)

(In general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group ^{that may have a substituent, and Ar 22} each independently represents a monovalent aromatic hydrocarbon group that may have a substituent. m represents an integer of 2 or 3 .) [3] The resin composition of [1] or [2], wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (A) is 0.1% by mass to 30% by mass . [4] The resin composition according to any one of [1] to [3], which further contains (C) an inorganic filler. [5] The resin composition according to [4], wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 30% by mass or more. [6] The resin composition according to any one of [1] to [5], which further contains (D) a thermosetting resin. [7] The resin composition of any one of [1] to [6], which is used for forming an insulating layer. [8] The resin composition of any one of [1] to [7], which is used for forming an insulating layer for forming a conductive layer. [9] A resin sheet comprising a support and a resin composition layer containing the resin composition of any one of [1] to [8] provided on the support. [10] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition of any one of [1] to [8]. [11] A multilayer flexible substrate comprising an insulating layer formed by a cured product of the resin composition of any one of [1] to [8]. [12] A semiconductor device comprising the printed wiring board of [10]. [13] A semiconductor device comprising the multilayer flexible substrate of [11]. [Effects of Invention]

According to the present invention, it is possible to provide a resin composition capable of suppressing curing shrinkage and a cured product having excellent dielectric rate, a resin sheet containing the resin composition, and printing with an insulating layer formed using the resin composition Wiring boards, multilayer flexible substrates, and semiconductor devices.

Hereinafter, the present invention will be explained in detail based on its suitable embodiments. However, the present invention is not limited to the following embodiments and exemplified materials, and can be modified and implemented arbitrarily within the scope of the present invention and its equivalent scope. In addition, the so-called dielectric rate means the specific dielectric rate unless otherwise specified.

[Resin composition] The resin composition of the present invention is a resin composition containing (A) a compound containing an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin. The content of the (B) component is such that When the non-volatile content is 100% by mass, it is 10% by mass or more and 50% by mass or less. In the present invention, by containing the component (A) and further containing the component (B) in a predetermined amount, a cured product can be obtained that can suppress curing shrinkage and is excellent in dielectric constant. In addition, hardened products with excellent dielectric tangent are usually also available.

The resin composition may be combined with the components (A) to (B), and further includes arbitrary components. Optional components include (C) inorganic fillers, (D) thermosetting resins, (E) hardening accelerators, and (F) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

＜(A) Compound containing aromatic ester skeleton and unsaturated bond＞ The resin composition contains (A) an aromatic ester skeleton and an unsaturated bond-containing compound as the (A) component. By including the component (A) in the resin composition, it is possible to obtain a cured product capable of suppressing curing shrinkage and having an excellent dielectric constant. (A) A component may be used individually by 1 type, and may use 2 or more types together.

(A) The component has an aromatic ester skeleton. The aromatic ester skeleton means a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Among them, it is more preferable to have an aromatic ring at both ends of the ester bond. Examples of groups having such a skeleton include arylcarbonyloxy, aryloxycarbonyl, arylcarbonyloxy, aryloxycarbonyl, arylcarbonyloxy arylene, and aryloxycarbonyloxy. Aryl, arylcarbonyloxy arylene, aryloxycarbonyl arylene, etc. In addition, the number of carbon atoms of the group having such a skeleton is preferably 7-20, more preferably 7-15, and still more preferably 7-11. Aromatic hydrocarbon groups such as an aryl group and an aryl group may have a substituent.

Regarding the aryl group, an aryl group having 6 to 30 carbon atoms is preferred, an aryl group having 6 to 20 carbon atoms is more preferred, and an aryl group having 6 to 10 carbon atoms is even more preferred. Examples of such aryl groups include phenyl, pyranyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, Pyridazinyl, pyrazinyl, triazinyl and other monocyclic aromatic compounds with one hydrogen atom removed; naphthyl, anthracenyl, phenanthryl, quinolyl, isoquinolyl, quinazolinyl , Phthalazinyl, pteridine, coumarin, indolyl, benzimidazolyl, benzopyranyl, acridinyl, etc., which have one hydrogen atom removed from a condensed ring aromatic compound, etc.

Regarding the aryl group, the aryl group having 6 to 30 carbon atoms is preferred, the aryl group having 6 to 20 carbon atoms is more preferable, and the aryl group having 6 to 10 carbon atoms is even more preferable. Examples of such arylene groups include phenylene, naphthylene, anthracenyl, and biphenylene (-C ₆ H ₄ -C ₆ H ₄ -).

(A) The component contains an unsaturated bond. As a result, the dielectric rate of the hardened material will be improved. In addition, unsaturated bonds contribute to the curing reaction of the resin composition. Since the unsaturated bond contributes to the hardening reaction, it is possible to prevent a part of the aromatic ester skeleton from being used for the hardening reaction. As a result, the hardening shrinkage rate is suppressed.

This unsaturated bond is preferably a carbon-carbon unsaturated bond. Regarding the unsaturated bond, it is preferable to have a substituent having at least one unsaturated bond. Examples of the unsaturated bond include unsaturated hydrocarbon groups such as alkenyl groups having 2 to 30 carbon atoms and alkynyl groups having 2 to 30 carbon atoms. The unsaturated bond preferably has a substituent having an aromatic hydrocarbon group at the end, and more preferably has a substituent having an aromatic hydrocarbon group at both ends.

Examples of alkenyl groups having 2 to 30 carbon atoms include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl. , 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadec-4,7-dienyl, hex -1,3,5-trienyl, pentadeca-1,4,7-trienyl, etc.

Examples of alkynyl groups having 2 to 30 carbon atoms include ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-pentynyl, and 4-pentynyl , 1,3-butadiynyl, etc.

Among these, the unsaturated bond is preferably an alkenyl group having 2 to 30 carbon atoms, an alkenyl group having 2 to 10 carbon atoms is more preferable, and an alkenyl group having 2 to 5 carbon atoms is even more preferable , Allyl, isopropenyl, 1-propenyl are even more preferred, and allyl is particularly preferred.

In addition to the aromatic ester skeleton, the component (A) may further have any one of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a group formed by a combination of these. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring, and the aromatic ring may be any one of a monocyclic ring, a polycyclic ring, and a heterocyclic ring.

Regarding the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferred, an arylene group and an aralkyl group are more preferable, and an aryl group is even more preferable. Regarding the aryl group, the aryl group having 6 to 30 carbon atoms is preferred, the aryl group having 6 to 20 carbon atoms is more preferable, and the aryl group having 6 to 10 carbon atoms is even more preferable. Examples of such arylene groups include phenylene, naphthylene, anthracenyl, and biphenylene. In terms of aralkylene, aralkylene having 7 to 30 carbon atoms is preferred, aralkylene having 7 to 20 carbon atoms is more preferred, and aralkylene having 7 to 15 carbon atoms is even more preferred . Among these, phenylene is more preferred.

As for the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferred, a divalent saturated aliphatic hydrocarbon group is more preferred, and an alkylene group and a cycloalkylene group are even more preferred. As for the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is even more preferred. As for the alkylene group, for example, methylene group, ethylene group, propyl group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1 -Dimethylethylene, 1,2-dimethylethylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, hexylene, etc.

Regarding the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferred, a cycloalkylene group of 3 to 15 is more preferred, and a cycloalkylene group of 5 to 10 is even more preferred. Regarding the cycloalkylene group, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cyclohexene, represented by the following formulas (a) to (d) The cyclic alkylene and so on. In formulas (a) ~ (d), "*" represents a bonding bond.

The aromatic ester skeleton, aromatic hydrocarbon group, aliphatic hydrocarbon group, and unsaturated hydrocarbon group may have a substituent. Examples of the substituent include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. The substituent may be contained alone or in combination of two or more kinds.

Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl , Isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, n-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, cyclooctyl, cyclononyl.

Although there are no particular restrictions on the alkoxy group having 1 to 10 carbon atoms, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, and hexyloxy group can be mentioned. , 2-ethylhexyloxy, octyloxy, nonyloxy, etc.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The above-mentioned substituent may further have a substituent (hereinafter referred to as a "secondary substituent"). The unsaturated hydrocarbon group is as described above. Regarding the secondary substituent, unless otherwise specified, the same one as the above-mentioned substituent can be used.

(一般式(A-1)中，Ar¹¹ 各自獨立地表示可具有取代基之1價的芳香族烴基，Ar¹² 各自獨立地表示可具有取代基之2價的芳香族烴基，Ar¹³ 各自獨立地表示可具有取代基之2價的芳香族烴基、可具有取代基之2價的脂肪族烴基、氧原子、硫原子或由此等之組合所成的2價的基。n表示0~10之整數。)

(一般式(A-2)中，Ar²¹ 表示可具有取代基之m價的芳香族烴基，Ar²² 各自獨立地表示可具有取代基之1價的芳香族烴基。m表示2或3之整數。)(A) The component is preferably any one of the compound represented by the following general formula (A-1) and the compound represented by the following general formula (A-2).

(In the general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group ^{that may have a substituent, Ar 12} each independently represents a divalent aromatic hydrocarbon group that may have a substituent, and Ar ¹³ each independently Ground means a divalent aromatic hydrocarbon group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination of these. n represents 0-10 Integer.)

(In general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group ^{that may have a substituent, and Ar 22} each independently represents a monovalent aromatic hydrocarbon group that may have a substituent. m represents an integer of 2 or 3 .)

In general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Examples of monovalent aromatic hydrocarbon groups include phenyl, pyrrolyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidine Groups, pyridazinyl, pyrazinyl, triazinyl, etc., where one hydrogen atom is removed from a monocyclic aromatic compound; naphthyl, anthracenyl, acridine, phenanthryl, quinolinyl, isoquinolinyl, quinazole A linyl group, phthalazinyl group, pteridine group, coumarin group, indolyl group, benzimidazolyl group, benzopyranyl group, acridinyl group, etc., which have one hydrogen atom removed from a condensed ring aromatic compound; etc., Among them, from the viewpoint of remarkably obtaining the effects of the present invention, a phenyl group is preferred. The monovalent aromatic hydrocarbon group represented by ^{Ar 11 may have a substituent.} The substituent is the same as the substituent which may have an aromatic ester skeleton. Among them, it is more preferable that ^{the substituent of Ar 11} contains an unsaturated bond.

In general formula (A-1), Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. As for the divalent aromatic hydrocarbon group, an aryl group, an aralkyl group, etc. can be mentioned, and an aryl group is preferred. Regarding the aryl group, the aryl group having 6 to 30 carbon atoms is preferred, the aryl group having 6 to 20 carbon atoms is more preferable, and the aryl group having 6 to 10 carbon atoms is even more preferable. Examples of such arylene groups include phenylene, naphthylene, anthracenyl, and biphenylene. In terms of aralkylene, aralkylene having 7 to 30 carbon atoms is preferred, aralkylene having 7 to 20 carbon atoms is more preferred, and aralkylene having 7 to 15 carbon atoms is even more preferred. Among these, phenylene is more preferred.

The divalent aromatic hydrocarbon group represented by ^{Ar 12 may have a substituent.} The substituent is the same as the substituent which may have an aromatic ester skeleton.

In general formula (A-1), Ar ¹³ each independently represents a divalent aromatic hydrocarbon group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, an oxygen atom, a sulfur atom, or the like The divalent base formed by the combination is preferably the divalent base formed by the combination. Divalent aromatic hydrocarbon aspect, the same system of FIG Ar ¹² divalent aromatic hydrocarbon group.

Regarding the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferable, an alkylene group and a cycloalkylene group are more preferable, and a cycloalkylene group is more preferable.

As for the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is even more preferred. As for the alkylene group, for example, methylene group, ethylene group, propyl group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1 -Dimethylethylene, 1,2-dimethylethylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, hexylene, etc.

Regarding the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferred, a cycloalkylene group of 3 to 15 is more preferred, and a cycloalkylene group of 5 to 10 is even more preferred. Regarding the cycloalkylene group, for example, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclopentylene group, cyclohexylene group, and those represented by the above formulas (a) to (d) Cycloalkylene groups and the like are preferably cycloalkylene groups represented by formula (c).

The divalent group formed by such a combination is preferably a divalent group formed by combining a divalent aromatic hydrocarbon group which may have a substituent and a divalent aliphatic hydrocarbon group which may have a substituent, A divalent group formed by alternately combining a plurality of optionally substituted divalent aromatic hydrocarbon groups and a plurality of optionally substituted divalent aliphatic hydrocarbon groups is more preferable. Specific examples of the aforementioned divalent group include the following divalent groups (A1) to (A8). In the formula, a1 to a8 represent an integer of 0 to 10, and preferably represent an integer of 0 to 5. "*" indicates a bonding bond, and the wave line indicates the structure obtained by the reaction of the aromatic compound, the oxyhalide of the aromatic compound, or the esterification of the aromatic compound used in the synthesis of component (A).

The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by ^{Ar 13 may have a substituent.} The substituent is the same as the substituent which may have an aromatic ester skeleton.

In the general formula (A-1), n represents an integer from 0 to 10, preferably when it represents an integer from 0 to 5, and more preferably when it represents an integer from 0 to 3. In addition, when the compound represented by general formula (A-1) is an oligomer or polymer, n represents the average value.

In general formula (A-2), Ar ²¹ represents an aromatic hydrocarbon group of m valence which may have a substituent. For the m-valent aromatic hydrocarbon group, the m-valent aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, and the m-valent aromatic hydrocarbon group with 6 to 20 carbon atoms is more preferred, with 6 to 10 carbon atoms. The m-valent aromatic hydrocarbon group is even better. The m-valent aromatic hydrocarbon group represented by Ar ^{21 may have a substituent.} The substituent is the same as the substituent which may have an aromatic ester skeleton.

In general formula (A-2), Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Ar ²² is the same as the aromatic hydrocarbon group represented ^{by Ar 11} in the general formula (A-1). The monovalent aromatic hydrocarbon group represented by ^{Ar 22 may have a substituent.} The substituent is the same as the substituent which may have an aromatic ester skeleton.

In general formula (A-2), m represents an integer of 2 or 3, and 2 is preferred.

(A) Specific examples of the component include the following compounds. In addition, specific examples of the component (A) include the compounds described in paragraphs 0068 to 0071 of International Publication No. 2018/235424 and paragraphs 0113 to 0115 of International Publication No. 2018/235425. However, the component (A) is not limited to these specific examples. In the formula, s represents an integer of 0 or more, and r represents an integer of 1-10.

(A) The component synthesized by a well-known method can also be used. (A) The synthesis of the component can be carried out, for example, by the method of International Publication No. 2018/235424 or International Publication No. 2018/235425.

(A) The weight average molecular weight of the component is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, more preferably 3000 or less from the viewpoint of remarkably obtaining the effect of the present invention. It is 2000 or less, more preferably 1500 or less. (A) The weight average molecular weight of the component is a weight average molecular weight in terms of polystyrene measured by a colloidal permeation chromatography (GPC) method.

(A) The unsaturated bond equivalent of the component is preferably 50 g/eq or more, more preferably 100 g/eq. or more, and still more preferably 150 g/eq. from the viewpoint of remarkably obtaining the effects of the present invention. It is preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, and still more preferably 500 g/eq. or less. The unsaturated bond equivalent is the mass of the component (A) including 1 equivalent of the unsaturated bond.

In terms of the content of component (A), from the viewpoint of obtaining a cured product that can suppress curing shrinkage and has an excellent dielectric rate, when the non-volatile content in the resin composition is 100% by mass, it is 0.1% by mass or more, which is more It is preferably 1% by mass or more, more preferably 3% by mass or more, 30% by mass or less, more preferably 28% by mass or less, still more preferably 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass %the following.

＜(B) Polyimide resin＞ The resin composition contains (B) polyimide resin as the (B) component. When the component (B) is contained in the resin composition, the cured product will have flexibility. As a result, a cured product can be obtained that can suppress curing shrinkage and is excellent in dielectric rate.

(B) The content of component, from the viewpoint of suppressing curing shrinkage, when the non-volatile content in the resin composition is 100% by mass, it is 10% by mass or more, preferably 13% by mass or more, and more preferably 15 Mass% or more, more preferably 20 mass% or more. The upper limit thereof is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

(B) If a component is a resin which has an imine bond in a repeating unit, it will not specifically limit. (B) The component generally includes the product obtained by the imidization reaction of a diamine compound and an acid anhydride. The component (B) also contains modified polyimide resins such as silicone modified polyimide resins. (B) A component may be used individually by 1 type, and may use 2 or more types together.

The diamine compound for preparing the component (B) is not particularly limited, but examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

As for the aliphatic diamine compound, for example, 1,2-ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6- Linear aliphatic diamine compounds such as hexamethylene diamine, 1,5-diaminopentane, 1,10-diaminodecane, etc.; 1,2-diamino-2-methyl Branched chain aliphatic diamine compounds such as propane, 2,3-diamino-2,3-butane and 2-methyl-1,5-diaminopentane; 1,3-bis(amine Methyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc. Alicyclic diamine compounds; dimer acid diamines (hereinafter also referred to as "dimer diamines"), etc. Among them, dimer acid diamines are more preferred.

The so-called dimer acid-type diamine refers to a diamine compound in which the two terminal carboxylic acid groups (-COOH) of the dimer acid are replaced by aminomethyl groups (-CH2-NH2) or amino groups (-NH2) . Dimer acid is a well-known compound obtained by diquantizing unsaturated fatty acids (preferably those with 11-22 carbons, particularly those with 18 carbons). The industrial manufacturing process has almost been used in the industry. standardization. Dimer acid can be easily obtained by dimerizing an unsaturated fatty acid with 18 carbon atoms such as oleic acid and linoleic acid, which can be obtained extremely cheaply, with a carbon number 36 as the main component. In addition, the dimer acid may contain any amount of monomer acid, trimer acid, other polymerized fatty acids, etc., depending on the manufacturing method, the degree of purification, and the like. In addition, after the polymerization reaction of the unsaturated fatty acid, although the double bond may remain, in this specification, a hydrogenated product further subjected to a hydrogenation reaction to reduce the degree of unsaturation is also included in the dimer acid. Dimer acid type diamines are commercially available, and examples include "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" manufactured by Croda Japan; "VERSAMINE 551" and "VERSAMINE 552" manufactured by Cognis Japan.

The aromatic diamine compound includes, for example, a phenylenediamine compound, a naphthalene diamine compound, a diphenylamine compound, and the like.

The so-called phenylenediamine compound means a compound formed from a benzene ring having two amino groups. Furthermore, the benzene ring herein may optionally have 1 to 3 substituents. The substituent system here is the same as the substituent which may have an aromatic ester skeleton in (A) component. The phenylenediamine compound includes, for example, 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, and 2,6-diaminotoluene , 3,5-diaminobiphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, etc.

The naphthalene diamine compound means a compound formed from a naphthalene ring having two amino groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. The substituent system here is the same as the substituent which may have an aromatic ester skeleton in (A) component. The naphthalene diamine compound includes, for example, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene, and the like.

The diphenylamine compound means a compound containing two aniline structures in the molecule. Furthermore, the two benzene rings in the two aniline structures may each further optionally have 1 to 3 substituents. The substituent system here is the same as the substituent which may have an aromatic ester skeleton in (A) component. The two aniline structures in the diphenylamine compound can be directly bonded, and/or can be bonded through 1 or 2 connection structures with 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms . The diphenylamine compound may include two aniline structures that are bonded by two bonds.

In terms of the "connection structure" in the diphenylamine compound, specific examples include -NHCO-, -CONH-, -OCO-, -COO-, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C( CF ₃ ) ₂ -, -CH=CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, -Ph-CO-O-Ph-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, represented by the following formulas (I) and (II) The base and the base formed by the combination of these. In this specification, "Ph" means 1,4-phenylene, 1,3-phenylene or 1,2-phenylene.

With regard to the diphenylamine compound in one embodiment, specifically, 4,4'-diamino-2,2'-di-trifluoromethyl-1,1'-biphenyl, 3,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4 '-Diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylene) Yl)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , Α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)benzene Yl)-1,4-diisopropylbenzene, 4,4'-(9-phenylene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2, 2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-bis Amino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)pyridium, 5-(4-aminophenoxy) Group)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan, etc., preferably 5-(4-aminophenoxy)-3 -[4-(4-Aminophenoxy)phenyl]-1,1,3-trimethylindan.

In another embodiment, regarding the diphenylamine compound, for example, a diamine compound represented by the following formula (B-1) and the like can be mentioned.

(式(B-1)中，R¹ ~R⁸ 係各自獨立地表示氫原子、鹵素原子、氰基、硝基、-X⁹ -R⁹ 、或-X¹⁰ -R¹⁰ ，R¹ ~R⁸ 之中至少1個為-X¹⁰ -R¹⁰ ，X⁹ 係各自獨立地表示單鍵、-NR^9’ -、-O-、 -S-、-CO-、-SO₂ -、-NR^9’ CO-、-CONR^9’ -、-OCO-、或 -COO-，R⁹ 係各自獨立地表示取代或無取代之烷基、或取代或無取代之烯基，R^9’ 係各自獨立地表示氫原子、取代或無取代之烷基、或取代或無取代之烯基，X¹⁰ 係各自獨立地表示單鍵、-(取代或無取代之伸烷基)-、-NH-、-O-、-S-、-CO-、-SO₂ -、-NHCO-、-CONH-、-OCO-、或-COO-，R¹⁰ 係各自獨立地表示取代或無取代之芳基、或取代或無取代之雜芳基。)

(In formula (B-1), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ , or -X ¹⁰ -R ¹⁰ , R ¹ to R ⁸ among at least one of -X ¹⁰ -R ^10, X ⁹ each independently represent a single bond ^{lines, -NR 9 '-, - O-} , -S -, - CO -, - SO 2 -, - NR 9 ^{'CO -, - CONR 9'} -, - OCO-, or -COO-, R ⁹ each independently represent a substituted-based or the unsubstituted alkyl group or a substituted or unsubstituted alkenyl group of, R ^{9 'are} each independently based Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, X ¹⁰ each independently represents a single bond,-(substituted or unsubstituted alkylene) -, -NH-, -O -, -S-, _{-CO-, -SO 2} -, -NHCO-, -CONH-, -OCO-, or -COO-, R ¹⁰ is each independently a substituted or unsubstituted aryl group, or substituted or Unsubstituted heteroaryl.)

^{The alkyl group represented by R 9} and R ^{9'in the} formula (B-1) refers to a linear, branched or cyclic monovalent saturated aliphatic hydrocarbon group. As for the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, Cyclopentyl, cyclohexyl, etc.

^{The alkenyl group represented by R 9} and R ^{9'in the} formula (B-1) refers to a linear, branched or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. As for the alkenyl group, an alkenyl group having 2 to 6 carbon atoms is preferred, and an alkenyl group having 2 or 3 carbon atoms is more preferred. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexene Group, 3-hexenyl, 5-hexenyl, 2-cyclohexenyl, etc. The substituents of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, but examples include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amine groups, and nitro groups. , Hydroxyl, carboxyl, sulfonic acid, etc. In terms of the number of substituents, 1 to 3 are preferred, and 1 is even more preferred.

The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" and the substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, but examples include halogen atoms and cyano groups. , Alkoxy, amine, nitro, hydroxyl, carboxyl, sulfonic acid, etc. In terms of the number of substituents, 1 to 3 are preferred, and 1 is even more preferred.

The alkoxy group refers to a monovalent group (alkyl-O-) formed by an alkyl bond on an oxygen atom. As for the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred, and an alkoxy group having 1 to 3 carbon atoms is more preferred. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyl. Oxy etc.

^{The alkylene represented by X 10} in the formula (B-1) refers to a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkylene having 1 to 6 carbon atoms. The alkylene group having 1 to 3 carbon atoms is more preferable. With regard to the alkylene group, for example, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )- , -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH(CH ₃ )-,- CH ₂ -CH(CH ₃ )-CH ₂ -, -CH(CH ₃ )-CH ₂ -CH ₂ -, -CH ₂ -C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -CH _2- Wait. The substituents of the alkylene group in the "substituted or unsubstituted alkylene group" are not particularly limited, but examples include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amine groups, Nitro group, hydroxyl group, carboxyl group, sulfonic acid group, etc. In terms of the number of substituents, 1 to 3 are preferred, and 1 is even more preferred.

^{Regarding the aryl group represented by R 10} in the formula (B-1), an aryl group having 6 to 14 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. Examples of such aryl groups include phenyl, 1-naphthyl, 2-naphthyl and the like, and phenyl is preferred. The substituents of the aryl group in the "substituted or unsubstituted aryl group" are not particularly limited, but examples include halogen atoms, cyano groups, alkyl groups, alkoxy groups, aryl groups, heteroaryl groups, and amino groups. , Nitro, hydroxyl, carboxyl, sulfonic acid, etc. In terms of the number of substituents, 1 to 3 are preferred, and 1 is even more preferred.

^{The heteroaryl group represented by R 10} in formula (B-1) refers to an aromatic heterocyclic group having 1 to 4 hetero atoms selected from oxygen atoms, nitrogen atoms, and sulfur atoms. The heteroaryl group is preferably a monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group with 5-12 members (preferably 5 or 6 members). Examples of such heteroaryl groups include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxa Azolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furazanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl , 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, Triazinyl and so on. The substituents of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" are the same as the substituents of the aryl group in the "substituted or unsubstituted aryl group".

R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ or -X ¹⁰ -R ¹⁰ . R ¹ to R ^{8 are} preferably each independently a hydrogen atom or -X ¹⁰ -R ¹⁰ .

At least one of R ¹ to R ^{8 is -X 10} -R ¹⁰ . Preferably, one or two of R ¹ to R ^{8 are -X 10} -R ¹⁰ , more preferably ^{one or two of R 5} to R ⁸ are -X ¹⁰ -R ¹⁰ , and still more Preferably, one or two of R ⁵ and R ^{7 are -X 10} -R ¹⁰ .

In one embodiment, it is preferable that one or two ^{of R 1} to R ^{8 are -X 10} -R ¹⁰ , and the other of R ¹ to R ⁸ are hydrogen atoms, more preferably R ⁵ to R ⁸ One or two of them are -X ¹⁰ -R ¹⁰ , and the other of R ¹ to R ⁸ are hydrogen atoms, and more preferably one or two ^{of R 5} and R ^{7 are -X 10} -R ¹⁰ , and the ^{rest of R 1} to R ⁸ are hydrogen atoms.

Based X ⁹ each independently represent a single ^{bond, -NR 9 '-, - O-} , -S -, - CO -, - SO 2 -, - NR 9' CO -, - CONR 9 '-, - OCO-, Or -COO-. R ⁹ is each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. X ^{9 is} preferably a single bond.

R ^{9 'each} independently represents a hydrogen-based atom, the substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group of. R ^{9 is} preferably a substituted or unsubstituted alkyl group.

X ¹⁰ is each independently representing a single bond,-(substituted or unsubstituted alkylene) -, -NH-, -O-, -S- _{, -CO-, -SO 2} -, -NHCO-, -CONH -, -OCO-, or -COO-. X ^{10 is} preferably a single bond.

R ¹⁰ each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ^{10 is} preferably a substituted or unsubstituted aryl group.

(式中，R¹ ~R⁶ 及R⁸ 係各自獨立地表示氫原子、鹵素原子、氰基、硝基、-X⁹ -R^{9 ，} 其他的記號係與式(B-1)相同。)

One embodiment is the diamine compound represented by the formula (B-1), preferably the compound represented by the following formula (B-2), and the compound represented by the following formula (B-3) (4-amino group) Benzoic acid 5-amino-1,1'-biphenyl-2-ester) is more preferred.

(In the formula, R ¹ to R ⁶ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ^{9 , and the} other symbols are the same as in the formula (B-1).)

A commercially available diamine compound can also be used, and one synthesized by a well-known method can be used. For example, the diamine compound represented by the formula (B-1) can be synthesized by the synthesis method described in Patent No. 6240798 or a method based thereon. A diamine compound may be used individually by 1 type, and may be used in combination of 2 or more types.

Although the acid anhydride used to prepare the component (B) is not particularly limited, in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. The aromatic tetracarboxylic dianhydride includes, for example, pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, diphthalic dianhydride, etc., preferably diphthalic dianhydride .

The benzene tetracarboxylic dianhydride means the dianhydride of benzene having 4 carboxyl groups, and the benzene ring here may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (B-4)). Pyromellitic dianhydride, specifically, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, etc. are mentioned.

The naphthalene tetracarboxylic dianhydride means a dianhydride of naphthalene having 4 carboxyl groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (B-4)). Regarding naphthalenetetracarboxylic dianhydride, specifically, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, etc. are mentioned.

The so-called anthracene tetracarboxylic dianhydride means an anthracene dianhydride having 4 carboxyl groups, and the anthracene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (B-4)). Specific examples of anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride.

The diphthalic dianhydride means a compound containing two anhydrous phthalic acid in the molecule, and the two benzene rings in the two anhydrous phthalic acid may each optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ¹³ -R ¹³ (the same as the definition of the following formula (B-4)). The two anhydrous phthalic acids in diphthalic dianhydride are directly bonded, or they can be bonded through a connection structure with 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms .

(式中，R¹¹ 及R¹² 係各自獨立地表示鹵素原子、氰基、硝基或-X¹³ -R¹³ ， X¹³ 係各自獨立地表示單鍵、-NR^13’ -、-O-、-S-、-CO-、-SO₂ -、-NR^13’ CO-、-CONR^13’ -、-OCO-、或-COO-， R¹³ 係各自獨立地表示取代或無取代之烷基、或取代或無取代之烯基， R^13’ 係各自獨立地表示氫原子、取代或無取代之烷基、或取代或無取代之烯基， Y表示單鍵，或者是可透過具有由碳原子、氧原子、硫原子及氮原子選出的1~100個骨架原子之連接構造， n1及m1各自獨立地表示0~3之整數。)As for the diphthalic dianhydride, the compound represented by formula (B-4) can be mentioned, for example.

(In the formula, R ¹¹ and R ¹² each independently represent a halogen atom, a cyano group, a nitro group, or -X ¹³ -R ¹³ , and X ¹³ each independently represents a single bond, -NR ^13' -, -O-, -S-, _{-CO-, -SO 2} -, -NR ^13' CO-, -CONR ^13' -, -OCO-, or -COO-, R ¹³ is each independently a substituted or unsubstituted alkyl group, Or substituted or unsubstituted alkenyl, R ^13' is each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond, or it can be transmitted through a carbon atom , Oxygen atom, sulfur atom and nitrogen atom selected from 1 to 100 skeleton atoms connected structure, n1 and m1 each independently represent an integer of 0 to 3.)

Y preferably has a connection structure of 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. n1 and m1 are preferably 0.

The "connected structure" in Y has 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. "The connection structure preferably represents -[A-Ph] _a -A-[Ph-A] _b- [In the formula, A systems each independently represent a single bond,-(substituted or unsubstituted alkylene) -, -O-, -S-, _{-CO-, -SO 2} -, -CONH-, -NHCO-, -COO-, or -OCO-, a and b each independently represent an integer of 0 to 2 (preferably It is a divalent group shown in 0 or 1)].

The "connection structure" in Y, specifically, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -O-, -CO-, -SO ₂ -, -Ph-, -O-Ph-O -, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, etc.

In terms of diphthalic dianhydride, specifically, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Acid dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3, 3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic dianhydride 2,2'-bis(3,4- Dicarboxyphenoxyphenyl) dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2, 2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-di Phthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1, 3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy) Base) phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis (3,4-Dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)bisphthalic dianhydride, etc.

The aromatic tetracarboxylic dianhydride can also be commercially available, and can also be synthesized by a well-known method or a method based thereon. Aromatic tetracarboxylic dianhydride may be used individually by 1 type, and may be used in combination of 2 or more types.

In one embodiment, the acid anhydride for producing the component (B) may contain other acid anhydrides in addition to the aromatic tetracarboxylic dianhydride.

In terms of other acid anhydrides, specifically, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4- Tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis (Cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4, 4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4, 4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, etc. Carboxylic dianhydride.

The content of the structure derived from aromatic tetracarboxylic dianhydride in the total structure of the acid anhydride that constitutes component (B) is preferably 10 mol% or more, more preferably 30 mol% or more, and 50 mol % Or more is better, 70 mol% or more is even better, 90 mol% or more is even better, and 100 mol% is particularly good.

(一般式(B)中，R⁵¹ 表示單鍵或源自酸酐之殘基，R⁵² 表示單鍵或源自二胺化合物之殘基。)The component (B) preferably has a structural unit represented by the following general formula (B).

(In general formula (B), R ⁵¹ represents a single bond or a residue derived from an acid anhydride, and R ⁵² represents a single bond or a residue derived from a diamine compound.)

R ⁵¹ represents a single bond or a residue derived from acid anhydride, preferably a residue derived from acid anhydride. The ^{acid anhydride-derived residue represented by R 51} refers to a divalent group after removing two oxygen atoms from the acid anhydride. The acid anhydride is as described above.

R ⁵² represents a single bond or a residue derived from a diamine compound, preferably a residue derived from a diamine compound. The residue derived from a diamine compound represented by R ⁵² refers to a divalent group obtained by removing two amine groups from the diamine compound. The diamine compound is as described above.

The component (B) can be prepared by a conventionally well-known method. A well-known method includes, for example, a method of heating and reacting a mixture of a diamine compound, an acid anhydride, and a solvent. The mixing amount of the diamine compound, for example, is usually 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents relative to the acid anhydride.

(B) Regarding the solvent used for the preparation of the component, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N-methyl Amine-based solvents such as methyl-2-pyrrolidone; ketone-based solvents such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ester-based solvents such as γ-butyrolactone; cyclohexane, methyl ring Hydrocarbon solvents such as hexane. In addition, in the preparation of component (B), an imidization catalyst, azeotropic dehydration solvent, acid catalyst, etc. may be used as needed. As for the imidization catalyst, for example, triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4 -Tertiary amines such as aminopyridine and pyridine. With regard to the azeotropic dehydration solvent, for example, toluene, xylene, ethylcyclohexane and the like can be mentioned. The acid catalyst includes, for example, anhydrous acetic acid. The usage amount of the imidization catalyst, azeotropic dehydration solvent, acid catalyst, etc. can be set appropriately if the industry is familiar with the field. (B) The reaction temperature for the preparation of the component is usually 100 to 250°C.

(B) The weight average molecular weight of the component is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 50,000 or less.

When the non-volatile component in the resin composition is 100% by mass, the content of component (A) is a1, and when the non-volatile component in the resin composition is 100% by mass, the content of component (B) is In the case of b1, a1/b1 is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, preferably 1 or less, more preferably 0.5 or less, and still more preferably 0.3 or less. By adjusting a1/b1 within this range, the effect of the present invention can be significantly obtained.

＜(C) Inorganic filler＞ In addition to the above-mentioned components, the resin composition may further contain an inorganic filler as the (C) component in terms of arbitrary components.

As for the material of the inorganic filler, an inorganic compound is used. Examples of materials for inorganic fillers include silica, alumina, glass, vermilionite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silicon oxide is particularly suitable. Regarding silica, examples thereof include amorphous silica, molten silica, crystalline silica, synthetic silica, and hollow silica. In addition, as for silica, spherical silica is preferred. (C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

(C) As for the commercially available components, examples include "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials; and "YC100C" manufactured by Admatechs. , "YA050C", "YA050C-MJE", "YA010C"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by TOKUYAMA; "SC2500SQ", "SO manufactured by Admatechs" -C4", "SO-C2", "SO-C1"; etc.

(C) The specific surface area of the component is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly ^{preferably 3 m 2} /g or more. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is calculated by the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the surface of the sample, and then calculating the specific surface area by the BET multipoint method.

(C) The average particle diameter of the component, from the viewpoint of remarkably obtaining the desired effect of the present invention, is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less , More preferably 2 μm or less, still more preferably 1 μm or less.

The average particle size of the component (C) can be measured by laser diffraction and scattering methods based on Mie scattering theory. Specifically, with the laser diffraction scattering type particle size distribution measuring device, the particle size distribution of the inorganic filler can be created on a volume basis, and the median diameter can be measured as the average particle size. For the measurement sample system, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed into a small glass bottle and dispersed by ultrasound for 10 minutes. Use a laser diffraction particle size distribution measuring device for the measurement sample, divide the wavelength of the light source into blue and red, measure the volume-based particle size distribution of the inorganic filler by the flow cell method, and calculate the average from the obtained particle size distribution The particle size is taken as the median diameter. Examples of laser diffraction particle size distribution measuring devices include "LA-960" manufactured by Horiba Manufacturing Co., Ltd., and the like.

(C) From the viewpoint of improving moisture resistance and dispersibility, the component (C) is preferably treated with a surface treatment agent. Surface treatment agents include, for example, vinyl silane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, Silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, etc. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, vinyl silane coupling agents, (meth)acrylic coupling agents, and aminosilane coupling agents are preferred. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

Commercial products of surface treatment agents include, for example, "KBM1003" (vinyl triethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM503" (3-methacryloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Ethoxysilane), "KBM403" (3-epoxypropoxytrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane) manufactured by Kogyo Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy siloxane manufactured by Shin-Etsu Chemical Co., Ltd.) Coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent, and more preferably between 0.2 parts by mass and 3 parts by mass, and more than 0.3 parts by mass. ~2 parts by mass is better for surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is ^{preferably 0.02 mg/m 2} or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin paint and the melt viscosity in the sheet form, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less Better.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, in terms of solvent, a sufficient amount of MEK is added to an inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. For carbon analyzers, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

(C) The content of the component, from the viewpoint of lowering the dielectric ratio, when the non-volatile content in the resin composition is 100% by mass, it is preferably 30% by mass or more, more preferably 40% by mass or more, and still more It is preferably 50% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

When the non-volatile component in the resin composition is 100% by mass, the content of component (A) is a1, and when the non-volatile component in the resin composition is 100% by mass, the content of component (B) is b1, when the non-volatile content in the resin composition is 100% by mass and the content of component (C) is c1, (a1+b1)/c1 is preferably more than 0.4, more preferably 0.43 or more, and still more It is preferably 0.45 or more, more preferably 1 or less, more preferably 0.6 or less, and still more preferably 0.55 or less. By adjusting (a1+b1)/c1 to be within this range, the effect of the present invention can be significantly obtained.

＜(D) Thermosetting resin＞ In addition to the above-mentioned components, the resin composition may further contain a thermosetting resin as the (D) component in terms of optional components. However, those that correspond to the components (A) to (B) are excluded. (D) Thermosetting resins include, for example, epoxy resins, phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, and carbodiimide resins. , Amine resins, acid anhydride resins, etc. (D) A component may be used individually by 1 type, and may be used combining 2 or more types at arbitrary ratios. Below, the system can be used such as phenol resin, naphthol resin, benzoxazine resin, active ester resin, cyanate ester resin, carbodiimide resin, amine resin, and acid anhydride resin. The resin that reacts with epoxy resin to harden the resin composition is generally called "hardener".

(D) Regarding the epoxy resin of the component, for example, bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF Type epoxy resin, dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-benzenediol type epoxy Resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane epoxy Resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the (D) component. From the standpoint of remarkably obtaining the desired effect of the present invention, the ratio of the component (D) relative to 100% by mass of the non-volatile content of the epoxy resin having two or more epoxy groups per molecule is preferably 50 Mass% or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

There are epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and solid epoxy resins at a temperature of 20°C (hereinafter referred to as "solid epoxy resins") . Regarding the component (D), the resin composition may include only a liquid epoxy resin, or only a solid epoxy resin, or may include a combination of a liquid epoxy resin and a solid epoxy resin.

As for the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

For liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine Type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin and Epoxy resins with butadiene structure are preferred, bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; and "828US", "jER828EL", and "Mitsubishi Chemical Corporation" manufactured by Mitsubishi Chemical Corporation. 825", "EPIKOTE 828EL" (bisphenol A epoxy resin); "jER807" and "1750" (bisphenol F epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol phenolic resin) manufactured by Mitsubishi Chemical Corporation Varnish type epoxy resin); "630" and "630LSD" manufactured by Mitsubishi Chemical Corporation (glycidylamine epoxy resin); "ZX1059" manufactured by Nippon Steel Chemical & Materials Co., Ltd. (bisphenol A epoxy resin and double Mixture of phenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "CELLOXIDE2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel ; "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type) manufactured by Nippon Steel Chemical & Materials Co., Ltd. Epoxy resin) and so on. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

Regarding the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups per molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups per molecule is preferable. The resin is better.

For solid epoxy resins, bis-xylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin , Phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin Resin, tetraphenylethane type epoxy resin is preferable, naphthalene type epoxy resin is more preferable.

For solid epoxy resins, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol type epoxy resin, Biphenyl type epoxy resin, naphthalene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthalene type tetrafunctional epoxy resin, naphthalene type epoxy resin Phenolic type epoxy resin and biphenyl type epoxy resin are more preferable. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation. N-690" (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (two Cyclopentadiene epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether) manufactured by DIC Corporation Type epoxy resin); "EPPN-502H" (ginseng phenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd. ", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd., "ESN485" (naphthol novolac type epoxy resin); Mitsubishi Chemical "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bis-xylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by the company; manufactured by Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (茀-type epoxy resin), "jER1010" (solid bisphenol Type A epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

(D) In terms of component, when a liquid epoxy resin and a solid epoxy resin are used in combination, the amount ratio (liquid epoxy resin: solid epoxy resin) is calculated by mass ratio, preferably 1: 0.1~1:20, more preferably 1:0.3~1:15, particularly preferably 1:1~1:10. When the ratio of the amount of the liquid epoxy resin to the solid epoxy resin is in this range, the desired effect of the present invention can be remarkably obtained. Furthermore, when used in the form of a resin sheet, it can have moderate adhesiveness. In addition, when it is generally used in the form of a resin sheet, sufficient flexibility can be obtained, and the operability can be improved. Furthermore, hardened products with very high breaking strength can usually be obtained.

(D) The epoxy equivalent of the epoxy resin in terms of ingredients is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., still more preferably 80g/eq.~2000g /Eq., and even more preferably 110g/eq.~1000 g/eq. In this range, the crosslink density of the cured product of the resin composition will have a sufficient cured product. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

(D) The weight average molecular weight (Mw) of the epoxy resin as a component is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably, from the viewpoint of remarkably obtaining the desired effect of the present invention 400~1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

(D) The content of the epoxy resin in the component aspect, from the viewpoint of obtaining a cured body showing good mechanical strength and insulation reliability, when the non-volatile content in the resin composition is 100% by mass, it is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit of the content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

(D) In terms of component, the ratio of the amount of epoxy resin to component (A) is the ratio of [total number of epoxy groups in epoxy resin]: [total number of unsaturated bonds in component (A)]. The range of 1:0.01~1:5 is preferred, 1:0.03~1:3 is more preferred, and 1:0.05~1:1 is even more preferred. Here, the "number of epoxy groups of the epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile content of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "number of unsaturated bonds of component (A)" refers to the total value obtained by dividing the mass of non-volatile components of component (A) present in the resin composition by the equivalent of unsaturated bonds. The effect of the present invention can be remarkably obtained by setting the ratio of the epoxy resin to the component (A) in this range.

When the non-volatile component in the resin composition is 100% by mass, the content of the (A) component is a1, and when the non-volatile component in the resin composition is 100% by mass, the component (D) is the ring When the content of the oxygen resin is d1, d1/a1 is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By adjusting so that d1/a1 falls within this range, the effect of the present invention can be significantly obtained.

(D) As for the active ester-based resin of the component, a resin having one or more active ester groups in one molecule can be used. Among them, active ester resins include ester groups having two or more phenol esters, thiophenol esters, N-hydroxy amine esters, and heterocyclic hydroxy compound esters in one molecule with high reactivity. The resin is better. The active ester resin is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred.

The carboxylic acid compound includes, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like.

In terms of phenol compounds or naphthol compounds, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-benzenetriol, 1,2,4-benzenetriol, bicyclic Pentadiene type diphenol compounds, phenol novolacs, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Preferable specific examples of active ester resins include active ester resins containing dicyclopentadiene-type diphenol structure, active ester resins containing naphthalene structure, and phenolic novolac-containing acetylated compounds. Ester-based resin, active ester-based resin containing phenol novolac-based benzoic acid. Among them, the active ester resin containing a naphthalene structure and the active ester resin containing a dicyclopentadiene type diphenol structure are more preferable. The so-called "dicyclopentadiene-type diphenol structure" means a bivalent structural unit formed by phenylene-bicyclopentylene-phenylene.

Commercially available active ester resins include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (DIC Company’s product) as an active ester resin containing a dicyclopentadiene-type diphenol structure; examples include "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", and "EXB-8150- 62T", "HPC-8150-60T", and "HPC-8150-62T" (manufactured by DIC Corporation) are active ester resins containing naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) as a phenol-containing novolac Active ester-based resins of acetylated compounds; Examples include "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based resin for phenolic novolac-containing benzyl compounds; Examples include "DC808" (Mitsubishi Chemical Corporation) Manufacture) Active ester-based resin as the acetone-based phenol novolac; examples include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) The active ester resin of the benzoyl compound of phenol novolac; and "EXB-8500-65T" (manufactured by DIC Corporation), etc.

(D) Regarding the phenol-based resin and naphthol-based resin as a component, it is preferable to have a novolak structure from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based resin containing a triazine skeleton is more preferred.

Specific examples of phenol resins and naphthol resins include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and "NHN", "Nippon Kayaku Co., Ltd." "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" "SN375", "SN395" manufactured by Nippon Steel Chemical & Materials Co., Ltd. ", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. manufactured by DIC.

(D) Specific examples of benzoxazine-based resins in terms of components include "JBZ-OD100" (benzoxazine ring equivalent 218) manufactured by JFE Chemical Co., Ltd., and "JBZ-OP100D" (benzoxazine Ring equivalent 218), "ODA-BOZ" (benzoxazine ring equivalent 218); "Pd" (benzoxazine ring equivalent 217) manufactured by Shikoku Chemical Industry Co., Ltd., "Fa" (benzoxazine ring equivalent 217); "HFB2006M" (benzoxazine ring equivalent 432) manufactured by Showa Polymer Corporation, etc.

(D) Regarding the cyanate ester resin of the component, for example, bisphenol A dicyanate, polyphenol cyanate, and oligo(3-methylene-1,5-phenylene cyanate) , 4,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate , 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) ) Methane, 1,3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide and bis(4-cyanate benzene) 2-functional cyanate resins such as ethers, etc.; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs; these cyanate resins are partially triazine-formed prepolymers; etc. Specific examples of cyanate resins include "PT30", "PT30S" and "PT60" (phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan, and "ULL-950S" (multifunctional Cyanate resin), "BA230", "BA230S75" (part or all of bisphenol A dicyanate is triazineized into a three-weight prepolymer), etc.

(D) Specific examples of carbodiimide resins in terms of components include CARBODILITE (registered trademark) V-03 (carbodiimide equivalent: 216, V-05 (carbon) manufactured by Nisshinbo Chemical Co., Ltd. Diamido equivalent: 216), V-07 (carbodiamido equivalent: 200); V-09 (carbodiamido equivalent: 200); Stabaxol manufactured by Rhein Chemie (registered trademark) P (carbodiimide equivalent: 302).

(D) As regards the amine-based resin of the component, resins having one or more amine groups in one molecule can be mentioned, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, from the viewpoint of exerting the desired effect of the present invention, aromatic amines are preferred. The amine-based resin is preferably a first-stage amine or a second-stage amine, and the first-stage amine is more preferred. Specific examples of amine-based resins include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiamino sulfide, and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, m-phenylenediamine, m-dimethylphenylene diamine, diethyltoluenediamine , 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl, 2,2'-dimethyl-4,4'-diamine Biphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4 ,4-Diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3 -Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'- Bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)supple, bis(4-(3-aminophenoxy)phenyl)supple, etc. . Commercially available amine resins can also be used, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS", and Mitsubishi Chemical manufactured by Nippon Kayaku Co., Ltd. "EPICURE W" made by the company, etc.

(D) As regards the acid anhydride resin of the component, a resin having one or more acid anhydride groups in one molecule can be mentioned. Specific examples of acid anhydride resins include anhydrous phthalic acid, tetrahydroanhydrous phthalic acid, hexahydroanhydrous phthalic acid, methyltetrahydroanhydrous phthalic acid, methylhexahydroanhydrous phthalic acid, methyl Nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydro anhydrous phthalic acid, dodecenyl anhydrous succinic acid, 5-(2,5-di-side oxytetrahydro-3-yl)-3 -Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene Tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(Tetrahydro-2,5-diside oxy-3-yl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride ester), styrene Polymeric acid anhydrides such as styrene and maleic acid resin copolymerized with maleic acid.

(D) In terms of ingredients, when epoxy resin and hardener are contained, the ratio of the amount of epoxy resin to all hardeners is [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener ] The ratio is preferably in the range of 1:0.01~1:5, 1:0.3~1:3 is more preferred, and 1:0.5~1:2 is even better. Here, the "number of epoxy groups of the epoxy resin" is a value obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the term "the number of active groups of the hardening agent" is a value obtained by dividing the mass of the non-volatile components of the hardening agent present in the resin composition by the equivalent of the active group and adding up all the values. (D) In terms of components, a cured body with excellent flexibility can be obtained by setting the ratio between the epoxy resin and the curing agent in this range.

(D) The content of the hardener on the component side, from the viewpoint of obtaining a hardened body with excellent flexibility, the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass relative to 100% by mass of non-volatile components. % Or more, still more preferably 1 mass% or more, more preferably 10 mass% or less, more preferably 5 mass% or less, and still more preferably 3 mass% or less.

(D) The content of the component, from the viewpoint of obtaining a hardened body with excellent flexibility, relative to 100% by mass of non-volatile components in the resin composition, preferably 5% by mass or more, more preferably 10% by mass or more, and It is more preferably 15% by mass or more, more preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

＜(E) Hardening accelerator＞ In addition to the above-mentioned components, the resin composition may further contain a hardening accelerator as the (E) component in terms of optional components. By containing the component (E), the polymerization by heat can be further promoted.

(E) In terms of component, for example, epoxy resin hardening accelerators such as phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, etc.; peroxides It is a thermal polymerization hardening accelerator such as a hardening accelerator. (E) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

Phosphorus-based hardening accelerators include, for example, triphenyl phosphine, phosphonium borate compounds, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium decanoate, ( 4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc., with triphenyl phosphine, tetrabutyl phosphonium thiocyanate, etc. Decanoate is preferred.

The amine-based hardening accelerators include, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, and (Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine, 1,8-diazabicyclo (5,4,0)-Undecene is preferred.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine Polycyanic acid adduct, 2-phenylimidazole cyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole Imidazole compounds such as morpholine and 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As for the imidazole-based hardening accelerator, commercially available products may also be used, and examples include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Regarding guanidine-based hardening accelerators, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, metformin Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc. Cyanamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

As for the metal-based hardening accelerator, for example, metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, organometallic complexes or organometallic salts can be mentioned. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetone acetone compounds, cobalt (III) acetone acetone compounds, and organic copper such as copper (II) acetone acetone compounds. Complexes, organic zinc complexes such as zinc (II) acetone compounds, organic iron complexes such as iron (III) acetone compounds, and organic nickel complexes such as nickel (II) acetone compounds Organic manganese complexes such as manganese (II) acetone compounds, etc. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Peroxide-based hardening accelerators include, for example, di-t-butyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, α,α'-bis( t-butylperoxy) diisopropylbenzene, t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t- Peroxides such as butyl peroxybenzoate.

Commercially available peroxide-based hardening accelerators include "PERHEXYL D", "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", and "PERBUTYL O" manufactured by NOF Corporation. , "PERBUTYL ND", "PERBUTYL Z", "PERCUMYL P", "PERCUMYL D", etc.

(E) The content of the component, from the viewpoint of remarkably obtaining the desired effect of the present invention, when the non-volatile content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.2% by mass % Or more, still more preferably 0.3% by mass or more, preferably 1% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.5% by mass or less.

＜(F) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives in terms of optional components. Examples of such additives include resin additives such as thermoplastic resins other than the (B) component, thickeners, defoamers, leveling agents, and adhesion imparting agents. These additives can be used alone or in combination of two or more. The content of each can be set appropriately if the industry is familiar with the field.

The preparation method of the resin composition of the present invention is not particularly limited, and for example, a method of adding a solvent or the like as needed, mixing using a rotary mixer, etc., dispersing the compound, etc. may be mentioned.

＜Physical properties and uses of resin composition＞ The resin composition contains the component (A) and the component (B) in a predetermined amount. Thereby, the curing shrinkage rate can be suppressed, and a cured product having an excellent dielectric rate can be further obtained. In addition, a cured product with excellent dielectric tangent can usually be obtained.

The cured product formed by thermally curing the resin composition at 190°C for 90 minutes exhibits a characteristic of low curing shrinkage. That is, hardening shrinkage is suppressed, thereby obtaining an insulating layer capable of suppressing warpage. Regarding the curing shrinkage, it is preferably 0.35% or less, more preferably 0.34% or less, and still more preferably 0.33% or less. The lower limit of the curing shrinkage rate is not particularly limited, and may be 0.01% or more. The curing shrinkage rate can be measured according to the method described in the below-mentioned examples.

The cured product formed by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of low dielectric constant. Therefore, the aforementioned hardened product has an insulating layer with a low dielectric constant. The permittivity is preferably 3.0 or less, more preferably 2.9 or less, and still more preferably 2.85 or less. The lower limit of the permittivity can be 0.001 or more. The dielectric constant can be measured according to the method described in the following examples.

The cured product formed by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of low dielectric tangent. Therefore, the aforementioned hardened product has an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.01 or less, more preferably 0.007 or less, and still more preferably 0.005 or less. The lower limit of the dielectric tangent can be 0.0001 or more. The dielectric tangent can be measured according to the method described in the following examples.

The resin composition of the present invention can suppress curing shrinkage and has an insulating layer with excellent dielectric constant. Therefore, the resin composition of the present invention is suitable for use as a resin composition for insulation applications. Specifically, it is preferably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductive layer) for forming a conductive layer (including a rewiring layer) formed on an insulating layer.

In addition, in the multilayer printed wiring board described below, it is preferably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), and for forming interlayer insulation of a printed wiring board. The resin composition of the layer (resin composition for forming an interlayer insulating layer of a printed wiring board), a resin composition for forming an insulating layer of a flexible substrate (a resin composition for forming an insulating layer of a flexible substrate).

Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring forming layer (rewiring layer) that forms an insulating layer for a rewiring layer. Formation layer formation resin composition) and semiconductor wafer sealing resin composition (semiconductor wafer sealing resin composition). When manufacturing a semiconductor chip package, a rewiring layer can be further formed on the sealing layer. (1) Laminating the temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming a sealing layer on the semiconductor wafer, (4) The step of peeling the substrate and the temporary fixing film from the semiconductor wafer, (5) A step of forming a rewiring forming layer as an insulating layer on the surface where the substrate of the semiconductor wafer and the temporary fixing film have been peeled off, and (6) Steps of forming a rewiring layer as a conductor layer on the rewiring forming layer

[Resin Sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

The thickness of the resin composition layer, even if the thickness of the printed wiring board is reduced and the cured product of the resin composition is a thin film, from the viewpoint of providing a cured product with excellent insulation, it is preferably 50 μm or less, more preferably 40 μm Hereinafter, it is more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and it can usually be 5 μm or more.

As for the support, for example, a film made of plastic material, metal foil, and release paper, preferably a film made of plastic material, or metal foil.

When a film made of a plastic material is used as a support, as for the plastic material, for example, polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PEN") Such as polyester, polycarbonate (hereinafter referred to as "PC"), polymethylmethacrylate (PMMA) and other acrylates, cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are more preferred, and cheap polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. For copper foil, foils made of a single metal of copper can be used, and foils made of alloys of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can also be used.

The support system can be subjected to matting treatment, corona treatment, and antistatic treatment on the surface joining with the resin composition layer.

In addition, as for the support, it can also be used for a support with a release layer having a release layer on the surface to be bonded to the resin composition layer. The release agent used in the release layer of the support with release layer includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The release agent. The support with a release layer can also use commercially available products. For example, a PET film with a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1" and "AL" manufactured by LINTEC. -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "unipeel" manufactured by UNITIKA, etc.

The thickness of the support is not particularly limited, but it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when a support with a release layer is used, the thickness of the entire support with a release layer is preferably within the above-mentioned range.

According to one embodiment, the resin sheet may include any layers as required. The optional layer includes, for example, a protective film that is provided on a surface that is not bonded to the support of the resin composition layer (that is, the surface opposite to the support) conforms to the support. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. With the laminated protective film, the adhesion or scratches of dust and the like on the surface of the resin composition layer can be suppressed.

The resin sheet can be manufactured by, for example, dissolving a resin composition in an organic solvent to prepare a resin paint, applying the resin paint on a support using a die coater or the like, and further drying it to form a resin composition layer.

In terms of organic solvents, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ethyl acetate, butyl acetate, cerusin acetate, propylene glycol monomethyl ether Acetate and carbitol acetate, etc.; carbitols such as Cyrus and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, Dimethylacetamide (DMAc) and N-methylpyrrolidone and other amide-based solvents. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

The drying system can be performed by well-known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and the organic solvent is dried so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin paint, for example, when using a resin paint containing 30% to 60% by mass organic solvent, you can dry it at 50℃~150℃ for 3 minutes~10 Minutes to form the resin composition layer.

The resin flakes can be rolled into a roller for storage. When the resin sheet has a protective film, the protective film can be peeled off and used.

[Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) after using the above-mentioned resin sheet. (I) Laminating on the inner substrate by bonding the resin composition layer of the resin sheet to the inner substrate (II) Step of thermally hardening the resin composition layer to form an insulating layer

The "inner substrate" used in step (I) is a member that becomes the substrate of the printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermal Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductive layer on one or both sides, and the conductive layer may be patterned. An inner substrate with a conductor layer (circuit) formed on one or both sides of the substrate can be referred to as an "inner circuit substrate". In addition, when manufacturing a printed wiring board, the intermediate product to be formed of the insulating layer and/or the conductor layer is also further included in the "inner substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner-layer board with built-in parts can be used.

The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by heating and pressing the resin sheet on the inner layer substrate from the support side. The member for heating and pressing the resin sheet on the inner substrate (hereinafter referred to as "heating and pressing member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller). In addition, instead of directly pressing the heat pressing member on the resin sheet, it is preferable to apply pressure through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner substrate.

The lamination system of the inner substrate and the resin sheet can be implemented by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to In the range of 1.47MPa, the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Laminating is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

The lamination system can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum press laminators manufactured by Meiji Seisakusho Co., Ltd., vacuum applicators manufactured by NIKKO Materials Co., Ltd., and batch vacuum press laminators.

After the lamination, under normal pressure (under atmospheric pressure), for example, the layered resin sheet may be smoothed by pressing a heating and pressing member from the support side. The pressing conditions of the smoothing treatment may be the same conditions as the heating and pressing conditions of the above-mentioned build-up. The smoothing treatment can be performed by a commercially available laminator. In addition, the layering and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

The support can be removed between step (I) and step (II), or after step (II).

In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and generally used conditions can also be used when forming the insulating layer of the printed wiring board.

For example, although the thermal curing conditions of the resin composition layer vary depending on the type of resin composition, etc., the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. ℃. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the resin composition layer is preheated at a temperature above 50°C but below 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less) More than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further implemented. These steps (III) to (V) can also be implemented according to various methods well known to those skilled in the field used in the manufacture of printed wiring boards. In addition, when the support is removed after step (II), the removal of the support can also be performed between step (II) and step (III), step (III) and step (IV), or step ( IV) and step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer of steps (II) to (V) may be repeated to form a multilayer wiring board.

Step (III) is a step of opening holes in the insulating layer, thereby forming through holes such as via holes and through holes in the insulating layer. Step (III) can also be implemented using, for example, drilling, laser, plasma, etc., in accordance with the composition of the resin composition used in the formation of the insulating layer. The size or shape of the through hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually in this step (IV), stain removal is also performed. The procedure and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid are sequentially performed to roughen the insulating layer. The swelling liquid used in the roughening treatment is not particularly limited, and examples include alkaline solutions, surfactant solutions, and the like. Alkaline solutions are preferred, and sodium hydroxide solution and potassium hydroxide solution are more preferred for the alkaline solution. Examples of commercially available swelling fluids include "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited. For example, it can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to a moderate degree, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment by an oxidant such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. In addition, as for the neutralization liquid used in the roughening treatment, an acidic aqueous solution is preferred. As for a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan can be mentioned. The treatment by the neutralization liquid can be performed by immersing the treated surface subjected to the roughening treatment by the oxidizing agent in a neutralization liquid at 30°C to 80°C for 1 minute to 30 minutes. From the viewpoint of workability, etc., the method of immersing the object subjected to the roughening treatment by the oxidizing agent in a neutralization solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured with a non-contact surface roughness meter.

Step (V) is a step of forming a conductive layer, which is to form a conductive layer on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium . The conductor layer can be a single metal layer or an alloy layer. For the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) The formed layer. Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel・The alloy layer of chromium alloy, copper, nickel alloy, copper and titanium alloy is preferable, and the single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or the alloy layer of nickel and chromium alloy is more preferable. Better, a single metal layer of copper is even better.

The conductor layer may have a single-layer structure, or may have a single-metal layer made of different types of metals or alloys, or a multiple-layer structure formed by stacking two or more alloy layers. When the conductor layer has a multiple-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

Although the thickness of the conductor layer depends on the design of the desired printed wiring board, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can be formed by plating. For example, by plating on the surface of the insulating layer by a well-known technique such as the semi-additive method and the full-additive method, a conductor layer with a desired wiring pattern can be formed, from the viewpoint of ease of manufacture Look, it is better to be formed by the semi-additive method. The following shows an example of forming the conductor layer by the semi-additive method.

First, a plating seed layer is formed by electroless plating on the surface of the insulating layer. Next, a part of the plating seed layer is exposed corresponding to the desired wiring pattern to form a mask pattern on the formed plating seed layer. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Multilayer flexible substrate] The multilayer flexible substrate includes an insulating layer formed by a cured product of the resin composition of the present invention. The multilayer flexible substrate may also include any member combined with the insulating layer. As for the arbitrary member, for example, an electronic component, a coating layer film, etc. can be mentioned.

The multilayer flexible substrate can be manufactured by a manufacturing method including a method of manufacturing a laminate sheet manufactured by laminating and curing plural resin compositions. Therefore, the multilayer flexible substrate is manufactured by a manufacturing method including (a) a step of preparing a resin sheet and (b) a step of laminating a plurality of resin composition layers using the resin sheet and curing.

The manufacturing method of the multilayer flexible substrate can be further combined with any of the aforementioned steps. For example, the method of manufacturing a multilayer flexible substrate provided with electronic components may also include the step of bonding the electronic components to the laminated sheet. The bonding condition between the laminated sheet and the electronic component can be any condition under which the terminal electrode of the electronic component and the conductor layer of the wiring provided on the laminated sheet can be connected to the conductor. Also, for example, a method for manufacturing a multilayer flexible substrate provided with a coating layer film may include a step of laminating a layered sheet and a coating layer film.

The multi-layer flexible substrate can generally be bent and used in such a way that one of the laminated sheets included in the multi-layer flexible substrate faces each other. For example, a multi-layer flexible substrate can be stored in a housing of a semiconductor device in a state of being bent to reduce its size. In addition, for example, a multilayer flexible substrate may be provided in a movable portion of a semiconductor device having a flexible movable portion.

[Semiconductor device] The semiconductor device of the present invention includes the printed wiring board or the multilayer flexible substrate of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board or the multilayer flexible substrate of the present invention.

Semiconductor devices include various semiconductor devices that are supplied to electrical products (for example, computers, mobile phones, digital cameras, and televisions, etc.) and riding tools (for example, motorcycles, automobiles, trams, ships, and airplanes).

The semiconductor device of the present invention is manufactured by mounting parts (semiconductor chips) on the conductive parts of the printed wiring board. The so-called "conduction point" is "the place where the electrical signals in the printed wiring board are transmitted". This place can be a surface or a buried place. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The mounting method of the semiconductor chip in the manufacture of semiconductor devices is not particularly limited as long as the semiconductor chip can operate efficiently. Specifically, there are wire bonding mounting methods, flip chip mounting methods, and bumpless mounting methods. The mounting method of the assembly layer (BBUL), the mounting method of the anisotropic conductive film (ACF), the mounting method of the non-conductive film (NCF), etc. Here, the "mounting method by bumpless assembly layer (BBUL)" refers to the "mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board" . [Example]

Hereinafter, examples are used to illustrate the present invention in more detail, but the present invention is not limited to these examples. In addition, in the following description, unless otherwise specified, "parts" and "%" respectively indicate "parts by mass" and "% by mass".

<Synthesis Example 1: Synthesis of Polyimide Resin 1> Put 9.13 g of 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-ester (compound of formula (B-3)) into a 500ml separable flask equipped with a nitrogen introduction tube and a stirring device (30 millimoles), 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride 15.61g (30 millimoles), N-methyl-2-pyrrolidone 94.64g, 0.47g (6 millimoles) of pyridine, 10g of toluene, and under nitrogen atmosphere at 180°C, by observing the toluene outside the system during the imidization reaction for 4 hours, the polyamide-containing compound was obtained. A polyimide solution of amine resin 1 (non-volatile content 20% by mass). In the polyimide solution, no precipitation of the synthesized polyimide resin 1 was seen. The weight average molecular weight of the polyimide resin 1 is 45,000.

<Synthesis Example 2: Synthesis of Polyimide Resin 2> Place the aromatic tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC JAPAN, 4,4'-(4,4'-iso) in a reaction vessel equipped with a stirrer, a water trap, a thermometer, and a nitrogen inlet pipe. Propylene diphenoxy) diphthalic dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g, and the solution was heated to 60°C. Next, 43.7 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were dropped, and the imidization was carried out at 140°C for 1 hour. reaction. Thereby, a polyimide solution containing polyimine resin 2 (non-volatile content 30% by mass) was obtained. In addition, the weight average molecular weight of the polyimide resin 2 was 25,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3> Prepare a 500mL separable flask equipped with a moisture quantitative receiver connected to a circulating cooler, a nitrogen introduction tube, and a stirrer. In this flask, add 4,4'-oxydiphthalic anhydride (ODPA) 20.3g, γ-butyrolactone 200g, toluene 20g and 5-(4-aminophenoxy)-3-[4 29.6 g of -(4-aminophenoxy)phenyl]-1,1,3-trimethylindan was stirred at 45°C for 2 hours under a nitrogen stream to perform the reaction. Next, the temperature of the reaction solution was raised, and while maintaining the temperature at about 160°C, the condensation water was azeotropically removed with toluene under a nitrogen stream. Confirm that there is a certain amount of water accumulated in the moisture quantitative receiver, and no water is seen flowing out. After confirmation, the reaction solution was further heated up and stirred at 200°C for 1 hour. After that, it was cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing polyimide resin 3 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 3 has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the aforementioned polyimide resin 3 is 12,000.

<Synthesis example 4: Synthesis of compound A (compound A) containing aromatic ester skeleton and unsaturated bond> In a reaction vessel, 89 parts by mass of o-allylphenol, dicyclopentadiene and phenol copolymer resin ( The softening point is 85°C, the hydroxyl equivalent is about 165g/eq.) 110 parts by mass, and 1000 parts by mass of toluene are dissolved in the container while nitrogen is substituted under reduced pressure. Next, 135 parts by mass of isophthalic acid chloride was put in and dissolved. Furthermore, 0.5 g of tetrabutylammonium bromide was added, and while purging the container with nitrogen, 309 g of a 20% sodium hydroxide aqueous solution was dropped over 3 hours. At this time, the temperature in the system is controlled below 60°C. After that, it was stirred for 1 hour to make it react. After the reaction, the reactants were separated and the water layer was removed. This operation is repeated until the pH of the water layer reaches 7, and toluene and the like are distilled off under heating and reduced pressure conditions to obtain compound A containing an aromatic ester skeleton and an unsaturated bond. The obtained compound A containing an aromatic ester skeleton and an unsaturated bond has an unsaturated bond equivalent calculated from the implantation ratio, which is 428 g/eq. Compound A is represented by the following formula, s represents an integer of 0 or more, and the average value of r calculated from the insertion ratio is 1. In addition, the wavy line is a structure obtained by the reaction of isophthalic acid chloride, a heavy addition reaction resin of phenol, and/or o-allyl phenol.

<Synthesis example 5: Synthesis of compound B (compound B) containing aromatic ester skeleton and unsaturated bond> Put 201 parts by mass of o-allylphenol and 1000 parts by mass of toluene in a reaction vessel, and reduce the pressure in the vessel Nitrogen dissolves while dissolving. Next, 152 parts by mass of isophthalic acid chloride was put in and dissolved. While cleaning the container with nitrogen, 309 g of 20% sodium hydroxide aqueous solution was dropped over 3 hours. At this time, the temperature in the system is controlled below 60°C. After that, it was stirred for 1 hour to make it react. After the reaction, the reactants were separated and the water layer was taken out and removed. This operation was repeated until the pH of the water layer reached 7, and toluene and the like were distilled off under heating and reduced pressure to obtain a compound B containing an aromatic ester skeleton and an unsaturated bond. The obtained compound B containing an aromatic ester skeleton and an unsaturated bond, the equivalent of the unsaturated bond is 199 g/eq. when calculated from the insertion ratio. Compound B has a structure represented by the following formula.

<Example 1: Preparation of resin composition 1> 5 parts of bis-xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 185g/eq.), naphthalene type epoxy resin (Nippon "ESN475V" manufactured by Ironsumijin Chemical Co., Ltd., epoxy equivalent of about 332g/eq.) 5 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238g/eq.) 10 parts, ring Hexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS", epoxy equivalent about 135g/eq.) 2 parts, polyimide resin 1 (non-volatile content 20% by mass) obtained in Synthesis Example 1 100 parts and ring In the mixed solvent of 10 parts of hexanone, it was heated and dissolved while stirring. After cooling to room temperature, 5 parts of the compound A obtained in Synthesis Example 4 and the triazine skeleton contained a cresol novolac hardener ("LA3018-50P" manufactured by DIC Corporation, with a hydroxyl equivalent of approximately 151 g/eq., 50% solid content of 2-methoxypropanol solution) 4 parts, spherical silica ("SC2500SQ" manufactured by Admatechs, average particle size 0.5μm, specific surface area 11.2m ² /g, with respect to 100 parts of silica in N -Phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM573) 1 part for surface treatment) 50 parts, amine hardening accelerator (4-dimethylaminopyridine (DMAP) )) 0.2 part and 0.03 part of peroxide-based hardening accelerator ("PERBUTYL C" manufactured by NOF Corporation) are mixed and uniformly dispersed in a high-speed rotary mixer, and then a cartridge filter ("SHP020" manufactured by ROKITECHNO) is used. Filter to prepare resin composition 1.

<Example 2: Preparation of resin composition 2> In Example 1, 5 parts of compound A" was changed to 10 parts of compound B (non-volatile content 50% by mass). Except for the above matters, the rest was carried out in the same manner as in Example 1, and the resin composition 2 was prepared.

<Example 3: Preparation of resin composition 3> In Example 1, 100 parts of polyimide resin 1 (non-volatile content 20% by mass) obtained in Synthesis Example 1 was changed to polyimide resin 2 (non-volatile content 30% by mass) obtained in Synthesis Example 2 66.7 Copies. Except for the above matters, the rest was carried out in the same manner as in Example 1, and the resin composition 3 was prepared.

<Example 4: Preparation of resin composition 4> In Example 1, 100 parts of polyimide resin 1 (non-volatile content 20% by mass) obtained in Synthesis Example 1 was changed to 100 parts of polyimide resin 3 (non-volatile content 20% by mass) obtained in Synthesis Example 3 . Except for the above matters, the rest was carried out in the same manner as in Example 1, and the resin composition 4 was prepared.

<Comparative example 1: Preparation of resin composition 5> In Example 1, 5 parts of compound A" obtained in Synthesis Example 4 was changed to an active ester hardener ("EXB-8000L-65TM" manufactured by DIC Corporation, with an active group equivalent of approximately 220 g/eq., and a non-volatile content of 65% by mass. Toluene: 1:1 solution of MEK) 7.7 parts. Except for the above matters, the rest was carried out in the same manner as in Example 1, and the resin composition 5 was prepared.

<Comparative Example 2: Preparation of Resin Composition 6> In Example 1, 5 parts of compound A" obtained in Synthesis Example 4 was changed to an active ester hardener ("EXB-8150-62T" manufactured by DIC Corporation, with an active group equivalent of about 230 g/eq., and 62% by mass of non-volatile content. Toluene solution) 8.1 parts. Except for the above matters, the rest was carried out in the same manner as in Example 1, and resin composition 6 was prepared.

＜Measurement of average particle size of inorganic fillers＞ Weigh 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a small glass bottle, and disperse it with ultrasound for 10 minutes. Using a laser diffraction particle size distribution measuring device (“LA-960” manufactured by Horiba Manufacturing Co., Ltd.), the wavelength of the light source used was adjusted to blue and red, and the particle size distribution of the inorganic filler was measured on a volume basis using a flow cell method . From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median diameter.

＜Measurement of the specific surface area of inorganic fillers＞ Using a BET automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), nitrogen was adsorbed on the surface of the sample, and the specific surface area was calculated using the BET multipoint method to measure the specific surface area of the inorganic filler.

<Measurement of curing shrinkage> (1-1) Preparation of resin flakes The resin composition of each example and comparative example was uniformly applied to the PET film treated with alkyd release agent using a die coater so that the thickness of the dried resin composition layer was 40 μm The release treatment surface (thickness: 38 μm) was dried at 80 to 120° C. (average 100° C.) for 6 minutes to obtain a resin sheet 1.

(1-2) Preparation of polyimide film with resin After processing this resin sheet 1 into a 200mm angle, using a batch-type vacuum pressure laminator (manufactured by Nichigo-Morton, 2-platform assembly laminator, CVP700), the resin composition layer and the polyimide film ( The center of the smooth surface of UPILEX 25S, 25μm thick, 240mm angle, manufactured by Ube Industries Co., Ltd., was laminated on one side to obtain a polyimide film with resin. The layering system was pressure-reduced for 30 seconds to make the air pressure 13 hPa or less, and then pressed at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(1-3) Measurement of the initial length The obtained polyimide film with resin was punched through the resin sheet support for about 20 mm from the 4 corners of the 200 mm angle resin. 4 holes (about 6mm in diameter) are formed (the holes are temporarily referred to as A, B, C, and D clockwise). After the support of the resin sheet is peeled off, a non-contact image measuring device (manufactured by MITUTOYO) is used. , Quick Vision Type: QVH1X606-PRO III_BHU2G) Measure the length L (L _AB , L _BC , L _CD , L _DA , L _AC , L _BD ) between the centers of the formed points (refer to Figure 1). In addition, in FIG. 1, X and Y indicate the longitudinal direction and the lateral direction of the resin sheet.

(1-4) Thermal curing of resin composition layer Finish measuring the length of the polyimide film with resin, and set the polyimide film surface on a 255mm×255mm glass cloth substrate epoxy resin laminated board with copper on both sides (0.7mm thickness, manufactured by Matsushita Electric Works) "R5715ES"), fix the four sides with a polyimide adhesive tape (width 10mm), and heat it at 190°C for 90 minutes to thermally harden the resin composition layer to obtain a cured product layer.

(1-5) Measurement of thermal hardening shrinkage rate After thermal hardening, peel off the polyimide adhesive tape, remove the polyimide film with the hardened layer from the laminate, and further remove the hardened layer from the polyimide _{The film is peeled off, and the hardened length L'(L' AB} , L' _BC , L' _CD , L' _DA , L' _AC , between the centers of the holes formed by (1-3) with a non-contact image measuring device L' _BD ) is measured in the same manner as L.

_{The length L AB} between the hole A and the hole B and the shrinkage rate s1 _AB after hardening are obtained by the following formula (1). In the same way, the shrinkage rates s1 _BC , s1 _CD , s1 _DA , s1 _AC and s1 _{DA of L BC} , L _CD , L _DA , L _AC and L _BD after curing were obtained. s1 _AB =(L _AB -L' _AB )／L _AB (1)

The curing shrinkage rate of the cured product layer is obtained by the following formula (2). Curing shrinkage rate [Shrinkage rate in xy direction: S1](%) = {(s1 _AB +s1 _BC +s1 _CD +s1 _DA +s1 _AC +s1 _DA )/6}×100 (2)

In addition, the curing shrinkage rate of the cured product layer was evaluated based on the following criteria. ○: The curing shrinkage rate is 0.35% or less ×: The curing shrinkage rate exceeds 0.35%

＜Measurement of dielectric properties (dielectric rate, dielectric tangent)＞ Using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiji Seisakusho Co., Ltd.), the resin sheet 1 produced in (1-1) above was laminated on a laminate board (manufactured by Hitachi Chemical Co., MCL-E-700G). Copper foil etching products). The build-up system was pressure-reduced for 30 seconds to make the air pressure less than 13 hPa, and then pressed at 120°C for 30 seconds at a pressure of 0.74 MPa. After that, the PET film was peeled off, and the resin composition layer was cured under curing conditions of 190°C for 90 minutes to obtain a cured product sample.

Cut the cured product sample into a test piece with a width of 2 mm and a length of 80 mm. For this test piece, using "HP8362B" manufactured by Agilent Technologies, a cavity resonance perturbation method was used to measure the frequency of 5.8 GHz and the measurement temperature of 23° C. to measure the dielectric constant and the dielectric tangent. The measurement was performed on 3 test pieces, and the average value was calculated. In addition, the permittivity was evaluated based on the following criteria. ○: The dielectric rate is 3.0 or less ×: The dielectric rate exceeds 3.0

＊表中，「(A)成分的含量」表示令樹脂組成物中的不揮發成分為100質量%的情況下(A)成分的含量，「(B)成分的含量」表示令樹脂組成物中的不揮發成分為100質量%的情況下(B)成分的含量，「(C)成分的含量」表示令樹脂組成物中的不揮發成分為100質量%的情況下(C)成分的含量。

＊In the table, "the content of (A) component" means the content of (A) component when the non-volatile content in the resin composition is 100% by mass, and "the content of (B) component" means the resin composition When the non-volatile content of is 100% by mass, the content of the component (B), and the "content of the component (C)" means the content of the component (C) when the non-volatile component in the resin composition is 100% by mass.

It has been confirmed that in Examples 1 to 4, even if the components (C) to (E) are not included, the results are the same as those in the above-mentioned Examples, although the degree is different.

[Fig. 1] Fig. 1 shows a schematic diagram of an example of a resin sheet when curing shrinkage is measured.

Claims (13)

A resin composition containing (A) a compound containing an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin, When the non-volatile content in the resin composition is 100% by mass, the content of the component (B) is 10% by mass or more and 50% by mass or less. The resin composition of claim 1, wherein the component (A) is any one of the compound represented by the following general formula (A-1) and the compound represented by the following general formula (A-2),

(In the general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group ^{that may have a substituent, Ar 12} each independently represents a divalent aromatic hydrocarbon group that may have a substituent, and Ar ¹³ each independently Ground means a divalent aromatic hydrocarbon group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination of these, and n represents 0-10 Integer);

(In the general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group ^{that may have a substituent, Ar 22} each independently represents a monovalent aromatic hydrocarbon group that may have a substituent, and m represents an integer of 2 or 3 ). The resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (A) is 0.1% by mass to 30% by mass. The resin composition according to claim 1, which further contains (C) an inorganic filler. The resin composition of claim 4, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 30% by mass or more. The resin composition according to claim 1, which further contains (D) a thermosetting resin. Such as the resin composition of claim 1, which is used for forming an insulating layer. Such as the resin composition of claim 1, which is used for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition of any one of claims 1 to 8. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition of any one of claims 1 to 8. A multilayer flexible substrate comprising an insulating layer formed by a cured product of the resin composition of any one of claims 1 to 8. A semiconductor device including the printed wiring board as claimed in claim 10. A semiconductor device comprising a multilayer flexible substrate as claimed in claim 11.

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